Ceramics International 48 (2022) 35689–35697

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Development of flat absorber black anodic coating on 3D printed

Al–10Si–Mg alloy for spacecraft thermal control application
Rahul Ghosh a, b, *, Arjun Dey a, **, M.K. Kavitha a, Hari Krishna Thota a, R. Uma Rani c,
A. Rajendra a, Karabi Das b
a
Thermal Systems Group, U. R. Rao Satellite Centre, Indian Space Research Organisation, Bengaluru, 560017, India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur, 721 302, India
c
Materials Management Group, U. R. Rao Satellite Centre Indian Space Research Organisation, Bengaluru, 560017, India

A R T I C L E I N F O A B S T R A C T

Keywords: Black anodic coating (BAC) is developed on 3D printed or additively manufactured (AM) Al–10Si–Mg alloy by
Anodization sulphuric acid based anodization technique at low (~9 ◦ C) temperature. The microstructural and surface
3D printed AlSiMg alloy properties of the coating are investigated by optical microscopy (OM), scanning electron microscopy (SEM),
Emittance
atomic force microscopy (AFM), X-ray diffraction (XRD) and water contact angle (WCA) measurement tech­
Nanoindentation
niques. The solar absorptance and infrared (IR) emittance of the coating have been evaluated in the range
Corrosion
Space qualification 200–2500 nm and 3–30 μm, respectively. Nanoindentation technique is employed with low load to evaluate the
hardness and modulus of the coating at microstructural length scale. The anodic coating shows superior hardness
(~3.95 GPa) and modulus (~96 GPa) as compared to reported literature values, possibly due to dense micro­
structure and the presence of harder ceramic phases, e.g., alumina and kyanite in anodic coating. Further, due to
dense microstructure, corrosion resistance improves significantly after anodization of AM alloy. Finally, thermo-
optical properties are not altered after the space environmental tests which ensures the usage of the present
anodic coating on AM Al alloy for spacecraft thermal control application. The solar absorptance (0.87) and IR
emittance (0.78) obtained for the present coating as flat absorber characteristics are higher than the coatings
processed on conventional wrought alloys. The present anodic coating shows substantial improvement in me­
chanical, thermo-optical and corrosion properties due to higher silicon content unlike conventional wrought
alloy and refinement in microstructure during additive manufacturing aiding continuous and uniform anodic
oxide layer.

1. Introduction
Aluminum alloys offer numerous advantages for its various appli­
cations in space industries owing to its lower density, heat treatability,
higher specific strength and compatibility for conventional machining
[1–4]. With recent advances in high throughput satellites; which de­
mand high intricacy in design and fabrication, the utilization of additive
manufacturing (AM), usually coined ‘3D printing’ has grown at a rapid
rate in both conceptualization stage and actual implementation [5]. In
view of this, AM has been attempted to replace existing parts made by
conventional methodologies (CM). The CM has inherent limitations in
terms of part fabrications, precision level, assembly intricacy and usage
of higher man-hour. However, AM eases the aforesaid restrictions and it
increases productivity, reduces both material and energy wastage and
produces rapid end-solution [6–8]. The Al–Si alloys especially
Al–10Si–Mg alloy has been used often to manufacture through AM due
to its inherent casting properties and near-eutectic composition (Al-12.5
wt%Si –eutectic composition) [9]. Besides, Al–10Si–Mg alloy has me­
chanical properties comparable to conventional wrought alloys pres­
ently used to fabricate spacecraft structures and mechanical
components.
Surface modifications by anodization of various wrought alloys
(AA6061, AA2024 etc.) play a major role in controlling thermal health
of spacecraft. The internal temperatures of the spacecraft components/
sub-systems are managed passively within the operating limits by tun­
ing the thermo-optical characteristics of the anodic surfaces, mainly,

* Corresponding author. Thermal Systems Group, U. R. Rao Satellite Centre Indian Space Research Organisation, Bengaluru, 560017, India,
** Corresponding author.,
E-mail addresses: rghosh@ursc.gov.in, rahulghosh71@gmail.com (R. Ghosh), arjun_dey@rediffmail.com, arjundey@ursc.gov.in (A. Dey).

https://doi.org/10.1016/j.ceramint.2022.05.289
Received 7 March 2022; Received in revised form 23 May 2022; Accepted 24 May 2022
Available online 28 May 2022
0272-8842/© 2022 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
R. Ghosh et al. Ceramics International 48 (2022) 35689–35697

solar absorptance (αs) and infrared emittance (εIR). Due to the presence Therefore, in the present study, a novel anodizing process has been
of vacuum in space, the convection and conduction of heat transfers are designed with optimal process parameters to obtain anodic coating on
not accounted, instead, thermal radiation which occurs mainly in the AM Al–10Si–Mg alloy having enhanced αs and εIR values. Subsequently,
infrared region is considered. For effective passive thermal control of the the coating is thoroughly characterized with respect to microstructure,
spacecraft, the surfaces of the spacecraft components and structures surface, thermo-optical, mechanical, and corrosion properties. Further­
must have a coating with high αs and εIR, called as flat absorber coatings. more, to establish the space worthiness of the developed coating, envi­
A flat absorber anodic coating absorbs all incident energy across the ronmental tests such as relative humidity, thermo-vacuum, and thermal
spectral range of ultraviolet (UV) to near-infrared (NIR). High αs and εIR shock cycling are carried out.
leads to uniformity in temperature across the components through ra­
diation coupling and the spacecraft’s temperature has been governed by 2. Materials and methods
the following heat balance equation [10,11].
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ 2.1. Preparation of anodic coating
T = 4 (SApα/σ Aε) (1)
The AM Al–10Si–Mg alloy manufactured via direct metal laser sin­
where S is considered as the solar constant as 1353 W/m2; α is the
tering (DMLS: M280 EOS, Germany), was utilized in the present work in
absorptance of the projected area, Ap is the exposed surface area of the
the form of a circular disc. Post DMLS processing, the alloy was aged at
satellite perpendicular to the Sun rays; σ signifies Stefan-Bolzman con­
175 ± 5 ◦ C followed by furnace cooling for relieving the residual stresses
stant of value 5.67 × 10− 12 W/cm2 k4; A is the total surface area of the
and imparting adequate mechanical properties. The preparation of
spacecraft; ε means infrared emittance of the surface area exposed; and
anodic coating involved three main consecutive steps viz. (i) Surface
finally T is the temperature of the satellite in steady state. The αs/εIR
pretreatments, (ii) anodizing, and (iii) sealing. First, AM Al–10Si–Mg
ratio (equation (1)) close to unity is obtained with high αs and εIR values
alloy coupons (Dia: 50 mm and thickness: 4 mm) were degreased in
and is generally preferred for obtaining effective thermal control.
trichloroethylene and then cleaned with an alkaline solution containing
Anodic coatings on Al alloys are generally processed electrochemi­
sodium carbonate (Na2CO3), 20 g L− 1 and tri sodium orthophosphate
cally in sulphuric acid as per MIL-A-8625-F [12] to improve the corro­
(Na3PO4.12H2O), 25 g L− 1 at 60 ± 5 ◦ C for a short duration of 2–3 min.
sion resistance, tribological properties, insulation properties,
Then it was neutralized in an aqueous solution of nitric acid (SG 1.42),
thermo-optical properties of the components; and also to avoid cold
25 mL L− 1 at room temperature (25 ± 5 ◦ C). The sample specimens were
welding against mating surfaces under space environment [13].
finally rinsed in distilled water.
Although anodizing on wrought Al alloys manufactured through con­
The AM alloy sample specimens were anodized using 15 wt% sul­
ventional technologies has been a widely studied subject, studies on
phuric acid solution at a low temperature (9 ± 2 ◦ C) with an air agitation
anodization, hard anodization (HA) and plasma-electrolytic oxidation
facility. The process was carried out inside a lead-lined tank (as cathode)
(PEO) on additively manufactured or 3D Al–10Si–Mg alloy are scarce in
and the specimen acted as anode. A constant current mode at 40 mA/
literature [14–19]. These reported studies [14–18] primarily focused on
cm2was employed for the anodizing process. The anodization duration
the effect of heat treatment and silicon content on the anodizing
was of 45 min. Next, the anodized sample specimens were washed in
behavior of the AM alloy in 3 M H2SO4 electrolyte at room temperature.
distilled water. The post-rinsed anodized sample specimens were finally
Further, these recent studies have not reported thermo-optical proper­
sealed in the presence of boiling water (pH = 6.5–7.0). The sealing
ties of the coating, its space-worthiness, and corrosion aspects. The
process was kept for 45 min.
coating thickness achieved in the above studies under the anodizing
The voltage-time response of the anodic coating on AM Al–10Si–Mg
conditions is on the lower side (~4.4 μm) which has limited applications
alloy is presented in Fig. 1. The voltage rose sharply to 36 V within 15
with respect to thermal control of the spacecraft. Lower thickness anodic
min (point a-b) indicating the formation of the barrier layer, and grad­
coatings possess lesser thermo-optical properties hindering effective
ually to 50 V in the next 30 min (14 V rise in 30 min-point b-c) indicating
thermal control of spacecraft. In a very recent study [19], authors have
initiation and growth of porous layer for thickness build-up. It is also
performed hard anodization on the AM alloy under very low tempera­
imperative that beyond point c in Fig. 1 the curve starts to flatten,
ture and longer duration and studied its wear behavior and mechanical
properties. The obtained mechanical properties are lower than the
properties envisaged by the authors in this study. To the best of the
authors’ knowledge, these few studies are only available in the literature
on the anodization of AM Al–10Si–Mg alloy. Hence, the authors in this
study realizing the knowledge on the gap have designed and developed
thicker anodic coatings using suitable anodizing parameters on addi­
tively manufactured Al–10Si–Mg alloywith high αs and εIR values.
Furthermore, the present developmental study on the anodization of AM
Al alloy is the first-ever attempt toward the spacecraft thermal control
application.
Cast Al–10Si–Mg alloy is defined by duplex microstructure having
primary α-Al dendrites and a eutectic of α-Al and Si [20]. The
larger-sized Si crystals present in this alloy show several challenges
during anodizing due to differential voltage requirements in the oxida­
tion process, as compared to anodizing on wrought alloys where much
lower Si contents favor oxidation and oxide growth. The thickness of
such anodic coatings on AM alloy would have a much lesser value and
often discontinuity has been observed at the coating/metal interface
[14,21]. On the other hand, AM Al–10Si–Mg alloy has a more uniform
and finer microstructure with Si distributed evenly [22] due to the
higher solidification rate inherent in the laser process (DMLS). Due to
this, a faster oxide growth rate and definite continuity at the oxide/­ Fig. 1. Typical voltage-time curve in 15 wt % sulphuric acid at a constant
current density of 40 mA/cm2(inset: showing the photograph of the anod­
metal interface are established.
ized sample).

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R. Ghosh et al.
indicating stable growth of anodic film with minimum change in
voltage. However, the specimens used for this study were taken out after
anodizing for 45 min and all characterizations were performed on the
same (inset, Fig. 1). The voltages obtained here are higher than other
wrought aerospace alloys (AA6061/AA6351/AA6082) primarily due to
simultaneous oxidation of Si present in the alloy along with Al [23,24].
2.2. Anodic coating characterizations
2.2.1. Microstructural investigations and surface characterizations
The detailed investigation of microstructure of the anodized coating
was carried out by scanning electron microscopy (SEM: NEON 40,
Germany) technique with an energy-dispersive X-ray spectroscopy
(EDS) attachment. To avoid charging, a 30–50 nm thick electrically
conducting gold film was deposited on the anodic coating specimen
before putting the specimen for SEM analysis. Further, elemental
composition of the anodic coating was explored using EDS facility
attached with SEM.
The thickness of the coating was measured by a coating thickness
measurement gauge (Model: FNS3, Positector 6000, DeFelsko, USA)
through eddy current method as per ASTM B244. The thickness value
reported is an average of ten measurements taken at various unbiased
locations over the anodic specimen.
X-ray diffraction (XRD) pattern of the anodic specimen was recorded
using a PANalytical, X-ray diffractometer, with Cu Kα radiation and the
scan rate was 2◦ per min with Bragg’s angle 2θ varying from 10 to 90◦ .
Surface topography of the anodic coating was analyzed through
atomic force microscopy (AFM: Nanosurfeasyscan 2, Switzerland)
technique and surface wetting of the anodic coating was studied by
quantifying the water contact angle (WCA) of the anodic coating, using
Acam-D2, Apex Instruments Co. Pvt. Ltd., Kolkata, India. While quan­
tifying the WCA, the water droplet volume of 10 μL was used and the
water was dispensed through a dispensing needle at the rate of 4 μL
min− 1. The specimen surface was maintained in a horizontal position
throughout the tests.Five repeated tests were carried out in this study on
five different unbiased locations to report the average WCA value at
atmospheric temperature and pressure.
2.2.2. Thermo-optical properties and space worthiness studies
Space environmental tests such as relative humidity, thermal shock
cycling, and thermo-vacuum cycling were performed and the detailed
test conditions areas presented in Table 1. Subsequently, the anodic
coating was examined visually under a magnification of 4× for any
degradation in physical appearance. Relative humidity test was con­
ducted to understand the coating response against humidity, since the
components used in spacecraft generally experience higher humidity in
the coastal environment prior to the launch phase. Thermal shock
cycling was conducted to understand the effect of extreme temperatures
encountered during the mission life due to direct solar load on one side
and cold deep space on the other side. Thermo-vacuum test was con­
ducted to understand the effect of thermal cycling under vacuum of
10− 5 Torr (simulating outer space conditions). In pre and post envi­
ronmental tests conditions (Table 1), the average optical properties,
such as, αs and εIR of the specimen; were recorded using a solar reflec­
tometer version 50, model SSR-ER and an emissometer model RD1,
respectively; from Devices and Services Co. (USA). The aforesaid
Table 1
Conditions for space environmental tests.
Test Test Conditions
Relative Humidity Humidity: 95% @ 50 ◦ C and duration: 48 h.
Thermal Shock Temperature limit: 75 to +125 ◦ C, dwell time: 5 min and
Cycling cycles: 1500 nos.
Thermo-Vacuum Vacuum limit:10− 5 torr, Temperature limit: 75 to +125 ◦ C,
dwell time: 2 h and cycles: 10 nos.
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instruments indicate an average value of αs and εIR over the entire solar
(200–2500 nm) and infrared regions (3–30 μm), respectively. Further,
reflectance spectra as a function of wavelength were also obtained by
the ultraviolet–visible–near-infrared (UV-VIS-NIR) spectrophotometer
(Lambda 950, PerkinElmer, USA) and Fourier transform infrared spec­
troscopy (FTIR) spectrophotometer (Spectrum 1000, PerkinElmer,
USA).
2.2.3. Nanomechanical properties
Nanomechanical properties e.g., hardness (H) and modulus (E) of the
anodic coating and the bare AM alloy were evaluated using G200, MTS-
Agilent, USA nanoindenter at 50 mN load. The experiments were con­
ducted under load control mode on the top surface/plan section of the
anodic coating, using Berkovich diamond indenter. The loading and
unloading durations were maintained at 15 s. Furthermore, the
maximum penetration depth was maintained well below the 10% of the
anodic coating thickness to negate any influence of substrate alloy. The
hardness and modulus of the coated specimen are evaluated using well
established Oliver-Pharr model [25].
2.2.4. Corrosion
The corrosion resistance of the specimens (anodically coated and
bare AM alloy) was evaluated through electrochemical impedance
spectroscopy (EIS) technique using a computer-controlled frequency
response analyzer (Autolab PGSTAT 302 N, Eco-chemie, The
Netherlands) driven by Nova 1.4 software. Tests were carried out using a
standard three-electrode setup with Ag/AgCl (saturated with KCl) as
reference electrode, Pt as counter electrode, and coated specimen as
working electrode in 3.5 wt% NaCl solution prepared with distilled
water exposed freely to the atmosphere. Impedance measurements were
carried out on the specimens in the frequency range of 50 kHz to 0.01 Hz
with an amplitude of ±10 mV. The corrosion of the anodic coating was
evaluated to assess the impact of the marine environment on the
spacecraft components during assembly and subsequent launch
activities.
3. Results and discussion
3.1. Microstructural investigations and surface characterizations
Microstructural characterizations were carried out on the bare alloy
using an optical microscope to ascertain the structure associated with
different planes (marked asA and B in Fig. 2a) in AM Al–10Si–Mg alloy.
Fig. 2b and c represent the morphologies observed for the surface par­
allel (A) and perpendicular (B) to the direction of built, respectively. The
microstructure of the specimen consists of very fine grains within the
melt pools (MPs) and coarse grains within the region of melt pool bor­
ders (MPBs), owing to varying cooling rates encountered during the
laser melting process; which has been extensively studied and reported
in the literature [26,27]. The MPs and MPBs have been indicated in
Fig. 2b and c, respectively. Elongated laser track morphology was
observed in surface A and scale-like morphology was observed in surface
B [17].
Fig. 3a indicates schematically the alloy surface (surface A) and
exposed surface (surface B) for anodization to develop anodic coating
layer. Fig. 3b and c represent the optical and SEM images of the cross-
section of anodic coating, respectively. The anodic coating thickness
of sample was achieved as 13 ± 2 μm. It is to be noted that there is no
presence of interfacial crack or discontinuity which can be verified from
the cross-sectional SEM study.
Fig. 4a represents the SEM morphology of the surface of the anodic
coating revealing the appearance of an earthy aggregate with numerous
micro-channels, irregularities and groves. The SEM morphology of the
anodic coating reported in this study is unique of additively manufac­
tured Al–10Si–Mg alloy and as per the authors knowledge it is being
reported for the first time. This morphology does not reveal typical pore
R. Ghosh et al. Ceramics International 48 (2022) 35689–35697

Fig. 2. (a) Schematic representation of the perpendicular surfaces (A and B) of the AM specimen. Optical image of the surface: (b) A, parallel to the direction of built,
and (c) B, perpendicular to the direction of built. (Discontinuous white lines with red arrows depict MPBs. Surfaces are etched with Keller’s reagent for revealing MPs
and MPBs.). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 3. (a) Schematic representation of the anodized surface ‘B’ of the AM specimen; (b) Optical and (c) SEM images of the cross-section of anodic coating.

network having hexagonal distribution, as reported in several literatures
till date for wrought alloys [28]. This may be probably due to the fact
that the microstructure is obtained under extreme rapid solidification
under laser heat source, where aluminum cells are decorated by fibrous
silicon network and movement of anodizing front is slower for fibrous
silicon network than the areas having aluminum cells [14]. It is inter­
esting to note that the oxide cell structure seen in Fig. 4a matches well
with the cell morphology (300–600 nm) of the bare AM specimen as
reported by Revilla et al. [14,16,17]. SEM micrographs showing white
particles (indicated in Fig. 4a) are uniformly dispersed silicon granules
[29]. Fig. 4b reveals the SEM-EDS analysis of the coating. It shows the
presence of Al, Si, O and trace amount of Mg in the coating as expected.
The XRD data of the anodic coating is presented in Fig. 5. The XRD
pattern reveals that the anodic coating is predominantly amorphous.
However, few peaks are observed which are indexed meticulously as per
ICSD ref. codes. The oxide phases were identified as Al2O5Si (Kyanite-
ICSD Ref. Code-98-003-8205) and Al2O3 (oxide-ICSD Ref. Code 98-010-
3821). Besides the aforesaid indicated peaks, high-intensity sharp
aluminum (-ICSD Ref. Code 98-006-2686) and silicon (Silicon-ICSD
Ref. Code 00-027-1402) peaks are present in the pattern due to the
substrate. Similar substrate influence has been also reported in several
studies involving anodic coating on aluminum alloys [19,30].

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R. Ghosh et al.
Fig. 4. (a) SEM photomicrograph of the anodic coating surface(e.g. plan section) and (b) corresponding EDS analysis of the surface of the anodic coating.
Fig. 5. XRD pattern of the anodic coating on AM Al–10Si–Mg alloy.
The AFM surface topography (Fig. 6a and b) of the anodic coating
confirms the mud-crack like morphology as depicted in Fig. 4a. The
surface roughness (Ra) data is in the range of 17 ± 3 nm indicating
uniform and smooth surface. As the presently developed anodic coating
is envisaged to be utilized in the interior of the satellite structure, high
level of surface-flatness is required for assembling critical packages on
the coated surface.
The WCA data of the bare AM alloy and anodic coating are presented
Fig. 6. The(a)3D and (b) 2D AFM images of the anodic coating on AM Al–10Si–Mg alloy.
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Ceramics International 48 (2022) 35689–35697
respectively in Fig. 7a and b. The WCA data are evaluated as 23±2◦ and
66±2◦ , respectively for bare AM alloy and anodic coating. Thus, WCA
has increased after anodization, however, still falls under moderate
hydrophilic in nature. This can be attributed to the fact that boehmite
(oxide hydroxide-AlOOH) formation inside the pores during hot water
sealing post anodization, leads to hydrophilicity due to the activation of
surface hydroxyl groups on the orthorhombic boehmite crystal [31,32].
It is believed that a hydrophilic surface is essential to hinder adsorption
of organic matter (anti-fouling characteristics [33,34]) onto the critical
spacecraft components handled by multiple agencies before launch
activity.
3.2. Nanoindentation studies
Representative load-depth curves for anodic coating and bare AM
alloy obtained from the nanoindentation test are shown in Fig. 8. It is
evident that the final depth after the elastic recovery is higher for bare
AM alloy than the anodic coating. The H and E values of the anodic
coating are measured as 3.95 ± 0.3 and 96 ± 3 GPa, respectively, while
AM bare alloy shows the H and E values of 1.8 ± 0.15 and 90 ± 2 GPa,
respectively. Li et al. [35] reported anodic coating hardness of 399.1 HV
(~3.91 GPa) after anodization of conventional Al–Si cast alloy (15.6 w.
% Si). In another study, Malayoglu et al. [36] reported indentation
hardness of 3–4 GPa and elastic modulus of 95–100 GPa for the anodic
coating on AA6082. A recent study by Mora-Sanchez et al. [19] on AM
Al–10Si–Mg reported the hardness and elastic modulus of much thicker
(~70 μm) anodic coating as 2–3 GPa and ~55 GPa, respectively. Thus,
the mechanical properties of lower thickness anodized coating in this
study are much superior to those reported for much thicker anodic
R. Ghosh et al. Ceramics International 48 (2022) 35689–35697

Fig. 7. WCA data of (a) bare AM alloy and (b) anodic coating.

coating on AM alloys. This has tremendous industrial impact owing to

reduction in turnaround time, less sophisticated power supply re­
quirements; minimized refrigeration requirements of the electrolyte
bath, and meeting very close tolerances with respect to anodic thickness
as required in critical spacecraft components. The nanomechanical
properties (Hardness-H: 3.95 ± 0.3 GPa) of the present coating are also
found to be higher than the crystalline anodic PEO (H~2 GPa) coatings
on conventional AA6061 wrought alloy [37].
The superior mechanical properties may be attributed to the better
compactness in the coating owing to lesser voltage during anodization as
higher voltage and time lead to many local discharges resulting in
increased pore size and hence affecting the modulus of the anodic
coating. Further, better mechanical properties may be also attributed to
the harder minor crystalline oxide phases, e.g., aluminosilicate-kyanite
and Al2O3 unlike a softer crystalline phase of SiO2 in the study re­
ported by Mora-Sanchez et al. [19].

3.3. Corrosion studies

Fig. 8. Typical load-depth curves of anodic coating and bare AM alloy. (Inset
Fig. 9a and b demonstrate the impedance data (Bode and Nyquist
shows the optical image @40Xof the indentation performed.
plots) obtained for the anodic coating and bare alloy after being dipped
in 3.5 wt% solution of NaCl for a duration of half an hour. The

Fig. 9. (a) Bode impedance and (b) Nyquist plots of anodic coating and bare AM alloy. Equivalent circuit for (c) anodic coating and (d) bare alloy in 3.5 wt%
NaCl solution.

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corresponding equivalent circuits are depicted in Fig. 9c and d. From the Table 2
bode-modulus plot in Fig. 9a, it is evident that the anodic coating has Summarized data for individual elements of equivalent circuit for anodic coating
demonstrated two order higher impedance values (about 2.78 MΩ) than and bare AM alloy.
the bare alloy (about 2.97 kΩ), indicating adequate corrosion protec­ Bare Alloy Anodic Coating
tion. A plethora of studies have been published to understand the porous Rs (Ω. Cdl Rt (kΩ. Rs (Ω. Cp Rp (kΩ. Cb
and barrier layer characteristics after anodization of aerospace alloys, cm2) (μFcm− 2) cm2) cm2) (nFcm− 2) cm2) (μFcm− 2)
through impedance equivalent circuits (EC) [38,39]. In the present
6.54 2.67 94.58 5.0 2100 8.2 11.20
work, satisfactory concurrence among experimental data and fitted
values with EC revealed in Fig. 9b and c, has been brought out. The
experimental impedance results are in conformity with numerous helps in calculating barrier layer thickness (db) from the experimentally
studies on anodized layers [40–42]. On scrutiny, it can be seen from the measured capacitance value (Cb) from the bode-modulus plot [Ref]:
Bode-modulus plot (Fig. 10 a) that there are three regions for a decently
db = (κ × κ0 × Aex)/Cb (2)
sealed anodic coating. The impedance values corresponding to the lower
frequency region (f ≤ 1 Hz) represent the barrier layer properties of the
where Aex, κ and κ0 are the 1 cm2 area exposed, dielectric constant of
anodic coating. In the intermediate frequency region, the
alumina = 8.5 and permittivity of vacuum = 8.854 × 10− 14 F/cm,
quasi-horizontal portion in the bode-modulus plot and the related
respectively. Considering a capacitance of the order of ~10− 6 Fcm− 2,
minima in the bode-phase plot indicate the resistive of the porous layer
the computed barrier layer comes around 7.5 nm. The lesser value of
of the anodic coating. Lastly, the steep region around the higher fre­
barrier layer may be primarily due to the underestimated value of the
quency in the bode-modulus signifies the capacitive characteristics of
dielectric constant of alumina (κ). It is opined that the chemical
the porous layer of the anodic coating. Based on this fundamental un­
composition of the barrier oxide layer is not pure alumina because of
derstanding, the capacitance of the barrier (Cb) and the porous layers
sulphate ions (SO−4 2) contamination of the anhydrous alumina and also
(Cp) can be evaluated by extrapolating the straight-line portions to the
due to diffusion of silicon in the barrier layer [40] during anodizing for
angular frequency f = 1 (10 ) and Cb and Cp are the non-ideal capaci­
◦

the present alloy system (10 wt% Si). This alters the oxide structure and
tances or constant phase element (CPE). Similarly, the resistance, Rp of
dielectric constant. Feliu et al. reported a dielectric constant of the
porous-layer is evaluated from the impedance value related to the
barrier layer as 17 for the anodic coating on aerospace grade aluminum
minimum phase angle in the bode-phase plot. In the case of the bare
alloys [28] and attributed the higher dielectric constant due to
alloy, the response of EIS data was fitted (in series) with Rs with
contamination of the anion from the electrolyte. Increase in κ, increases
single-time-constant (Cdl/Rt). Where Cdl signifies double-layer capaci­
the barrier layer thickness to the order of 15–20 nm for the present
tance and Rt means the charge transfer resistance.
system which is in accordance with the literature for sulphuric acid
The data for the elements present in the equivalent circuit (EC) are
anodizing [24].
tabulated in Table 2. The values for the anodic coating are of the order of
The potentiodynamic polarization plots obtained for the specimens
nFcm− 2, μFcm− 2 and kΩ.cm2 for Cp, Cb and Rp, respectively indicating
in 3.5% NaCl are shown in Fig. 10. The electrochemical parameters such
adequate hot water sealing of the anodic oxide. The values reported in
as corrosion potential (Ecorr), corrosion current density (icorr) and tafel
Table 2 are in accordance with the study by Kumar et al. [42] where they
constants (ba and bc) derived from the polarization plots are shown in
have studied the anodizing aspect of AA2024 with higher Cu content. It
Table 3.
is to be noted that aluminum alloys with higher alloying elements
An examination of the polarization curves indicates that anodic
behave differently during anodization owing to the competing actions of
coating exhibit slower icorr value of 4.45E-03 indicating better corrosion
the alloying elements taking part in anodic oxidation [14,29,43]. This
resistance. Contrarily, bare alloy exhibits higher icorr value of 6.10E-01.
particular phenomenon decides the oxide growth rate, its chemical
The Ecorr value (− 0.59 V) of anodic coating is sufficiently higher or more
composition, crystallinity and other thermo-optical properties.
electropositive than the Ecorr value of the bare alloy (− 1.01 V). This
It is imperative that the higher impedance gives better corrosion
indicates that the anodic coating has established adequate corrosion
resistance in chloride containing environments essentially due to barrier
resistance under polarizing conditions. The corrosion rate in millimetre
layer properties of the anodic coating [44]. The following equation (2)
per year (mm/year) was also evaluated using Tafel extrapolation
method (refer equation (3)), based on Faraday’s law [45,46] and tabu­
lated in Table 3. The corrosion rate of the anodic coated specimen is ~
two orders lower than the bare alloy.
/
Corrosion rate (mm / year) = (3.27 × 10− 3 × icorr × E.W.) D (3)

where icorr is the corrosion current density (μA/cm2), E.W. is the

equivalent weight in grams, and D is the density of the metal (g/cm3).
The above potentiodynamic polarization results are in line with the
impedance values (Table 2).

3.4. Thermo-optical properties and space environmental studies

The variation of αs and εIR as a function of wavelength are plotted in

Table 3
Fitting results obtained from potentiodynamic polarization plots.
ba (V/ bc (V/ Ecorr, (V) vs icorr (μA/ Corrosion Rate,
dec) dec) Ag/AgCl cm2) mm/year

Bare Alloy 0.18 0.09 − 1.01 6.10E-01 66E-04

Anodic 0.19 0.12 − 0.59 4.45E-03 0.48E-04
Fig. 10. Potentiodynamic polarization curves for the bare alloy and
coating
anodic coating.

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R. Ghosh et al. Ceramics International 48 (2022) 35689–35697

Fig. 11. Spectra of (a) solar absorptance and (b) infrared emittance of the anodic coating as a function of wavelength.

Fig. 11a and b, respectively. Further, the average αs (in the wavelength
Table 4
range: 200–2500 nm) and average εIR (in the wavelength range: 3–30
Thermo-optical properties of the anodic coating before and after space qualifi­
μm) are measured as 0.87 and 0.78, respectively. On the other hand, the
cation tests.
average αs and εIR of the bare AM alloy are measured as 0.21 and 0.04,
Tests Before Testing After Testing
respectively. Subsequently, the anodic coated specimens were exposed
to specific qualification tests to understand the space worthiness of the αs (±0.01) εIR (±0.02) αs(±0.01) εIR (±0.02)
coating as per Table 4. The variations in thermo-optical properties Relative Humidity 0.88 0.78 0.88 0.77
before and after space qualification tests are summarized in Table 4. It is Thermal Shock Cycling 0.88 0.79 0.88 0.78
important to note that there is no alteration in functional properties Thermo-Vacuum 0.87 0.79 0.87 0.78
which confirms the successful qualifications of the anodic coating to­
wards space worthiness aspect.
Declaration of competing interest
The αs of the present anodic coating are significantly higher (~0.88
vs ~0.365) than the anodic coating fabricated on conventional alloy
The authors declare the following financial interests/personal re­
[47]. Higher solar absorptance results in (αs/εIR) ratio close to unity
lationships which may be considered as potential competing interests:
(refer equation (1)) and is generally preferred for obtaining effective
Rahul Ghosh, Arjun Dey, M. K. Kavitha, Hari Krishna Thota, R. Uma
spacecraft thermal control, unlike similar anodic coatings on conven­
Rani, A. Rajendra and Karabi Das.
tional wrought alloys where the (αs/εIR) ratio is substantially deviated
from unity owing to lower αs. It is to be noted that the improvement in
Acknowledgments
the mechanical and thermo-optical properties of the anodic coating on
AM Al–10Si–Mg alloy is primarily due to higher silicon content of the
The authors express their sincere thanks to Director, URSC for
alloy unlike conventional AA6061 wrought alloy and refined micro­
permitting to publish the paper.
structure achieved during additive manufacturing favouring continuous
and uniform anodic oxide layer.
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Flat absorber black anodic coating of thickness ~13 μm is developed
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