Surface & Coatings Technology 411 (2021) 126993

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Surface & Coatings Technology

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Effective corrosion protection of aluminum alloy AA2024-T3 with novel

thin nanostructured oxide coating
Maido Merisalu, Lauri Aarik, Jekaterina Kozlova, Hugo Mändar, Aivar Tarre,
Väino Sammelselg *
Institute of Physics, University of Tartu, W. Ostwald Str. 1, 50411 Tartu, Estonia

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

Keywords: Effective corrosion protection via a thin ceramic coating on an Al-alloy AA2024-T3 is demonstrated. The
Aluminum alloy preparation of the coating consists of two steps. First, with a special anodizing process, a chemically homoge­
Pitting corrosion neous thin base layer is formed on the substrate. Then, the nanoscale pores in the base layer are sealed, and the
Nanostructured protective coating
entire surface is covered with a chemically resistant Al2O3/TiO2 nanolaminate using atomic layer deposition. The
Amorphous structure
Atomic layer deposition
sample surface is thoroughly characterized, including linear sweep voltammetry (LSV) and electrochemical
Surface engineering impedance spectroscopy (EIS) and testing by long-term immersion in a salt solution. The coating withstands LSV
up to 10 V versus saturated calomel electrode (SCE) and salt solution immersion of 7152 h (298 days).

1. Introduction
The high-strength aluminum alloy AA2024-T3 [1] is used in various
applications, in the aviation, space and automobile industries but it is
also used for making clock and computer parts, valve bodies, fastenings,
and military devices and parts, where light weight and good mechanical
properties and workability are required [2–5]. These properties are
achieved by the insertion of alloying elements and by special thermal
treatments, which lead to the formation of intermetallic inclusions that
hinder the movement of dislocations. It is well known that these inter­
metallic phases (referred to as IMPs or inclusions), for example
Al2CuMg, Al2Cu, Al20Cu2Mn3 and Al7Cu2Fe, have different electro­
chemical activities than the surrounding matrix, and in contact with an
electrolyte, they create localized galvanic couples, which cause pitting
corrosion of the aluminum alloy [6–26]. For instance, in S-phase
Al2CuMg inclusions Mg and Al are more active than the Cu, which leads
to dealloying at the IMP and its enrichment of Cu, which itself turns the
IMP gradually more cathodic than the surrounding matrix
[16,18,22–25]. In contrast, θ-phase Al2Cu acts as a cathode from the
start, causing accelerated corrosion of the anodic Al-rich matrix nearby
and the formation of a pit [16].
Ultimately, the progression of IMP-induced corrosion of AA2024
could further lead to grain boundary corrosion and catastrophic dete­
rioration of the mechanical properties of the alloy [27].
Therefore, various techniques have been developed that can disable
the galvanic couple between the IMP and the surrounding matrix. One of
the most commonly used methods is the application an aluminum
cladding layer [5,28], which covers both sides of the alloy plates and
provides cathodic protection to the exposed edges. A widely used
alternative is the chemical conversion of the surface of the Al alloy into
an electrochemically inert layer, which also disables the galvanic couple
between the matrix and the cathodic IMPs [29–36].
However, the surface of the alloy can also be made inert by utilizing
an electrochemical process known as anodizing [37–50]. During the
anodization, the substrate material is electrochemically oxidized,
creating an anodic oxide layer at the cost of the metal matrix. Tradi­
tionally, a simple potentiostatic process is used for anodizing [3]. Also,
anodizing by potentiodynamic polarization in various electrolytes has
been studied in detail [42,48].
The oxide layers obtained by anodizing aluminum alloys are porous
and the pores are going through the whole thickness of the anodic layer.
Such pores need to be sealed to prevent corrosive substances such as
chloride ions reaching the metal surface [43]. Two common solutions
for this problem are painting/lacquering the anodized surface and
treating the anodized alloy with hot water (i.e., hydrothermal treat­
ment), which causes the walls of the pores in the anodic aluminum oxide
(AAO) layer to be converted into aluminum hydroxide, which takes up
more space and therefore seals the nanoscale pores. Due to the hot water
sealing mechanism it usually corks the pore openings, and as the corking
material is porous, therefore not a good ion barrier, such kind of coating

* Corresponding author.
E-mail address: vaino.sammelselg@ut.ee (V. Sammelselg).

https://doi.org/10.1016/j.surfcoat.2021.126993
Received 15 October 2020; Received in revised form 10 February 2021; Accepted 11 February 2021
Available online 20 February 2021
0257-8972/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. Merisalu et al.
cannot withstand a long-term immersion test [40]. In addition, even
slight scratching could open the pores fully in the scratched area. On the
other hand, it has been shown that sealing the pores with hydrothermal
treatment also slightly increases the hardness of the AAO layer [38].
Although polymer-based coatings can be used to seal the pores, thus
achieving good corrosion resistance, one of the main problems is that the
lower part of the pores may not be filled completely owing to air trapped
in the nano-size pores [50]. Mechanical damage to the surface of the
coating might reopen the pores and provide a path for the corrosive
species to reach the metal below. Furthermore, polymer-based coatings
that are commonly used for the protection of metal substrates are rela­
tively thick (tens or even hundreds of microns), and this may lead to
problems of dimensional tolerance, which is unacceptable in some ap­
plications. Therefore, a more efficient sealing method is required to
enhance the corrosion resistance of anodizable metal alloys by
completely filling the pores in the anodic oxide layer without decreasing
the mechanical properties or increasing the size of the protected
substrate.
Over the last few decades, atomic layer deposition (ALD) has been
demonstrated to be a suitable technique for depositing a variety of thin
films by utilizing sequential self-limiting surface reactions [51–53].
Furthermore, the possibility of synthesizing thin layers of different
materials with this technique, even on substrates with a sophisticated
three-dimensional shape, has led to several studies that propose the use
of ALD for making ultrathin corrosion-resistant coatings [54–64].
Considerable corrosion protection improvement has been observed by
the utilization of Al2O3 and TiO2 nanolaminates prepared by ALD as they
are superior to single-compound films [54,59,62,63]. For instance,
Al2O3 ALD films are dielectric and exhibit good diffusion barrier prop­
erties, but in moist environments, Al2O3 slowly converts into aluminum
hydroxide, and thus the film eventually fails [54,58,60,61]. TiO2 films
are chemically more stable across a broad pH range, but they are
semiconductors and poor ion barriers, and thus they also fail to provide
long-term corrosion protection for the underlying metal substrates
[54,55]. Another study demonstrated the chemical resistance of Al- and
Ti-oxides synthesized by ALD over a broad range of growth temperatures
(80–900 ◦ C) [64]. However, in the case of Al2O3/TiO2 nanolaminates
prepared by ALD, the two materials compensate for each other’s
weaknesses, making a more efficient nanostructured coating. Further­
more, several studies have shown that ALD can be used to coat the walls
of the nano-scale pores in an AAO [65,66], but not for sealing the pores
for corrosion protection purposes.
In this study, we demonstrate the advantages of our novel (sub)
micrometric nanocomposite coatings [67], which provides long-term
corrosion protection for the readily corroding aluminum alloy
AA2024-T3. To obtain the best protection of the alloy surface requires
proper electrochemical treatment of the alloy, which creates a homo­
geneous nanoporous aluminum oxide base layer. Subsequently, by uti­
lizing the ALD method, the porous base layer is transformed into a
nanocomposite, over which a top layer is deposited. The nanocomposite
is formed by sealing the pores to the bottom with a suitable material and
the top layer by depositing the nanolaminate. This top layer works as an
ion barrier and significantly enhances the chemical resistance of the
coating.
2. Experimentals
2.1. Mechanical and electrochemical treatment of the substrates
Small and large substrates with dimensions of 20 × 20 and 40 × 110
mm2, respectively, were cut from a 3-mm thick plate of an AA2024-T3
Al alloy (GoodFellow). The alloy consists of 3.8–4.9 mass% Cu as the
main alloy element; its full standard composition is given in the Sup­
plementary material (Table S1). The obtained plate was covered with an
aluminum cladding layer that was removed by milling before using the
cut substrates. The samples were polished with corundum abrasive
2
Surface & Coatings Technology 411 (2021) 126993
paper P240 (Mirka), followed by cleaning in an ultrasonic bath in three
steps: 3 min in toluene (Sigma-Aldrich; purity 99.5%), followed by 3 min
in acetone (Sigma-Aldrich; purity 99.5%), and finally 3 min in iso­
propanol (Sigma-Aldrich; purity 99.8%).
The anodizing process was carried out at room temperature 23 ±
2 ◦ C in a stainless steel bath, where the anodized sample was the anode
and the bath acted as the cathode. The small substrates were anodized in
a three-electrode setup using an additional saturated calomel reference
electrode and a potentiostat/galvanostat Reference 600 (Gamry). The
large substrates were anodized in a two-electrode setup using a PS 8360-
10 DT 1 kW (Elektro-Automatik GmbH) power supply. The electrolytes
used for anodizing were either 15% sulfuric acid (Honeywell, Fluka
95–97%), denoted as SA, or a mixture of 1% boric (Honeywell, Fluka
99.5%) and 5% sulfuric acid, denoted as BSA. The total surface area,
including both sides and all edges of the substrate as well as the section
of the Al alloy contact wire that was in contact with the electrolyte
during the anodizing process, was approximately 10 and 100 cm2 for the
small and large substrates, respectively. The use of a three-electrode
system for anodizing the small substrates allowed us to gain additional
information on the anodizing process, which included the removal of
IMPs and the formation of the AAO layer. The anodizing process was
carried out in two steps by initially cycling the potential five times be­
tween 0 and 2 V at a scan rate of 10 mV/s. This was followed by cycling
the potential 50 times between 0 and 10 V vs. SCE at a scan rate of 300
mV/s. All the potential values in this work are given versus the SCE
potential unless otherwise defined.
The polarization curves of two small substrates anodized in the two-
step potentiodynamic process are shown in Fig. 1. The curves obtained
using both electrolytes are given for SA (Fig. 1a, b) and BSA (Fig. 1c, d).
The curves in Fig. 1a and c show that IMPs consisting primarily of Cu
were almost entirely removed from the surface during the first anodizing
step (see the peaks near +0.05 V). During the second step, a wider and
quicker potential scan was applied (Fig. 1b, d), which increased the
overall thickness of the AAO layer.
Anodization the large substrates was carried out in the two-electrode
setup by using conditions similar to those for the small substrates.
2.2. Coating of the substrates by ALD
To seal the AAO pores and grow the top layer, ALD was used to de­
posit an Al2O3/TiO2 nanolaminate on the top of the anodized samples
and on a bare substrate for comparison. A low-pressure flow-type lab­
oratory ALD reactor [68] was used for the small samples, and a Picosun
R200 ALD reactor was used for the large ones [69], both at a tempera­
ture of 125 ◦ C. The Al2O3 layers were synthesized from trimethylalu­
minum (TMA; Strem Chemicals; purity 98%) and H2O vapors, and the
TiO2 layers were synthesized from TiCl4 (Aldrich; purity 99.9%) and
H2O. Nitrogen gas (Linde Gas AS; purity 99.999%) was used as both the
carrier and purging gas. The pulse times used in the ALD process were
chosen so that the precursor gases and reaction by-products could suc­
cessfully diffuse into and out of the pores of the AAO, respectively [67].
The growth of the ALD nanolaminates started with a fixed number of
Al2O3 deposition cycles, followed by the same number of TiO2 deposi­
tion cycles. This super-cycle was repeated three times, leading to the
formation of an Al2O3/TiO2 nanolaminate having three layers of both
Al2O3 and TiO2. Nanolaminates 50–500 nm thick were applied by
altering the cycling numbers for the sublayers, with TiO2 always as the
top layer.
2.3. Physical characterization of the samples
First, both the polished sample surfaces and ALD coatings were
studied using an optical microscope Nikon Eclipse LV150 (Nikon Corp.)
at different magnifications. A DualBeam™ having the columns of high-
resolution scanning electron microscope (HR-SEM) and focused ion
beam (FIB) a Helios NanoLab™ 600 (FEI Company) was used for the
M. Merisalu et al.
Fig. 1. Polarization curves showing the anodizing the alloy with (a, b) SA and (c, d) BSA in the (a, c) first and (b, d) second steps.
sample surface and cross-sectional studies. The cross-sections and
lamellae for scanning transmission microscopy (STEM) studies were
prepared in the near-surface regions of the sites of interest using the FIB.
The Helios microscope was also equipped with an energy-dispersive X-
ray (EDX) analyzer INCA Energy 350 (Oxford Instruments) having an X-
Max 50 mm2 silicon drifted detector (SDD), which allows local element
analysis of IMPs and mapping of the areas surrounding the particles. In
both cases, the analyses were carried out in two stages. First, the ele­
ments present were identified. This step used a library of element lines
provided by the analyzer manufacturer. No serious line overlap problem
was observed during the qualitative analysis of the samples analyzed.
Second, quantitative analysis of the identified elements was carried out
by a standardless quantification procedure using a program Quantify
(Oxford Instruments). The program is based on the XPP model proposed
by Pouchou and Pichoir [70,71]. The program uses a pre-installed
standardization database (Oxford Instruments) not needing analysis of
any standard element, but needing periodical calibration of the detector.
In the analysis, normalization of the concentration sum to 100% was
used. In addition, the average elemental compositions of the alloy and
the coatings were analyzed using a six-crystal X-ray fluorescence (XRF)
analyzer ZSX 400 (Rigaku) with a Thin Film Program (Rigaku) for
analysis of thin multilayer structures on the substrates of known
composition. The STEM studies were carried out with a probe-corrected
Titan 200 (FEI) analytical electron microscope equipped with Chem­
iSTEM 4 SuperX SDD EDX system (FEI/Bruker), allowing both high-
resolution high-angle annular dark-field (HAADF) images and element
maps. The crystalline phases of the Al alloy and ALD films were char­
acterized by X-ray diffraction (XRD) and Raman spectrometry. The
symmetrical θ–2θ Bragg-Brentano XRD analysis was performed on an X-
ray diffractometer SmartLab (Rigaku) using Cu Kα and a rotating anode
operated at 45 kV and 180 mA. Diffraction databases ICDD PDF-2 (2011)
[72] and the Inorganic Crystal Structure Database (ICSD, FIZ Karlsruhe,
Germany, 2016) [73] were used as references for phase identification.
Raman spectra were recorded using a Renishaw inVia μ-Raman spec­
trometer with a laser with a wavelength of 514 nm and beam power of
10 mW at the sample surface. The spectra were recorded with a spectral
resolution of 1.5 cm− 1 and from a spot with a diameter of approximately
2 μm if no defocusing was used.
2.4. Corrosion testing of the coatings
The corrosion resistance of the coated and uncoated substrates was
studied by linear sweep voltammetry, electrochemical impedance
spectrometry, and immersion tests. All tests were performed in a natu­
rally aerated 0.5 M NaCl (Sigma Aldrich; purity 99.5%) aqueous solution
with pH ≈ 6.5. The immersion tests lasted from several hours to 7152 h
(298 days). We performed a careful visual inspection of every sample
3
Surface & Coatings Technology 411 (2021) 126993
before the test and after every testing period. Both sides of the substrates
were periodically photographed before and after the tests, using the
high-resolution digital camera of a mobile phone and a homemade
sample illumination system and analyzed afterwards using the higher-
magnification digital images. Before that, the samples were washed
with deionized water and dried in airflow.
Fast electrochemical corrosion tests were carried out using a Paint
Test Cell PTC1™ (Gamry) and the potentiostat Reference 600. The
three-electrode setup for testing included the sample as the working
electrode, a Pt wire as the counter electrode, and an SCE as the reference
electrode. A repeatable well-defined surface area of 1.0 cm2 on the
working electrode was achieved with PortHoles™ electrochemical
sample masks (Gamry), which had a 1.0 cm2 opening. The performance
of the coatings was explored in a broad potential range of − 1 V to +2 V
at a scan rate of 1 mV/s. The best coatings were also tested in a potential
range from − 1 V to +10 V at a scan rate of 300 mV/s.
EIS measurements were carried out at open circuit potential (OCP)
after 30 min and 24 h immersion in the electrolyte in the frequency
range of 10− 2–106 Hz with an AC perturbation amplitude of 10 mV
(RMS). The interpretation of EIS data with the equivalent circuit models
(ECM) was carried out using Echem Analyst™ (Gamry) software.
3. Results
3.1. Characterization of AA2024-T3 alloy
The SEM image and EDX elemental maps of the surface of a me­
chanically treated and cleaned AA2024-T3 substrate are shown in Fig. 2.
As can be seen from the SEM image in Fig. 2a, the surface was covered
with microscopic scratches of various depths. Furthermore, in some of
these features, the upper edges protruded outwards, slightly overlapping
the surface below (see the top left corner in Fig. 2a). Most importantly,
however, there were numerous sites (e.g. sites II–VI in Fig. 2a) that were
lighter in appearance than the surrounding matrix (see region I in
Fig. 2a). These sites are known as IMPs [6–26], and the higher yield of
electrons in these regions can be explained by the higher average atomic
number of the sites in comparison with the surrounding area [74].
Mapping the elements by EDX in the same region (Fig. 2a) revealed
that the Al content in some sites was significantly lower than that in the
main matrix (Fig. 2b), whereas the oxygen content was slightly higher in
the other sites (Fig. 2c). These could be some oxidized particles, such as
corundum particles from the abrasive paper or locally corroded places.
However, in the areas with less Al (Fig. 2b), there was a much higher
content of alloying elements such as Cu (Fig. 2d), Mg (Fig. 2e), Fe
(Fig. 2f), and Mn (Fig. 2g). The largest of the IMPs are sized up to 10 μm
and have a higher content of Cu and Mg (Fig. 2d, e). The second-largest
IMPs were up to a few microns in size and had higher contents of Cu, Fe
M. Merisalu et al. Surface & Coatings Technology 411 (2021) 126993

Fig. 2. SEM image of a polished surface of the AA2024-T3 substrate (a) showing the distribution of surface IMPs on the surface and EDX mapping of elements (b) Al,
(c) O, (d) Cu, (e) Mg, (f) Fe, and (g) Mn in the same area. Data of localized elemental analysis performed at sites I–VI in the central points of the marked areas are
given in Table 1.

and Mn (Fig. 2d, f, g). and some of them were exposed at the surface. The latter is important
To obtain additional information about the IMPs, we measured the because when in contact with an electrolyte, a galvanic couple forms
average elemental composition of the region shown in Fig. 2a and per­ between the surface IMP and the surrounding matrix, as shown in the
formed localized elemental analysis at sites I–VI (Table 1). The analyzed SEM image in Fig. 3b, which was taken from the surface of the alloy after
100 × 100 μm2 area showed that the average elemental composition of 24 h immersion in the salt solution. The damage caused by this localized
the alloy conforms to the conventional AA2024-T3 alloy (Table S1). corrosion appears to be the most severe in the immediate vicinity of the
As for the region between the IMPs, site I in Fig. 2a had the highest IMP owing to the electrochemical nature of the process. Similar SEM
content of Al and lowest content of Cu, Fe, and Mn in comparison with images of galvanic corrosion near IMPs were reported by Boag et al.
the other measured sites. Sites II to V, however, had very similar com­ [16]. As can be seen from the photographs in Fig. 3c and d, this localized
positions, consisting mostly of Al, Cu and Mg, indicating Al2CuMg or S- galvanic corrosion on a microscopic scale also changed the visual
phase particles as reported in many other studies appearance of the surface of the alloy.
[6,8,9,14,16–19,22–25]. Furthermore, the smaller micrometric IMP in Based on these observations and earlier studies [6–26], it is clear that
site VI consisted mostly of Al, Cu, Fe and Mn, likely indicating an Al3(Cu, Al–Cu alloys like AA2024-T3 are highly vulnerable to corrosion. To
Fe,Mn) particle [14]. However, it must be noted, that the character­ counter the problem, it is necessary to disable the possibility of acti­
ization of IMPs with SEM-EDX only gives a rough estimation of the vating galvanic couples between the surface IMPs and the surrounding
possible phase composition of the inclusion. This is because the primary matrix.
electron–sample interaction volume is often larger than that of a sub­
micron/micrometric IMP, creating additional signals from the sur­
rounding matrix and/or other nearby IMPs [74]. The latter is possible, as 3.2. ALD coatings deposited directly onto the substrate
in many cases different IMPs could be interfused [16]. Additional
characterization of the alloy by XRD is discussed in Supplementary The deposition was carried out at 125 ◦ C to avoid degradation of the
material. mechanical properties of the alloy, which was obtained by specific
A cross-section of the alloy was made using FIB, and the freshly cut thermal treatments [2–5]. The low deposition temperature is also rele­
edge was imagined by SEM (Fig. 3a). The cross-sectional image showed vant to the energetic efficiency for obtaining amorphous coatings, thus
that both micrometric and nano-scale IMPs were present in the alloy, preventing the growth of crystallite/grain defective boundaries as
possible diffusion channels for corrosive species. The Raman spectros­
copy results of the TiO2 sublayers in the nanolaminate showed that
Table 1 titania remained amorphous (spectrum is not given). This was not sur­
Results of the semiquantitative EDX analysis of the IMPs at the sites marked in prising as previous XRD and Raman spectroscopy analyses demonstrated
Fig. 2a. that the TiO2 films deposited by ALD on Si substrates with the TiCl4-H2O
Analysis place Cua Mg Fea Mna Al Congruous phase process and the Al2O3 films deposited with the TMA-H2O process
m% remained amorphous up to 200 [52] and 600 ◦ C, respectively [76].
The SEM-FIB results showed that all the IMPs and the surrounding
The whole 4.7 1.2 0.1 0.5 85.4 Average for the alloy
area matrix on the surface of the AA2024-T3 substrate were uniformly coated
Site I 4.0 1.2 0 0.4 89.3 Matrix without larger by the nanolaminate, such that no uncoated areas, pinholes, cracks, or
IMPs other coating defects were detected (Fig. 4a, b). The thickness of the
Site II 36.0 13.9 0.2 0.0 44.1 Al2CuMg nanolaminate measured from the cross-section depicted in Fig. 4b was in
Site III 32.1 11.7 0.0 0.1 47.8 Al2CuMg
Site IV 27.9 10.7 0.4 0.2 51.2 Al2CuMg
the range of ~130 nm. A similar thickness was also measured by XRF
Site V 36.0 15.0 0.0 0.1 43.3 Al2CuMg using the Thin Film Program for the Si reference substrate that was
Site VI 23.0 0.4 6.4 3.0 56.3 Al3(Cu,Fe,Mn) coated with the nanolaminate during the same ALD run as the Al alloy
S-phaseb 44.8 17.1 – – 38.1 S-phase: Al2CuMg substrate.
a
Element electrochemically more noble than Al on base of Galvanic series Fast corrosion testing by LSV showed that coating the substrates with
measured in 5% NaCl solution at room temperature [75]. the nanolaminate significantly lowered the current in cathodic region
b
Calculated stoichiometric composition of S-phase, for comparison. (Fig. 5a). However, the current rapidly increased for all substrates

4
M. Merisalu et al. Surface & Coatings Technology 411 (2021) 126993

Fig. 3. SEM images of the AA2024-T3 substrate, showing an FIB-made cross-section of (a) freshly polished sample and (b) a site with an Al2CuMg IMP after 24 h
immersion in a salt solution. The digital photographs of the large samples (c) before and (d) after immersion.
SEM images in the insets, I and II, show the alloy surface at an Al2CuMg IMP also before and after the immersion, respectively.

Fig. 4. Backscattered electron images of (a) the AA2024-T3 alloy surface coated with the nanolaminate with a large IMP of Al2CuMg in the center and (b) the FIB-
made cross-section of the same region.

Fig. 5. LSV curves for corrosion testing of the small

substrates across a broader potential range. The
substrates were either just mechanically treated
(bare) or coated with 50-, 100-, 250- or 500-nm-thick
nanolaminates; the curves are marked with the same
symbols. In the digital photos, larger samples coated
with the 100-nm-thick nanolaminate are shown (c)
before and (d) after a 129-h immersion test in a 0.5 M
NaCl solution (corrosion sites are marked with circles
and a pit is indicated by the arrow).

during the potential scan in anodic region (Fig. 5a,b). Nevertheless, at performance was shown for nanolaminates with thicknesses of 250 nm
+2.0 V, the current measured for the nanolaminate-coated substrates and above.
was still significantly lower than that of the bare substrate. The best The corrosion resistance of a large nanolaminate-coated substrate by

5
M. Merisalu et al.
immersion in salt solution for 129 h (Fig. 5d) showed clear improvement
in comparison with the bare substrate tested under similar conditions for
only 24 h (Fig. 3d). The general appearance of the nanolaminate-coated
surface hardly changed compared to that of the uncoated one. Large
corrosion sites located close to the edges of the substrate (marked with
circles in Fig. 5d), could be a result of scratching of the coating before
the test, as the sides of the substrates were not lacquered after the ALD
process. To obtain a better understanding of the coating failure mech­
anism, we studied several local corrosion sites by SEM and EDX.
The evolution of one corrosion pit, which was detected after 24 h
immersion in the salt solution, is shown in Fig. 6a–c. As can be seen from
these SEM images, the coating first started to crack (Fig. 6a), followed by
delamination (Fig. 6b) and then by further destruction of both the
coating and the substrate at the local site (Fig. 6c). Additional EDX
elemental mapping of the region showed the presence of a micrometric
IMP, which seemed to consist of several smaller particles of different Cu-
rich compounds, and an IMP that had a higher content of Fe and Mn
(Fig. 6e,f). The study also revealed several IMPs with higher contents of
Cu and Mg (possibly the previously observed Al2CuMg phase). However,
the nanolaminate coating on top of these IMPs appeared to remain intact
during the immersion test (compare Fig. 6a with Fig. 6d and h). It should
also be noted that we studied numerous local corrosion sites, but many
of them were covered with corrosion products soon after the start of the
test. Therefore, the mechanism of the initial failure of the coating at
these sites could not be investigated by SEM. In consequence, the SEM
and EDX studies showed that using only an approximately 0.1-μm-thick
nanolaminate directly on the substrate provides protection to the sur­
face, but it is not possible to achieve long-term corrosion protection for
AA2000 alloys in heavily corrosive environments.
The studies and tests of this section showed that mechanical pre-
treatments and thorough cleaning with organic solvents alone are not
sufficient to produce a clean and chemically homogeneous surface,
Fig. 6. SEM image (a–c) of the evolution of a pit during 129-h immersion on a polished Al alloy sample with a 100 nm nanolaminate coating. EDX mappings of the
same region after 87-h immersion show the distribution of (d) Cu, (e) Fe, (f) Mn, (g) Al, (h) Mg, and (i) O. Possible near-surface Al2CuMg IMPs are marked with circles
and a crack in the coating with arrows in the SEM image (a).
6
Surface & Coatings Technology 411 (2021) 126993
which is essential for the nanolaminates to work effectively. One way to
achieve the latter goal for light-weight metal alloys such as AA2024-T3
is to convert the surface of the alloy into a chemically homogeneous
oxide layer by anodization.
3.3. Anodized AA2024-T3 surface
In addition to creating a nanoporous oxide layer, the anodizing
process cleans loose particles and other contaminants from the surface,
but, more importantly, it also removes near-surface IMPs. This is the
main reason Al–Cu alloys (e.g., AA2000 series) are complicated to
anodize [42]. Therefore, we next studied the anodization of the alloy in
two popular electrolytes, SA and BSA.
The anodization of the alloy was carried out through potentiody­
namic polarization in two steps, as described previously. The idea of the
first, slower anodizing step was to achieve a clean and homogeneous
surface with an AAO layer in which the IMPs are removed. During the
second step, in which we investigated higher potentials and faster scan
rates, the homogeneous AAO layer became thicker, up to the value
needed for the required application. In this study, the investigated
thicknesses of the AAO layers were ≤2 μm and ≤0.5 μm for SA and BSA,
respectively.
As seen in Fig. 1a and c an intense peak appeared at approximately
50 mV during the first polarization cycle of the first anodizing step,
which practically disappeared in case of using SA but remained
detectable after the fifth cycle in the case of using BSA. This peak rep­
resents mainly the oxidation of Cu-rich IMPs, where Cu is dissolved into
the solution. At the same time, the Al component in the alloy was
oxidized, forming a much less soluble AAO layer, and its thickness was
practically achieved during the first cycle of this step. The oxidation of
Al was faster and went much deeper at higher anodic potentials (see
Fig. 1b,d). In this step, the most significant homogenization of the AAO
M. Merisalu et al.
layer took place during the first cycles. In all polarization plots, the
current values decreased with each sequential cycle as the IMPs were
removed and the Al component in the alloy was converted into a
nonconductive passivation layer comprising a mixture of Al2O3 and Al
(OH)3.
SEM studies of the anodized surface after the second anodizing step
confirmed the removal of all IMPs as micrometric-size hollows appeared
(Fig. 7a,d). Many of the large cavities were likely left behind after
extracting the previously observed Al2CuMg inclusions (see Fig. 2a).
Higher-magnification images of the surface (Fig. 7b,e) also revealed
cylindrical holes. Based on the XRD measurements discussed in Section
3.1 and the HR-SEM images shown in Fig. S2, these holes were probably
created by removing sub-micrometric Al20Mn3Cu2 inclusions. The HR-
SEM images of the anodized surfaces showed the nanoporous structure
of the AAO layer (Fig. 7b,e). However, studying just the surface of the
AAO layer was insufficient; therefore, the layer was studied in more
detail by utilizing the SEM-FIB cross-sectioning technique (Fig. 7c,f).
Prior this study, the pores were filled with TiO2 using ALD to create
sufficient contrast between the pores and the AAO matrix. The pores
were completely sealed with titania, and they appear darker in the im­
ages because TiO2 is more conductive than the surrounding Al2O3,
which is slightly charged under the electron beam and therefore appears
brighter [74]. Furthermore, the pores in the AAO of the alloy appear to
form a sophisticated three-dimensional network, branching and/or
inclining in numerous directions at specific points.
Comparing Fig. 7c and f suggests that anodizing in BSA resulted in a
thinner and denser AAO layer owing to the smaller density of pores
compared to the anodic layer got by anodizing in SA. A similar effect was
shown in the work of Du, et al. [45] for BSA with a low concentration of
boric acid. The thickness of the AAO layer obtained in the BSA process
was up to five times smaller, 300–400 nm, as shown in Fig. 7c, in
comparison to approximately 1.8 μm for the SA process (Fig. 7f). The
reduced thickness of the AAO layer obtained in the BSA anodizing
process is mostly related to the lower content of sulfuric acid in the
mixture, which caused both lower chemical activity and reduced con­
ductivity of the electrolyte [47].
3.4. The novel coating: AAO layer sealed and covered by ALD
HR-SEM cross-sectional images of two samples anodized in BSA and
SA followed coverage with the ALD nanolaminate, and STEM images of
the first sample, are shown in Fig. 8. The SEM images in Fig. 8a and b
show clearly the structure of the ALD nanolaminate. The first deposited
Fig. 7. SEM images of the surfaces of the samples anodized with (a–c) BSA and (d–f) SA, showing the removal of (a, d) micrometric and (b, e) nano-scale surface
inclusions; (c, f) FIB cross-sections of the corresponding samples after sealing the AAO pores with TiO2.
7
Surface & Coatings Technology 411 (2021) 126993
alumina sublayer, the lighter strip, seems to be somewhat thinner than
the next two alumina sublayers. The reason for this is that during the
first alumina sublayer deposition, some of the synthesized material was
used to seal the anodic layer pores. The diameters of the pores were in
the range of 5–10 nm, and the planned thickness of the alumina sub­
layers was approximately 18 nm; thus, in this particular case, the pores
were sealed during the deposition of the first alumina sublayer. It is
therefore not possible to see from this image whether the pores were
sealed to bottom because both the anodic layer and the material
deposited into the pores consisted of the same nonconductive material,
which decreased the image contrast in this region.
To overcome the limitations of SEM imaging, we prepared FIB thin
lamellae from the samples for further STEM studies (Fig. 8c–f). Fig. 8c
and d show STEM bright-field images of the novel coatings prepared by
anodizing in BSA and SA, respectively. The images clearly show the
structure of the ALD nanolaminate, but here the titania sublayers are
darker than the alumina ones because of higher density of the titania
sublayers. The images also show the structure of the sealed AAO layers
because the high-energy (200 keV) primary electrons of the electron
beam did not charge this dielectric layer. Thus, the image shows suc­
cessive sealing of the pores in AAO by alumina. A few larger gaps (<100
nm), left during the anodizing process after the removal of some cylin­
drical IMPs, were partly filled and are therefore visible as small, light
spots in the sealed AAO. Fig. 8e shows an HAADF image of the upper
part of the novel coating with an EDX Cl map overlay, both obtained
simultaneously in STEM mode. Detailed analysis of this image is given in
the Section 4. Finally, to demonstrate more directly the sealing of the
pores to the bottom Fig. 8f shows a Ti map of the AAO, in which pores
were sealed with titania via ALD, as shown in Fig. 7c. It can be seen that
the titania filling reaches the interface between the AAO and the alloy.
Using ALD for sealing the nano-scale pores in the AAO and covering
the surface with a thin, chemically inert top layer greatly improved the
corrosion resistance of the Al alloy (Fig. 9). As can be seen from the
polarization curves in Fig. 9a, the current values measured for the coated
substrates were several orders of magnitude lower than that of the
polished sample. Furthermore, no significant pitting was detected, even
when the coated samples were scanned up to an anodic potential of 10 V
(Fig. 9b). Comparing the results for the substrates anodized in SA and
BSA followed by coating by ALD (Fig. 9b, curves 2 and 3, respectively) it
can be seen that the current values at the investigated anodic potentials
are only slightly higher for the BSA samples.
To study the long-term performance of the coating, a control sample
and a sample anodized in BSA and coated with the nanolaminate were
M. Merisalu et al. Surface & Coatings Technology 411 (2021) 126993

Fig. 8. Cross-sectional images of the novel nanostructured coatings: (a, b) HR-SEM secondary electron images of the coatings prepared with anodizing in BSA and SA,
respectively, (c, d) STEM-BF images of the same, (e) STEM-HAADF image with Cl map overlay of the coating prepared with anodizing in BSA, and (f) STEM-EDX map
of Ti of the lower part of the AAO sealed with titania by the help of ALD, similar to that shown in Fig. 7c.

tested by immersion for 7152 h (298 days) in 0.5 M NaCl solution. The
photographs that were taken before (Fig. 9c) and after (Fig. 9d) the test
showed that the coated sample remained practically unharmed, whereas
the substrate subjected to polishing alone was corroded within the first
24 h (Fig. 3d).
Because the cut edges of the sample and its holes were not protected
with lacquer before anodization or before the immersion test, the areas
showed some corrosion damage. There was some pitting where the
edges were touched by tweezers during installation into the ALD reactor
chamber but other edge parts survived the test well (Fig. 9d). The
damage was more apparent near the hole edges that were in contact with
the Al wire used to obtain electrical contact during anodizing and to
hold the substrates in the vertical position in the ALD reactor.
3.5. EIS analysis of the coatings
The EIS measurements depicted in Fig. 10 and presented in Table 2
exhibit good reproducibility for the two novel coatings that were
anodized in SA and BSA prior to enhancement by ALD. The measure­
ments were done twice, first after the stabilization of the sample
potential for 30 min at OCP in a naturally aerated neutral 0.5 M NaCl
solution (marked in the graphs as “0 h”) and then after immersion of the
coated samples for 24 h in the same solution (marked as “24 h”). In the
ECM-s depicted in Fig. 10 the marks are as follows: R.E. is the reference
electrode, W.E. is the Al alloy substrate acting as the working electrode,
Rsoln is the electrolyte resistance between R.E. and W.E., Rpo is the pore
resistance (describes a coating with pores), Rcor is the charge transfer
resistance (describes corrosion in defects), and Ø represent the constant
phase elements (CPEs) that take into account coating capacitance (Cc)
and double-layer capacitance (Ccor) in the coating substrate interface.
The exponents n1 and n2 used in the calculation of the impedances of the
first and second CPE, respectively, indicate the deviation of the in­
sulators of the capacitors from ideal dielectric behavior, where n = 1 for
an ideal capacitor and n = 0 for an ideal resistor [77].
The impedance amplitude, (|Z|) and phase angle (θ) Bode plots
describing the behavior of the nanolaminate on a polished sample are
shown in Fig. 10a. The |Z| plot before immersion (0 h) is almost a
straight line in the frequency range of 10− 2–105 Hz. In addition, the θ
plot retains an approximately 90◦ level across a wide frequency range,
all of which indicate that the coating initially worked as a capacitor with

8
M. Merisalu et al. Surface & Coatings Technology 411 (2021) 126993

Fig. 9. Corrosion tests using LSV: (a, b) a polished sample (curve 1), a sample anodized in SA and coated with the nanolaminate (curve 2), and a sample anodized in
BSA and coated with the nanolaminate (curve 3) (a) in a narrower potential range near the corrosion potential region and (b) in a broader potential range; (c, d)
photos of a large sample anodized in BSA and coated with the nanolaminate (c) before and (d) after the 7152-h (298 days) immersion in 0.5 M NaCl solution.

Fig. 10. Bode plots for Al alloy substrates (a) coated just with 100 nm nanolaminate and (b) anodized in BSA and (c) anodized in SA, both coated with 100-nm-thick
nanolaminate; (d) ECM used for modeling of the plots in (a) and (e) ECM used for modeling of the plots in (b) and (c).

a relatively low capacitance owing to its large thickness of 100 nm.
However, after 24 h of immersion, the |Z| plot changed significantly,
showing two capacitive parts with a resistive part between them in the
frequency range of 1–100 Hz. In addition, the θ plot has a minimum in
the marked range. To model the behavior of these plots requires an ECM
with two time constants, as shown in Fig. 10d. The modeled values for
the ECM given in Table 2 (100-nm-thick nanolaminate) show that the
values of Rpo and Rcor, which were reasonably high at the start, indicated
no noticeable defects in the coating. These values decreased by two
orders of magnitude after 24 h immersion, indicating remarkable
corrosion processes through the pores/defects in the coating, which
were generated and/or enlarged during the immersion.
For the two novel coatings, the |Z| plots were perfect straight lines
throughout the spectrum, which did not change before and after the 24 h
immersion test. These straight lines show the capacitive character of the
coatings down to the lower frequency end, which indicates that the
charge transfer kinetics were extremely slow in the coatings. In addition,
the θ plots of the two coatings remained near the 90◦ level in a wide
frequency range, which confirms the ideal capacitor properties of the
structure with the novel coatings. Based on these results, it is reasonable
to model the Bode plots using the single time constant model given in
Fig. 10e. The characteristic values obtained by modeling with this ECM

9
M. Merisalu et al. Surface & Coatings Technology 411 (2021) 126993

Table 2 one could ask whether the alumina sublayer was sufficient as an ion
Calculated ECM variables (Fig. 10d, e) for the coated Al alloy substrates before barrier for preventing the diffusion of chlorine atoms/ions from the
and after the immersion test. titania sublayer through the alumina sublayer to reach the alloy
Immersion time & Coatings considering that diffusion is much faster at elevated temperatures as
EMC variables
100 nm BSA anodized + SA anodized +
during the nanolaminate deposition process. Based on our STEM studies
nanolaminate 100 nm 100 nm (see Fig. 8e), we can declare that no chlorine species diffusion through or
nanolaminate nanolaminate into the alumina sublayers occurred. In the Fig. 8e, chlorine EDX map
Immersion time, h 0 24 0 24 0 24 overlays the nanolaminate cross-section HAADF image (orange dots
Rsoln, Ω cm2 9.2 8.5 10.0 10.0 10.0 10.0 mark registered X-ray quanta) from the same area, which shows no in­
Rcor, Ω cm2 1.3 × 2.1 × – – – – crease in the chlorine intensity in the alumina sublayers, including the
108 106 first one. The few orange dots one can see in the alumina sublayers and
Rpo, Ω cm2 3.2 × 7.7 × – – – –
107 104
in the substrate area belong to the X-ray background radiation quanta.
Rc – – 7.5 × 7.4 × 1.2 × 1.3 × Thus, no chlorine from the titania sublayers or from the salt solution
108 108 109 109 during the immersion tests could reach the substrate through the novel
− 2 n1–1
Ccor, F cm s 1.2 × 1.8 × – – – – coating. Based on the results of possible chlorine species in the nano­
10− 7 10− 6
laminate, we can declare that the other corroding species listed above
n1 0.68 0.71 – – – –
Cc, F cm− 2 n2–1
s 1.0 × 1.5 × 1.8 × 1.9 × 7.2 × 7.2 × cannot diffuse through the nanolaminate. This fact is important in terms
10− 7 10− 7 10− 8 10− 8 10− 9 10− 9 of the commercial introduction of the novel coating as the TiCl4 pre­
n2 0.97 0.94 0.97 0.97 0.97 0.97 cursor is less expensive than its metal-organic analogs, and it allows the
use the of low-temperature ALD processes for coatings.
are given in Table 2 as data for the “BSA/SA anodized + nanolaminate”
4.2. Commercial potential of the novel nanostructured coating
coatings. From the results, the Rc and Cc values of the novel coatings did
not change before and after the 24 h immersion test. The Rc values of the
To overcome the ultrathin protective coating failure problem, two-
novel coatings were larger than the Rpo value of the nanolaminate-only
step anodization of the alloy sample is proposed to be implemented
coating by one order of magnitude before and four orders of magnitude
before the ALD deposition of the nanolaminate. We showed that the
after the immersion test. Finally, in the last ECM, the coating capacity is
removal of most surface IMPs could be achieved by a few slower dy­
described by a CPE to take into account the roughness of the novel
namic scans from 0 to 2 V via a potentiostat. We also showed that the
coatings, which was mainly induced by the removal of the micrometric
process can be precisely controlled in a three-electrode cell that allows
IMPs from the sample surface. However, modeling showed that in this
monitoring the decrease of the copper oxidation peak at +0.05 V. Thus,
case, the value of the exponent n2 = 0.97 ≅ 1.0; thus, the CPE in the
during the first anodizing step, a thin, chemically homogeneous AAO
ECM could be replaced with just a pure capacitor Cc, which we did, and
layer is created, and the second anodizing step is necessary only for
the results did not show a remarkable change in the value of modeling
further increasing the thickness of the AAO layer. However, this type of
goodness.
setup for the removal of IMPs from the surfaces of large samples and in
In conclusion, the EIS analysis showed that the nanolaminate
industrial processes is too complicated if not impossible. For this reason,
deposited on the polished substrate provided the alloy with limited
we proposed using lower potential scans in the first anodizing step fol­
corrosion protection, but corrosion sites evolved during the 24-h im­
lowed by several higher potential scans (see Fig. 1). This procedure al­
mersion in the salt solution. These sites were then verified by visual
lows the growth of a homogeneous AAO layer with the required
inspection and microscopy studies, and it was found that the nano­
thickness without needing to check the electrochemical process in
laminate coating had several defects, similar to those shown in Fig. 6a.
detail.
In contrast, the novel coatings behaved as perfect dielectric layers that
Nanostructured coatings made by anodizing as a pre-treatment and
well withstood the immersion tests.
ALD sealing and coating of the base layer with the nanolaminate per­
formed well in both quick electrochemical tests and in long-term im­
4. Discussion
mersion in a salt solution. This can be explained by the removal of
abnormally large IMPs and their clusters from the sample surface, which
4.1. Failure mechanisms of the ultrathin nanolaminate coating on
were associated with sites of failure on the nanolaminate-coated sub­
AA2024-T3 substrates
strates, see more in Supplementary material. However, the sealed AAO
layer also acted as a thick barrier layer between the underlying IMPs in
In this study, we showed that in the alloy, many micrometric IMPs
the alloy and the corrosive species in the nanolaminate and on its sur­
reached the sample surface, as shown in Figs. 2a, 3a, and 4b, and some of
face. Furthermore, during the anodizing process, the surface of the alloy
them, especially those that contained copper, increased local corrosion,
was slightly etched, which removed contaminants, otherwise weaken
even in a sample coated with the ALD nanolaminate only in a corrosive
the adhesion of the coating or hindering the growth of the coating
environment (see Fig. 6, showing the development of a local corrosion
during ALD. The AAO layer also ensured excellent adhesion with the
site). The start of the coating failing mechanism is still not clear. Careful
nanolaminate, and the whole nanostructured coating was more compact
HR-SEM and SEM-FIB studies of the as-prepared coatings on many
and mechanically more durable than the nanolaminate alone, which
samples of the alloy prepared in different deposition runs did not reveal
became apparent in sample handling. Overall, the novel nanostructured
any defects in the coatings, such as pinholes or (nano)cracks. Thus, no
coatings were far superior to the nanolaminates, and the two-step
direct contact of corrosive species such as Cl− , OH− , O2, H2O, etc., with
preparation process can be easily scaled up for practical industrial ap­
the metal substrate could have occurred. One hypothesis of possible
plications for the protection of precision details or when parts/equip­
corrosion under the “perfect” ALD coating is related to the presence of
ment made of Al alloys such as AA2024-T3 are used in corrosive
some amount of chlorine in the titania sublayers of the nanolaminate.
environments.
Namely, using a low-temperature ALD process (125 ◦ C) and TiCl4 and
Although the novel corrosion protective coating with micrometric or
H2O precursors resulted some percentage of chlorine residue in the
submicrometric AAO thicknesses worked well (see Figs. 9 and 10), the
deposited titania material [78]. The titania sublayer was separated from
anodizing processes used are still not optimized; for example, we do not
the alloy by 8-nm-thick alumina sublayer in the case of 50-nm-thick
know the minimal required thickness of the AAO layer or whether a
nanolaminate deposited directly onto the alloy substrate. Therefore,
potentiostatic anodization is suitable for preparation of the novel

10
M. Merisalu et al.
coatings. Also, the structure of the nanolaminate needs optimization.
Further studies are also required to understand ways to save on mate­
rials and energy output. Finally, the hardness and wear resistance of the
coating must be studied.
5. Conclusions
In this study, we demonstrated a significant enhancement in the
corrosion resistance of the highly vulnerable to corrosion Al alloy
AA2024-T3 by using a novel nanostructured protective coating. We
prepared, developed, and tested the thin ceramic coating thoroughly.
The coating consisted of a thin, chemically homogeneous anodic oxide
base layer that was prepared with a special electrochemical treatment
and a chemically resistant Al2O3/TiO2 nanolaminate top layer synthe­
sized by ALD. The first layer eliminates the surface IMPs and the second
layer seals the nanopores and cracks in the base layer to the bottom,
transforming the anodic oxide into a chemically/electrochemically
resistant nanocomposite.
Our studies showed that by depositing the 50–500-nm-thick nano­
laminate directly onto a mechanically polished and cleaned AA2024-T3
substrate it was possible to disable the formation of galvanic couples
between the surface IMPs and the surrounding anodic/cathodic matrix
to enhance the corrosion resistance of the alloy. However, the first
microscopic sign of corrosion appeared during 24-h immersion in a salt
solution, making the nanolaminate coating insufficient for long-term
protection in applications involving corrosive environments.
Next, we showed that the localized failure of the nanolaminate
coating in many cases is related to the underlying IMPs with a higher
content of Cu and possibly Fe and Mn, but not Mg. The latter may have
been removed due to rapid dealloying when exposed to salt water. At
these sites, the adhesion of the coating could be weaker, thus local, so far
not detected nano-cracks may evolve, which promote the permeation of
the corrosive species through the coating and lead to the enlargement of
the coating defect(s) if exposed to a corrosive environment. Eventually,
the corrosive species would migrate through these defects leading to a
cascade of corrosion processes that gradually destroy the coating and the
metal alloy.
The main result of our work is the demonstration that by utilizing a
specific electrochemical treatment of the alloy in sulfuric acid or bor­
ic‑sulfuric acid mixture, it is possible to remove near-surface IMPs. The
treatment converts the near-surface layer of the alloy into a chemically
homogeneous and porous AAO layer. The pores are sealed to bottom and
the full coating is converted to a nanostructured chemically resistant
solid composite material by covering the AAO surface with a ceramic
nanolaminate using a low-temperature ALD process. The novel coating
is easily paintable and can be introduced into the surface finishing in­
dustry. The developed coating exhibited excellent corrosion resistance
in the tests of short-term anodic polarization up to 10 V and immersion
in a salt solution for 7152 h (298 days).
We hope that the novel thin coatings and the new technology for
their preparation will be used in next generation cars and in the aircraft
industry, as well as meet the needs of space exploration.
CRediT authorship contribution statement
Maido Merisalu: Investigation, Methodology, Validation, Visuali­
zation, Writing- Original draft preparation.
Lauri Aarik: Investigation, Writing- Original draft cowriter.
Jekaterina Kozlova: Investigation, Original draft cowriter.
Hugo Mändar: Investigation, Methodology, Original draft cowriter.
Aivar Tarre: Investigation.
Väino Sammelselg, corresponding author: Conceptualization,
Methodology, Validation, Funding acquisition, Project acquisition, Su­
pervision, Writing- Review & Editing.
11
Surface & Coatings Technology 411 (2021) 126993
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
Authors thank Alma-Asta Kiisler and Peeter Ritslaid for technical
assistance, dr. Ahti Niilisk for the help at Raman spectroscopy and dr.
Mihkel Rähn for the help at STEM measurements. The study has been
supported by Estonian Ministry of Education and Research by granting
the projects IUT2-54, TLTFY14054T, IUT2-24, PSG448, and by the EU
through the European Regional Development Fund under project TK141
(2014-2020.4.01.15-00).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.surfcoat.2021.126993.
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