j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7

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journal homepage: www.elsevier.com/locate/jmrt

Original Article

Electrochemically obtained Al2O3 nanoporous

layers with increased anticorrosive properties of
aluminum alloy

Lidia Benea a,*, Nicoleta Simionescu e Bogatu a,b, Roxana Chiriac a,c,**
a
Competences Center: Interfaces-Tribocorrosion-Electrochemical Systems, Dunarea de Jos University of Galati, 47
Domneasca  Street, RO-800008, Galati, Romania
b
Faculty of Engineering, Dunarea de Jos University of Galati, 47 Domneasca Street, RO-800008, Galati, Romania
c
Faculty of Medicine and Pharmacy, 35 Al. I. Cuza Street, Galati, Romania

article info abstract

Article history: The nanoporous layers of aluminum oxide obtained by means of the anodic oxidation
Received 30 November 2021 process, in 1 M H2SO4 in which 1 g/L Al2(SO4)3
18H2O was added, at constant potential and
Accepted 7 February 2022 three oxidation times, are subjected to corrosion tests in 3.5% NaCl solution, pH ¼ 5.75, to
Available online 11 February 2022 evaluate their anticorrosive properties compared to the unmodified surface of the Al1050
aluminum alloy. Electron microscopy and EDX compare the morphology of nanostructured
Keywords: aluminum oxide surfaces with their composition and layer thicknesses. Also, by analyzing
Nanoporous Al2O3 the X-ray diffraction, the aluminum oxide is highlighted by the specific diffraction peaks.
Anodic oxidation The evaluation of the corrosion resistance is performed by the electrochemical methods
Aluminum alloy like evolution of the free potential depending on the immersion time and electrochemical
Electrochemical characterization impedance spectroscopy. From the analysis of the obtained results, a uniform and size
Corrosion resistance distribution of the nanopores is observed, between 17.8 nm and 47 nm, depending on the
anodic oxidation time. All nanoporous layers of aluminum oxide obtained have improved
anticorrosive properties compared to untreated aluminum alloy.
© 2022 The Author(s). 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/).

has been the optimal solution for the development of new

1. Introduction materials, advanced layers and functional surfaces. The
development of nanotechnologies and thus of functional
In recent decades, research activities have focused on the surfaces has allowed an increase in productivity in industry, a
development of nanomaterials and nanotechnologies but also more efficient use of material and energy resources, a lower
on the transfer of knowledge from research laboratories to impact of pollution produced by industry and transport on the
industry. The rapid progress of today's society confirms that environment and human health [1e8].
research in the fields of nanomaterials and nanotechnologies

* Corresponding author.
** Corresponding author.
E-mail addresses: Lidia.Benea@ugal.ro (L. Benea), roxana.chiriac10@yahoo.com, ladyly2030@gmail.com (R. Chiriac).
https://doi.org/10.1016/j.jmrt.2022.02.038
2238-7854/© 2022 The Author(s). 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/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7 2637

Pure aluminum is a reactive metal according to its position Compared to the results presented in the literature, this
in the series of reactivity of metals. Due to the native layer of research aims to obtain nanoporous layers of aluminum oxide
aluminum oxide that covers the metal upon exposure to air, with different layer thicknesses by anodic oxidation that can
aluminum has an increased resistance to corrosion. At room improve the anticorrosive properties of Al1050 alloy.
temperature, the thickness of the native layer of aluminum The novelty of this study compared to the works in the
oxide is between 2.5 and 10 nm [1,2]. Aluminum and its alloys literature consists in obtaining nanoporous layers of
can be used in a wide range of environments, without addi- aluminum oxide through the anodic oxidation process
tional protection, relying only on the protection provided by following the influence of time on increasing the thickness of
the native layer of aluminum oxide. Al2O3 layers in order to increase the anticorrosive perfor-
The porous Al2O3 film obtained by the anodic oxidation mance of the obtained layers.
process has become an area of interest for researchers in
various fields, due to its high versatility, low equipment costs,
but also the high physical, mechanical and anticorrosive 2. Materials and methods
properties of the aluminum oxide layers obtained [9]. The
anodic oxidation process involves the formation of a layer of 2.1. Fabrication of nanoporous aluminum oxide on
aluminum oxide at the metal-electrolyte interface, with a Al1050 alloy
variable thickness, which will provide improved properties to
the substrate, especially an increased corrosion resistance. 1050 aluminum alloy is used as a substrate for growth of
During the anodic oxidation process, the anodizing voltage, nanoporous layers of aluminum oxide by anodic oxidation
the type of electrolyte and the time strongly modulate the process. To obtain the nanoporous layers of aluminum oxide,
characteristics, especially the pores, the size and the thick- the material used as a substrate is cut to the size of
ness of the obtained layers [5]. 0.2
3
3.5 cm. After cutting, a mechanical polishing of the
Anodizing is one of the electrochemical processes per- samples is necessary in order to remove the layer of native
formed to produce a much thicker oxide layer than the aluminum oxide formed on their surface in contact with the
naturally occurring oxide layer, with improved physical and environment as well as macroscopic defects [1].
chemical properties. After the anodizing process, there are The cleaning protocol of the samples after the mechanical
two types of oxide layers that form on the surface of polishing process is the following: rinsing with distilled water,
aluminum. The first layer that behaves like an electrical chemical cleaning for 30 s in 5 M sodium hydroxide solution,
insulator that is thin, hard and resistant to wear. The second is followed by washing with distilled water for 60 s. Then the
a thicker pore layer called the anodic aluminum oxide layer. samples are dried for 60 min in the oven at 50  C. After this
Anodizing aluminum into acid electrolyte solutions improves process, the active surface of the samples is established at
the mechanical properties of the material, such as excellent 6.5 cm2 by delimitation with epoxy resin. The samples thus
hardness, increased corrosion resistance and abrasion. The prepared are stored in the desiccator until their use in the
anodized aluminum oxide layer is part of the aluminum and anodic oxidation process [1].
not a separate layer, such as powder coating or paint. The To control the potential applied during the anodizing of
anodized layer is much larger than the aluminum substrate, Al1050 samples a TDK LAMBDA GEN 300-8 voltage source is
measuring nine on the Mohs hardness scale (the diamond is used [1]. In order to obtain nanoporous layers of aluminum
10 on the Mohs scale) [10]. oxide, several types of electrolytes were tested, but the best
Nanoporous layers of aluminum oxide, due to their prop- and reproducible results are obtained with 1 M H2SO4 elec-
erties, are used in a wide range of industries, from nano- trolyte in which 1 g/L Al2(SO4)3 octadecahydrate is added [1].
technologies where they are used in the manufacture of Fig. 1 shows the classic electrochemical cell in which the
sensors or as templates for obtaining nanowires, nanotubes of anodic oxidation process took place where the anode is un-
various sizes [9e13], practical nanofabrications of membranes treated Al1050 alloy with an active surface of 6.5 cm2 and the
[14], energy storage [15] to the field of anticorrosive surfaces cathode is also made of Al1050 alloy with an area of 12 cm2.
with complex structure [16], from the field of wastewater The volume of electrolyte used is 200 mL [1].
treatment or selective filtration of chemical pollutants [17] to After identifying the values of the optimal parameters for
the medical field where they are used as a support for cell the formation of nanoporous layers of aluminum oxide, as
growth in incubators [18]. primarily the potential of 21 V, the anodic oxidation time was
The versatility of aluminum oxide in these areas is largely varied between 25 and 45 min to observe its influence on
due to its specific properties, such as low density, high morphological, compositional and structural characteristics
ductility, good oxygen barrier properties, good mechanical as well as the anticorrosive properties compared to unoxi-
and wear resistance, high thermal and electrical conductivity dized alloy.
and improved prevention capacity of corrosion [19,20]. The anodically oxidized 1050 aluminum alloy surfaces
Some authors have studied the influence of sealing were extracted from the resin and then prepared to be char-
methods on anticorrosive properties after anodic oxidation of acterized both morphologically, compositionally, structurally
three alloys, 1070, 2024 and 7075, by the potentiodynamic and in terms of anticorrosive properties.
method in 1 M NaCl solution [16]. It has been shown that the The morphological and compositional characterization of
application of different sealing methods on oxidized the nanoporous layers of aluminum oxide was performed
aluminum alloys have different influences on the corrosion with the help of the scanning electron microscope coupled
behavior. with the dispersed X-ray analyzer type FEI QUANTA 200.
2638 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7

Fig. 1 e Schematic drown of electrochemical oxidation of Al1050 alloy: (a) Electrochemical cell showing the cathodic and
anodic processes as well as the overall oxidation reaction; (b) SEM surface morphology of a nanoporous Al2O3 surface with
measurement of nanopores size; (c) Cross section of an oxidized aluminum alloy surface with a layer thickness of 14.2 mm;
(d) Cross section of an oxidized aluminum alloy surface with a layer thickness of 26 mm.

X-ray diffraction method (Dron-3 equipment) was used in three different oxide layer thicknesses were connected to a
order to evaluate the structural characterization of aluminium copper wire and then insulated with epoxy resin to obtain an
oxide nanoporous layers obtained by anodic oxidation. active surface on each sample of 1.6 cm2. The experiment was
The XRD method was used to identify the phases of the performed four times in order to verify de reproducibility of
nanoporous layers of aluminum oxide compared to the pha- the experimental data.
ses of the untreated alloy. XRD diffractograms were recorded The physical-chemical parameters of the used solution for
using a Molybdenum anode (Mo, lKa ¼ 0.71073  A) at a voltage evaluation of anticorrosive properties of nanoporous
of 35 KV and a current of 20 mA, in a range between 10 and 90 aluminum oxide layers are presented in Table 1.
with a step of 0.05 /s, and then were analyzed using the The experimental protocol used to evaluate the corrosion
computer program MATCH 3 connected to the Crystallog- resistance consisted of the following electrochemical
raphy Open Database. methods:
The evaluation of the anticorrosive properties by electro-
chemical methods of untreated or electrochemically treated - Free potential assessment or open circuit potential (OCP)
aluminum surfaces is performed in 150 mL 3.5% NaCl solution for a period of 17 h;
(which simulates the aggressiveness of the marine - Electrochemical impedance spectroscopy (EIS) curves
environment). versus free potential, in the frequency range: 105 Hz -
The electrochemical cell used to evaluate the anticorrosive 10 mHz, by imposing a sinusoidal signal with an amplitude
performances of the nanoporous layers of aluminum oxide of 10 mV and 10 points per decade were recorded;
obtained is composed of an inert glass container, an auxiliary
electrode a PteRh network, the reference electrode Ag/AgCl
(saturated KCl, þ199 mV vs. NHE) and the working electrode
consisting of untreated Al1050 samples and anodically
oxidized samples at various parameters. The electrochemical Table 1 e Physical-chemical parameters of the 3.5% NaCl
solution used in the corrosion tests.
cell was connected to a VoltaLab PGZ 301 electrochemical
station controlled by Voltamaster 4.0 software. pH Salinity [ppt] Conductivity [mS/cm]
Both untreated Al1050 samples and anodically oxidized 5.75 ± 0.5 25 ± 0.1 39.8 ± 0.3
Al1050 samples at 21 V and three oxidation times, having
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The evaluation of the free potential and the electro- Table 2 shows the average values of the thicknesses of the
chemical impedance spectroscopy curves, being non- nanoporous layers of aluminum oxide obtained by anodic
destructive methods, were determined on the same sample oxidation in a 1 M H2SO4 electrolyte in which 1 g/L Al2(SO4)2-
of unoxidized or anodically oxidized Al1050 alloy.
18H2O was added, varying the times imposed in the elec-
The determination of the electrochemical impedance trochemical processes at the imposed potential of 21 V.
spectroscopy curves are performed 17 h after immersion in Table 2 shows a trend of increasing the thickness of the
the 3.5% NaCl solution, during which the steady state of the nanoporous layers of aluminum oxide simultaneously with
tested surface in the electrochemical cell is reached. the increase of the duration of the anodic oxidation process.
The recorded experimental data were processed using the
specialized software Zview 3.4f which allow fitting the 3.2. SEM surface morphology and layer thicknesses
experimental data to an electrical equivalent circuit model.
The quality of the fittings is evaluated using the chi-square SEM micrographs of unoxidized 1050 aluminum alloy and
element (chi2), whose value is less than 103, confirming the anodically oxidized sample surfaces at room temperature
validity of the equivalent electrical circuit used. (~25  C) at 21 V and a duration of 25 min, 35 min and 45 min are
shown in Fig. 2(aeh). It can be seen from Fig. 2(a) that the
native layer of aluminum oxide covering the analyzed sample
3. Results and discussion is uneven and has pits with a random distribution and which
may represent locations for the development of nanopores
3.1. Obtaining aluminum oxide layers by anodic during the anodic oxidation process.
oxidation As can be seen from these Figures, the morphologies of the
anodic oxidized surfaces are influenced by the variation of the
The purpose of the anodic oxidation process is to form a duration of the anodic oxidation process and differ greatly
nanoporous layer of aluminum oxide on the surface of the from the morphology of the untreated surface shown below in
1050 aluminum alloy so that the surface properties are much Fig. 3.
improved. During the anodic oxidation process, under the Fig. 2(c) shows the SEM micrograph of the surface of the
influence of electric charge, the aluminum substrate is sub- nanoporous layer of aluminum oxide obtained at the potential
jected to an oxidation process and simultaneously there is an of 21 V with a duration of the oxidation process of 25 min and a
increase in the nanoporous layer of aluminum oxide on the layer thickness of 16 mm. On the analyzed surface can be
substrate surface, like a top-down nanotechnology. observed the formation of a large number of pores, which
The formation of nanoporous layers of aluminum oxide is have an uneven distribution and their walls have the largest
observed when the applied potential is around 21 V and the thickness. Also visible are some defects, which due to the
duration of the anodic oxidation process varies between 25 short duration of the anodic oxidation process have not been
and 45 min. Too short an oxidation duration and/or too low a removed.
potential causes an electrochemical polishing phenomenon Increasing the duration of the anodic oxidation process
and a too high-imposed potential causes a dissolution of the from 25 min to 35 min and the thickness of the oxide layer to
Al1050 substrate. The nanoporous layers of aluminum oxide 25 mm, Fig. 2(e), leads to a decrease in the number of defects on
are analyzed using the scanning electron microscope in cross the surface of the nanoporous layer of aluminum oxide ob-
section in order to be able to observe the influence of the tained. In addition, the density and diameter of the nanopores
anodic oxidation time on their thickness. In order to deter- increased, keeping the same uneven distribution.
mine the average thickness of the nanoporous layers of The increase of oxidation time up to 45 min in the condi-
aluminum oxide, at least three measurements were per- tion of maintaining the other constant parameters, de-
formed, in different areas, on the surface of the cross section termines the obtaining of a surface with a very small number
observed in the SEM micrographs, thus calculating an average of defects, but with a very high porosity according to Fig. 2(g).
thickness of the obtained layers. In addition, nanopores formed during the process of anodic
oxidation at a potential of 21 V and a duration of 45 min of the
anodic oxidation process, have the most regular shape and the
Table 2 e Layer thicknesses determined from SEM uniform distribution of nanopores.
micrographs in cross section. The same trend of decreasing the number of defects on the
analyzed surfaces with increasing period of the anodic
Surface type Parameters of anodic Layer thickness
oxidation [mm] oxidation process was observed by other authors [21] who
analyzed the influence of the oxidation process on the nano-
Potential Time
[V] [minutes] porous layers of aluminum oxide formed on the surface of
pure aluminum in 0.3 M oxalic acid solution.
Untreated e e e
From Fig. 2(d), (f) and (h) it can be seen that an increase in
Al1050
Al1050eAl2O3 21 25 16 ± 0.8
the duration of the anodic oxidation process produces an in-
layer crease in the thickness of the nanoporous layer of aluminum
Al1050eAl2O3 21 35 25 ± 1.22 oxide. Thus increasing the duration of the anodic oxidation
layer process from 25 min, Fig. 2(d) to 35 min, Fig. 2(d) and 45 min
Al1050eAl2O3 21 45 32 ± 1.56 Fig. 2(h) causes an increase in the aluminum oxide layer from
layer
16 mm to 25 mm and 32 mm, respectively.
2640 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7

Fig. 2 e SEM analysis of untreated Al1050 alloy surface: (a) surface morphology; (b) cross section on native oxide layer, (c)
surface morphology and (d) cross section on Al2O3 layer obtained at 21 V and 25 min of anodic oxidation process, (e) surface
morphology and (f) cross section on Al2O3 layer obtained at 21 V and 35 min of anodic oxidation process and (g) surface
morphology and (h) cross section on Al2O3 layer obtained at 21 V and 45 min of anodic oxidation process.

3.3. Nanopores size and SEM-EDX composition percentage for the aluminum element, which confirms the
formation of the nanoporous layer of aluminum oxide on the
SEM e EDX analyzes were performed on the entire surface of surface of the 1050 aluminum alloy.
the samples of untreated Al1050 alloy, Fig. 3(aec), and anod- Fig. 3(del) show that the mass percentage of the oxygen
ized oxidized aluminum alloy as well as the measurement of element proves an increasing trend with increasing duration
the nanopore size for the aluminum oxide layers as shown in of the anodic oxidation process. The mass percentages of the
Fig. 3(del) so as to obtain an overview of the chemical aluminum element show a stationary trend simultaneously
composition of nanoporous layers of aluminum oxide. with the increase of the duration of the anodic oxidation
From the SEM e EDX analyzes on the untreated alloy, process.
Fig. 3(aec), and the nanoporous layers of aluminum oxide, Fig. 3(f), (i) and (l) show the SEM micrographs recorded on
Fig. 3(del), aluminum and oxygen are identified as main the surfaces of the nanoporous layers of aluminum oxide
elements. obtained at a potential of 21 V for a duration of the electro-
The analysis of the SEM e EDX spectrum corresponding to chemical process between 25 min and 45 min. The increase of
the surface of the unoxidized 1050 aluminum alloy, presented the durations of the anodic oxidation processes implies an
in Fig. 3(aec) show that aluminum is the majority element, increase of the nanopores density in the aluminum oxide
having a mass percentage of 89.28%. In addition, for the oxy- layers but also a decrease in their diameter.
gen element a much lower mass percentage is determined, If for the surface of the nanoporous layer of aluminum oxide
with a value of 10.72%, proving that aluminum alloy is spon- obtained at a duration of 25 min of the anodic oxidation process
taneously oxidized in air having a very thin oxide layer. the formed nanopores are unevenly distributed and their di-
The SEM e EDX spectra and the mass percentages corre- ameters have values between 17.8 nm and 23.8 nm, Fig. 3(f), by
sponding to the elements identified for the nanoporous layers increasing the duration of the anodic oxidation process causes
of aluminum oxide are shown in Fig. 3(del). These were ob- an increase in the nanopores density on the oxidised surfaces
tained by applying a constant potential of 21 V and varying the of the aluminum alloy and the formed nanopores have di-
duration of the anodic oxidation process from 25 min to ameters between 22 nm and 47 nm for 35 min of oxidation time,
35 min and 45 min, respectively. Fig. 3(i), respectively between 24.3 nm and 38.9 nm for dura-
The comparative analysis of the SEM - EDX spectra in tions of anodic oxidation processes of 45 min, Fig. 3(l).
Fig. 3(ael) demonstrates an increase in the mass percentage The increase of the duration of the anodic oxidation pro-
for the oxygen element compared to the mass percentage of cess induces the appearance of the self-ordering phenomenon
the unoxidized Al1050 surface shown in the SEM - EDX spec- of the nanopores distribution as well as a smaller variation of
trum in Fig. 3 (aec). There is also a decrease in mass their diameters.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7 2641

Fig. 3 e SEM-EDX analysis of untreated Al1050 alloy surface: (a) EDX spectrum; (b) EDX elemental analysis; (c) surface
micrograph, analysis of Al2O3 nanoporous layer formed on Al1050 alloy surface by anodic oxidation at 21 V and 25 min,
having 16 mm thicknesses: (d) EDX spectrum; (e) EDX elemental analysis; (f) surface micrograph with nanopores size, (g) EDX
spectrum; (h) EDX elemental analysis; (i) surface micrograph with nanopores size of Al2O3 nanoporous layer formed on
Al1050 alloy surface by anodic oxidation at 21 V and 35 min, having 25 mm thicknesses and analysis of Al2O3 nanoporous
layer formed on Al1050 alloy surface by anodic oxidation at 21 V and 45 min, having 32 mm thicknesses: (j) EDX spectrum; (k)
EDX elemental analysis; (l) surface micrographic with nanopores size.

Establishing the potential imposed in the anodic oxidation The XRD diffraction spectra recorded for anodically
processes at 21 V together with a duration of the anodic oxidized surfaces at 21 V for a duration of 25 min, 35 min and
oxidation process of 25e45 min induces an ordering of the 45 min, having the layer thicknesses of 16, 25 and 32 mm
nanopores as well as a decrease in their diameter. respectively are shown in Fig. 4(2e4).
From these Figures it is observed that the peaks corre-
3.4. Structural aspects of nanoporous Al2O3 layers sponding to Al2O3 layers are identified also as to a-Al2O3 and to
g-Al2O3 having 2q positions similar to those recorded for the
Fig. 4 shows the XRD diffraction patterns recorded for the unoxidized Al1050 surface, Fig. 4(1), but with different
untreated Al1050 surface. From the analysis of the XRD intensities.
diffraction patterns exposed in Fig. 4(1) were identified 2 peaks Thus, for the 16 mm aluminum oxide layer, Fig. 4(2), the
(maximum) of high intensity diffraction corresponding to intensities of the peaks corresponding to a-Al2O3 from 2q
metallic aluminum (2q ¼ 28.51 and 2q ¼ 33.58 ), according to equal to 29.82 increase, those corresponding to 2q of 25.4
the COD pdf standard. no. 96-150-2690. 62.25 , 71.35 decrease and similar intensity has the peak from
Also on the untreated Al1050 diffraction, patterns were 2q equal with 44.8 as compared with diffraction patterns of
observed several peaks corresponding to the a-Al2O3 untreated Al1050 alloy. On the same 16 mm aluminum oxide
aluminum oxide (according to the standard COD pdf. No. 96- layer the peaks corresponding to g-Al2O3 from 2q equal to
100-0033) and g-Al2O3 aluminum oxide (according to the 20.17 , 17.87 , 46.35 and 59.5 are increasing, while the peaks
standard COD pdf. No. 96-201-5531). The peaks corresponding corresponding to 2q equal to 38.8 , 50.75 and 55.95 are
to a-Al2O3 are identified at 2q values of 29.82 , 25.4 , 44.8 , decreasing as compared with diffraction patterns of unoxi-
62.25 and 71.35 , while the peaks corresponding to g-Al2O3 dized Al1050 alloy.
are identified at 2q values of 20.17 , 17.87 , 38.8 , 46.35 , 50.75 , The same trend of increasing or decreasing of aluminum
55.95 and 59.5 . The aluminum oxide is formed on the surface oxide peaks intensities is also observed for the layer thick-
of the Al1050 substrate during the process of surface prepa- nesses of 25 and 32 mm, Fig. 4 (3e4) for a-Al2O3 as well as for g-
ration, cleaning and drying, knowing very well that aluminum Al2O3.
oxidizes almost instantly in air.
2642 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7

Fig. 4 e XRD diffraction patterns of: (1) untreated Al1050 alloy; (2) Al2O3 layer having 16 mm thickness; (3) Al2O3 layer having
25 mm thickness; (4) Al2O3 layer having 32 mm thickness.

The peaks related to metallic aluminum show a decrease in potential over time or a slowing down of the material-
intensity for all aluminum oxide layers from 16 to 32 mm, the electrolyte interaction, which manifests itself with a poten-
most decreasing being for aluminum oxide layer having 32 mm tial at more electropositive values as compared to the poten-
thickness. tial of the alloy without passive film.
The increase in the intensity of the peaks related to the The monitoring of the open circuit potential was the first
aluminum oxide confirms the formation on the Al1050 alloy electrochemical method initiated after the immersion of the
surface subjected to the anodic oxidation process of some samples subjected to corrosion tests, in order to observe the
nanoporous aluminum oxide layers. interaction of the aluminum alloy and the nanoporous layers
Other authors [22] who analyzed the XRD diffraction pat- of aluminum oxide with the corrosive 3.5% NaCl solution. The
terns recorded for anodically oxidized aluminum surfaces duration of monitoring the open circuit or free potential is
(96% purity) at 20 V and 30 V in 10% oxalic acid found that the 17 h, in order to reach stable values (steady state value).
peaks with the highest intensity correspond to metallic Fig. 5 shows the open circuit potentials recorded after im-
aluminum and the aluminum oxide is mostly amorphous. mersion in 3.5% NaCl solution for 17 h of untreated Al1050
Other authors [23,24] also observed that the main three samples and nanoporous Al2O3 layers obtained by the anodic
phases of the aluminum oxide layers obtained by anodic oxidation process at a potential of 21 V at a duration of 25 min,
oxidation are Al2O3 phases a, g and amorphous phase. The "a" 35 min and 45 min, respectively, having 16, 25 and 32 mm layer
phase of aluminum oxide is actually present in the native thicknesses.
aluminum oxide that forms on the surface of aluminum such It can be seen that the nanoporous layers of aluminum
as corundum, while the "g" phase and the amorphous phase oxide have more positive values of the free potentials, curves
are obtained by the oxidation process [23,24]. Given the re- (2)e(4) from Fig. 5, regardless of the thickness of the oxide
ported results, we can say that the Al2O3 layers obtained in films respectively the parameters imposed in the anodic
this study can be considered a mixture of amorphous Al2O3, oxidation processes, compared to the value of the free po-
"a" and "g". tential recorded for the surface of untreated Al1050, curve (1)
from Fig. 5.
3.5. Anticorrosive properties of Al2O3 layers For the untreated Al1050 aluminum sample subjected to
corrosion tests, a stabilization of the free potential is observed
3.5.1. Evolution of open circuit potential around 700 mV vs. Ag/AgCl, saturated KCl, due to the
Free potential or open circuit potential is an electrochemical penetration of the thin oxide layer by chloride ions and the
method that provides information about the corrosion change of the pH of the electrolyte near its surface [25].
behavior of a material after its immersion in a corrosive so- The analysis of the evolution of the values recorded for the
lution, indicating the tendency of its interaction with the open-circuit potentials related to the nanoporous layers of
corrosive environment. aluminum oxide shows a stabilization of the free potentials
The evolution of the free potential over time provides in- after approximately 300 min after immersion, regardless of
formation about the interactions at the material-electrolyte the parameters used in the production process or the thick-
interface such as oxidation of the material and the forma- ness of the aluminum oxide layers, Fig. 5(2e4). The more
tion of a passive layer that provides a stabilization of the free difficult stabilization of the potential can be caused by the
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7 2643

Fig. 5 e Time evolution of open circuit potential for: (1) untreated Al1050 alloy; (2) Al2O3 layer having 16 mm thickness; (3)
Al2O3 layer having 25 mm thickness; (4) Al2O3 layer having 32 mm thickness.

infiltration of the electrolyte through the nanoporous layers of impedance spectroscopy maintains the steady state at the
aluminum oxide, which causes heterogeneous reactions, in level of the electrochemical cell and by applying a small, dis-
the presence of chloride ions in the electrolyte, due to the turbing signal it is observed how the steady state is affected
morphology, structure and uneven composition of the nano- and especially how it returns to the initial state.
porous layers. In general, a low frequency disturbing signal is applied to
After approximately 300 min after immersion, the values of the steady state electrode potential and a response is recorded
the free potentials in open circuit corresponding to the in the form of a frequency dependent electric current. If the
nanoporous layers of aluminum oxide stabilize, confirming time-dependent disturbing signal is in the form:
that a passive layer of aluminum oxide has formed on the
Et ¼ E0 sinðutÞ (1)
analyzed surfaces that protects them from the action of
aggressive chloride ions in the electrolyte. The recorded response is in the form:
From Fig. 5 (curves 2e4) it can be seen also that an increase
in the duration of the oxidation process or oxide layer thick- It ¼ I0 sinðut þ 4Þ (2)
ness causes a decrease in the values of the free potential where:
values of the nanoporous layers of aluminum oxide. Et ¼ potential at time t;
Increasing the duration of the anodic oxidation process from E0 ¼ the amplitude of the disturbing signal at time t0;
25 min to 35 min and layer thickness from 16 to 25 mm causes a u ¼ angular frequency, defined as the number of vibrations
decrease in the stationary value of the free potential from per unit time (frequency f, Hz) multiplied with 2p (radiani/
450 mV vs. Ag/AgCl to 510 mV vs. Ag/AgCl, both with a second), u ¼ 2pf ;
downward trend. An increase in the duration of the anodic It ¼ current to time t;
oxidation process up to 45 min and layer thickness to 32 mm, I0 ¼ current amplitude at time t0;
determines an even greater decrease of the free potential, up 4 ¼ phase angle.
to a value of 555 mV vs. Ag/AgCl. The decrease of the free Applying Ohm's law for a potential with a sinusoidal fre-
potential values simultaneously with the increase of the quency, time-dependent, polarization resistance or imped-
anodic oxidation processes is due to the increase of the ance can be calculated using the formula [27]:
porosity of the obtained surfaces (Fig. 3 (del)), which allows
the electrolyte to penetrate inside the pores and facilitates the Et E0 sinðutÞ
Z¼ ¼ (3)
interaction of aggressive chloride ions with the nanopore It I0 sinðut þ 4Þ
layer. Among the advantages of the EIS, method can be listed:
performing accurate, reproducible measurements because
3.5.2. Electrochemical impedance spectroscopy the equilibrium state within the electrochemical cell un-
Electrochemical impedance spectroscopy is an electro- dergoes very small changes and a linear dependence can be
chemical method used to obtain complete information about established between the disturbing signal and the response
the kinetics of the processes that take place at the electrode e provided by the system.
electrolyte interface (corrosive medium) [26]. Electrochemical
2644 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7

Fig. 6 e Electrochemical impedance spectroscopy results obtained in NaCl solution for: untreated Al1050 alloy (1) in diagram
(a); nanoporous Al2O3 layers in diagram (b) as follow: (2) Al2O3 layer having 16 mm thickness; (3) Al2O3 layer having 25 mm
thickness; (4) Al2O3 layer having 32 mm thickness. (c) Equivalent circuit used to simulate the EIS data and calculate the
specific resistance (R) for all surfaces.

The representation of the electrochemical impedance potential, they have the shape of a flattened semicircle, the
spectroscopy curves can be done both in the form of a Nyquist impedance can be expressed by the relation:
diagram and in the form of Bode diagrams [28].
1
The Nyquist diagram or the complex representation of the ZC ¼ a (6)
CðjuÞ
EIS curves involves the representation of the real part of the
impedance on the abscissa and the imaginary part of the where a is dependent on the angle of rotation of a pure
impedance on the ordinate. The size of the impedance capacitor in a complex plane.
modulus vector, |Z|, represents the absolute value of the The use of the exponent a has no clear physical explana-
impedance and the angle between the vector |Z| and abscissa tions, mostly being associated with the inhomogeneity of the
represents the change of the phase angle (4). surface of the analyzed material.
Bode diagrams assume the representation of the frequency Depending on the value of a, the impedance can have a
in logarithmic scale on the abscissa and on the ordinate the capacitive character when a ¼ 1, an inductive character when
absolute value of the impedance in logarithmic scale or the a ¼ 1, a resistive character when a ¼ 0 or a diffusive character
phase angle (4). The electrochemical impedance correspond- when a ¼ 0.5. At any other value of a, the impedance is
ing to a subcircuit (ReC) consisting of a polarization resistance expressed by a constant phase element (CPE).
or a charge transfer resistance (R) in parallel with the capac- With the help of specialized software, EIS diagrams can be
itance of the electric double layer at the metal-electrolyte modeled in the form of equivalent electrical circuits. The EIS
interface (C) is expressed by the relation: diagrams are fitted with the help of electrical circuits and thus
the physicalechemical properties of the tested material can
1
ZC ¼ (4) be correlated with various circuit elements (physical ele-
juC
ments), thus extracting the numerical values corresponding to
pffiffiffiffiffiffiffi
where: j ¼ 1, u is angular frequency (u ¼ 2pf, f is frequency them.
ı̂n Hz), C is capacitance of electric double layer expressed by: Fig. 6 shows the impedance spectroscopy diagrams ob-
tained for both the untreated aluminum alloy, Fig. 6(a) and the
1 three layers of aluminum oxide obtained by anodic oxidation,
C¼ (5)
um R Fig. 6(b). The electrochemical impedance spectroscopy data
where: um ¼ the resonant frequency at the maximum value of are presented in Nyquist form. In Fig. 6(c) the equivalent
the Zreal axis and R is the intersection between the impedance electrical circuit used for modeling and fitting the obtained
diagram and the Zreal axis. impedance data is presented. The same system of represen-
Due to the fact that electrochemical impedance diagrams tation of EIS diagrams was maintained the experimental re-
for corrosion processes are measured at the corrosion sults were represented by means of symbols, and the results
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7 2645

tests can be deduced by extrapolating the arc to the inter-

Table 3 e The values of the elements of the equivalent
section with the abscissa or by fitting the experimental results
circuit used for fitting the experimental data
corresponding to the unoxidized aluminum alloy and the using the electrical equivalent circuit.
anodic oxidized surfaces to a potential of 21 V having the Thus, from Fig. 6(c) it can be seen that Rs is the resistance of
layer thicknesses of 16, 25 and 32 mm. the solution, R1 and CPE1 represent the polarization resistance
Elements of Untreated Al2O3 thickness [mm] or specific resistance and the corresponding constant phase
electrical Al1050 element related to the aluminum oxide on the unoxidized
16 25 32
equivalent circuit alloy or the nanoporous layer on the oxide layers obtained by
Rs [U ] 11.2 13.2 16.2 16.2 anodic oxidation. R2 and CPE2 represent the polarization
R1 (oxide) [U cm2] 56000 4.8E8 2.9E9 9.9E9 resistance and the constant phase element related to the
CPE1 [F cm2] 5.46 E-6 5.9 E-7 6.96E7 4.96 E-7 aluminum alloy under the thin oxide layer or at the base of the
a1 0.865 0.964 0.955 0.955 nanopores. The total resistance of studied surface is the sum
R2 [U cm2] bulk 4800 4800 4800 4800
of R1þR2.
CPE2 [F cm2] 5.6E5 5.6 E-5 8.6 E-5 5.6 E-5
The EIS diagram in the Nyquist representation of the
a2 0.86 0.98 0.94 0.99
Chi2 1.037E4 1.5666E4 1.5123 E-4 1.741 E-4 unoxidized Al1050 surface, Fig. 6 (1) has the shape of a circular
arc, with a low height, which confirms a much lower corrosion
resistance compared to the corrosion resistance of anodically
obtained by fitting with the help of equivalent electrical cir- oxidized surfaces. The values of the elements in the electrical
cuits are represented by means of continuous lines. equivalent circuit are presented in Table 3. The fitting of the
From Fig. 6 it can be seen that the shape of the EIS diagrams EIS diagram corresponding to the surface of unoxidized
for the nanoporous layers of aluminum oxide is that of cir- Al1050 resulted in a resistance value of 60.800 kU cm2.
cular arcs having an almost capacitive character and whose Table 3 shows that for the 16 mm thickness of the anodi-
height increases with increasing duration of the anodic cally oxidized layer the specific resistance has a value of
oxidation process. The only impedance diagram that in the 4.800048 E8 kohm cm2, being much higher as compared to the
Nyquist representation forms a complete semicircle, inter- value of the polarization resistance determined for the surface
secting the Zreal axis is the one obtained for the unoxidized of the unoxidized alloy of 60.800 kU cm2. The increase of the
Al1050 alloy. duration of the anodic oxidation process and therefore of the
The experimental data of electrochemical impedance thickness of the nanoporous aluminum oxide layers at 25 mm
spectroscopy are fitted using the equivalent circuit in Fig. 6(c) and 32 mm respectively determines the obtaining of increased
and the values determined for the elements of the equivalent values of the specific resistances, at 2.9000048 E9 kU cm2
electrical circuit are shown in Table 3. respectively 9.9000048 E9 kU cm2.
The polarization resistance (when the circle seems to The impedance modulus values at low frequencies can be
intersect the Zreal axis) or the specific resistance (when the arc ascribed to processes occurring on the aluminum alloy/elec-
does not intersect Zreal) of the surfaces subjected to corrosion trolyte interface or nanoporous Al2O3/electrolyte interface

Fig. 7 e The low-frequency impedance modulus (at 0.01 Hz) obtained in NaCl solution for different samples: (1) untreated
Al1050 alloy; (2) Al2O3 layer having 16 mm thickness; (3) Al2O3 layer having 25 mm thickness; (4) Al2O3 layer having 32 mm
thickness.
2646 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7

where corrosion occurs [29e33] and can be used as effective oxide, the free potential presents nobler values, only that they
tool for determining the corrosion resistance properties of the present a downward trend with increasing duration imposed
investigated system material/electrolyte [34]. in the anodic oxidation process.
The values of the low-frequency impedance modulus, Fig. 7, The method of electrochemical impedance spectroscopy
of the untreated Al1050 alloy and aluminum oxide layers show showed that the thickness of the oxide layer and therefore the
the increased anticorrosive properties of nanoporous Al2O3 time required in the anodic oxidation process influences the
layers, having thicknesses of 16, 25 and 32 mm. So if impedance anticorrosive properties of the nanoporous layers of
modulus, Z0.01Hz of untreated Al1050 alloy is around aluminum oxide obtained.
77.859 kU cm2 it increases at 27323 kU cm2 for Al2O3 16 mm With the increase of the duration of the anodic oxidation
thickness, at 29227 kU cm2 for Al2O3 25 mm thickness and at process to constant potential, the specific resistances ob-
highest value of 34834 kU cm2 for Al2O3 32 mm thickness. tained by fitting the experimental data with the help of
Based on all the presented results for anticorrosive prop- equivalent electrical circuits, corresponding to the nano-
erties of investigate surfaces, it can be concluded that porous layers of aluminum oxide show an ascending trend.
aluminum oxide layers obtained by anodic oxidation could be The impedance modulus values at low frequencies,
beneficial in the corrosion protection of Al1050 alloy, Z0.01Hz, extracted from electrochemical impedance spectros-
increasing the corrosion resistance several times. copy results confirm the beneficial anticorrosive properties
obtained for nanoporous aluminum oxide layers anodically
growth on Al1050 surface.
4. Conclusions Based on all the presented results for SEM-EDX, XRD
diffraction patterns and anticorrosive properties of the
The surfaces of the nanoporous layers of aluminum oxide investigated surfaces, it can be concluded that aluminum
obtained through the anodic oxidation process, in 1 M H2SO4 oxide layers obtained by anodic oxidation could be beneficial
in which 1 g/L Al2(SO4)3
18H2O is added, at the parameters in the corrosion protection of Al1050 alloy, increasing the
imposed by 21 V and three different times show porosity corrosion resistance several times.
evenly distributed with the size of the nanopores depending
on the anodic oxidation time.
The morphology of the nanoporous layers of aluminum Credit authorship contribution statement
oxide obtained by anodic oxidation has changed compared to
the morphology of the unoxidized aluminum alloy. An in- Lidia Benea: Conceptualization, Methodology, Software Nic-
crease in the duration of the oxidation process to constant oleta Bogatu.: Data curation, Writing- Original draft prepara-
potential and therefore an increase in the thicknesses of the tion. Lidia Benea and Nicoleta Bogatu: Visualization,
nanoporous layers of aluminum oxide leads to obtaining more Investigation. Lidia Benea: Supervision.: Lidia Benea: Soft-
uniform layers. ware, Validation.: Nicoleta Bogatu Roxana Chiriac and Lidia
The thickness of the aluminum oxide layers increases with Benea: Writing- Reviewing and Editing.
increasing anodic oxidation time imposed at a constant
oxidation potential.
From the analysis of the mass percentages of the elements Declaration of Competing Interest
determined by the SEM-EDX spectra for the unoxidized alloy
and the anodically oxidized surfaces, an increase of the mass The authors declare that they have no known competing
percentage is observed for the oxygen element and for financial interests or personal relationships that could have
aluminum element a decrease of the mass percentage. appeared to influence the work reported in this paper.
Analysis of XRD diffraction patterns reveals an increase in
the intensity of some peaks corresponding to the aluminum
oxide as a-Al2O3 and g-Al2O3 at the same time as a decrease in
Acknowledgments
the intensity of the metallic aluminum peaks for the nano-
porous layers of aluminum oxide compared to the unoxidized
All the experimental work was performed at Competences
Al1050 surface. The oxidized nanoporous layer seems to be a
Center Interfaces - Tribocorrosion and Electrochemical Sys-
mixture of a-Al2O3, g-Al2O3 and an amorphous phase.
tems (CC-ITES) laboratories Applied Electrochemistry for Ma-
The anticorrosive properties of the nanoporous layers of
terials and Environmental Science and Engineering
aluminum oxide are evaluated in comparison with the surface
(LEASIMM), Electrochemistry and Corrosion from Dunarea de
of the unmodified alloy.
Jos University of Galati. The authors would like to express
From the analysis of the diagrams in which the evolution of
appreciation for Prof. Jean-Pierre Celis from Katholieke Uni-
the free potentials in time is presented, both for the unoxi-
versity of Leuven, Belgium and Prof. Pierre Ponthiaux from
dized Al1050 surface and for the anodically oxidized surfaces,
Ecole Centrale Paris, France for they valuable scientific advice.
it is observed that for the nanoporous layers of aluminum
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 7 : 2 6 3 6 e2 6 4 7 2647

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