j m a t e r r e s t e c h n o l .

2 0 2 0;9(x x):8766–8779

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Original Article

Corrosion performance of plasma electrolytic

oxidation grown oxide coating on pure aluminum:
effect of borax concentration

Getinet Asrat Mengesha a,b , Jinn P. Chu a , Bih-Show Lou c,d , Jyh-Wei Lee b,e,f,g,∗
a Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taiwan
b Department of Materials Engineering, Ming Chi University of Technology, New Taipei City, Taiwan
c Chemistry Division, Center for General Education, Chang Gung University, Taoyuan, Taiwan
d Department of Nuclear Medicine and Molecular Imaging Center, Chang Gung Memorial Hospital, Taoyuan, Taiwan
e Center for Plasma and Thin Film Technologies, Ming Chi University of Technology, New Taipei City, Taiwan
f Department of Mechanical Engineering, Chang Gung University, Taoyuan, Taiwan
g Plastic and Reconstructive Surgery, and Craniofacial Research Center, Chang Gung Memorial Hospital, Taoyuan, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: Plasma electrolytic oxidation (PEO) is a widely applied surface treatment method which can
Received 2 April 2020 improve the corrosion resistance of valve metals and their alloys. In this study, PEO treat-
Accepted 6 June 2020 ment was conducted on pure Al using a power supply under a bipolar pulsed mode at fixed
duty cycle and frequency. The effect of different concentrations of borax in the electrolyte on
the corrosion resistance of PEO grown oxide coatings in 3.5 wt% NaCl solution was compre-
Keywords: hensively studied by a potentiodynamic polarization test and electrochemical impedance
Plasma electrolytic oxidation spectroscopy method. We found that the average pore size and porosity on the PEO grown
Pure aluminum oxide coating decreased with increasing borax concentration. The dense microstructure of
Borax oxide coating can be seen when the borax concentration in the electrolyte was high. The
Corrosion resistance corrosion resistance of PEO coating increased with increasing borax content. The corrosion
Potentiodynamic polarization resistance of pure Al was greatly improved up to 23,058 times higher by the formation of a
Electrochemical impedance PEO layer treated in the electrolyte containing 6 g L−1 borax due to its ability to grow a dense
spectroscopy ␥-Al2 O3 phase with less defects.
© 2020 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/).

∗
Corresponding author.
E-mails: getgetuw@gmail.com (G.A. Mengesha), jpchu@mail.ntust.edu.tw (J.P. Chu), blou@mail.cgu.edu.tw (B. Lou),
jefflee@mail.mcut.edu.tw (J. Lee).
https://doi.org/10.1016/j.jmrt.2020.06.020
2238-7854/© 2020 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 m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779
1. Introduction
Plasma electrolytic oxidation (PEO) is a surface modification
method that has been applied on aluminum, magnesium,
titanium, zirconium and their alloys for producing particu-
lar metal oxide coatings with improved corrosion and wear
resistance [1–4]. PEO process can produce the electrochemical
and plasma chemical reactions on the substrate materi-
als immersed in the electrolyte [5,6]. One of the promising
benefits of PEO technique is the opportunity of achieving
desired coating properties through modifying the process-
ing conditions and electrolyte compositions, and organic and
inorganic nanoparticle additives, such as ZrO2 , SiO2, Al2 O3 ,
TiO2, Si3 N4 [7–12]. Meanwhile, PEO surface treating process
is an eco-friendly, economical and more convenient surface
engineering technique [13].
PEO treatment can be applied to aluminum which yields
an oxide ceramic layer over the aluminum surface. Several
PEO processing parameters such as, chemical compositions
of electrolyte, current density, waveforms of voltage and cur-
rent, process time, and substrate composition can influence
the micro-discharge behavior as well as the microstructure of
oxide layer [14–19]. Among these parameters, chemical com-
positions of electrolyte have a significant influence on the
breakdown voltage, discharge characteristics, electrochemical
reactions, which can further affect the surface morphol-
ogy, phase, and layer thickness of PEO coatings and their
corresponding corrosion resistance and anti-wear behaviors
[20–22].
The setup of voltage, current parameters, and electrolyte
compositions can affect the dissolution of metal and their-
oxides, melting of compounds, and oxide formations during
the process of PEO treatment of Al and its alloys [23]. Using a
power supply with a pulsed bipolar mode for PEO produces a
uniform coating thickness, fewer defects and a more compact
structure as compared to coatings formed by direct current
(DC) mode and pulsed unipolar mode [24–27]. Hussein et al.
[26] reported that altering the setup of the current mode of
PEO from unipolar to bipolar mode improved the corrosion
resistance of PEO coating due to the reduction of strong plasma
discharge events.
In the PEO process, discharge characteristics and oxide
formation are mainly controlled by the electrolyte contents
and their concentrations [28–32]. Becerik et al. [33] reported
that properly increased the concentration of Na2 SiO3 in the
electrolyte can efficiently improve the corrosion resistance
of 6060 aluminum alloy. In other work, the corrosion resis-
tance of magnesium alloy was enhanced by increasing the
concentration of Na2 SiO3 [34,35] and NaAl2 O4 [14] in the elec-
trolyte solution. The phase compositions, morphologies, and
corrosion resistance of the PEO coatings on Al alloys were
affected by altering the concentration of Na2 WO4 [36]. As
compared to other electrolytes, borax (Na2B4O7 ·10H2O), an
environmentally stable substance, has been widely used in
metallurgy, glass and non-ferrous metal making and ceramic
industries [37,38]. Due to the promoting growth of oxide
film by the fast decomposing of B4 O7 2− and providing oxy-
gen to metal, borax has been adopted in the electrolyte for
the PEO of magnesium alloy [39]. Zhang et al. [40] studied
8767
the corrosion resistance of PEO coating on AZ91HP mag-
nesium alloy by adding different concentrations of sodium
borate in the electrolyte solution. However, no improve-
ment in corrosion resistance was observed [40]. Although
the effect of borax addition in PEO electrolyte has been
reported [41,42], the influence of borax concentrations on the
anti-corrosion properties of pure aluminum and its alloys
is seldom studied. In our previous work [12], the addition
of borax in electrolyte showed positive effect on the cor-
rosion resistance improvement of Al. However, the borax
contents were fixed at 0 and 5 g L−1 and effect of borax
concentration in the electrolyte of PEO treatment on the corro-
sion resistance improvement of Al substrate was not studied
[12].
The usage of aluminum and its alloys covers a wide spec-
trum in recent decades. Automobile and aerospace industries
are the main users of aluminum and its alloys due to their low
density and lightweight for the reduction of fuel consump-
tion [43]. Although different parts of automobiles and aircraft
are made of aluminum alloys, the high corrosion rate and low
wear resistance of Al alloys significantly limit their further
application.
In this study, we employed pure aluminum as substrate
material due to its simple chemical composition, which
reduces the influence of other alloy elements. The PEO coat-
ings on pure aluminum were grown by a bipolar mode power
supply using electrolytes containing different borax concen-
trations at a fixed frequency and duty cycle. As compared
with our previous research [12], the influence of borax concen-
trations on the plasma characteristics, microstructure, layer
thickness and corrosion resistance of PEO grown oxide lay-
ers on pure aluminum were systematically studied in this
work.
2. Materials and methods of PEO coatings
2.1. Preparation of the PEO coatings
The PEO experiments were carried out by using a bipo-
lar pulsed DC power supply (YSTC-600-005HD, Taiwan). The
anode voltage, anode current, cathodic voltage and cathodic
current were set to 600 V, 4 A, 100 V and, 1 A, respectively. The
schematic plot of voltage versus time for bipolar pulsed mode
is depicted in Fig. 1. The process parameters of PEO treat-
ment were fixed at a frequency of 1000 Hz, 25% duty cycle
and deposition time for 5 min. In the PEO treatment, a dimen-
sion of 50 mm × 50 mm × 1 mm of pure aluminum substrate
was employed. The Al plates were ultrasonically cleaned ini-
tially, by using acetone, ethanol and deionized water for 5 min,
respectively. Five different concentrations of borax were added
in the electrolyte, respectively. The PEO electrolyte concentra-
tions, process conditions and specimen designations are listed
in Table 1. In addition, B0 and B6 coatings were PEO treated for
30 and 80 s for understanding the microstructure change at the
short period of time. To stabilize the temperature of electrolyte
during PEO treatment temperature, the water-cooling system
was kept at room temperature. Finally, the PEO treated sam-
ples were again ultrasonically cleaned by deionized water and
dried with warm flowing air.
8768 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779

Table 1 – Process conditions and specimen description of PEO coatings.

Sample designation B0 B1.5 B3 B4.5 B6

Na2 SiO3 ·5H2 O (g L )

-1
7.0
KOH (g L-1 ) 1.0
Electrolyte concentration
Na3 PO4 ·12H2 O (g L-1 ) 5.0
Na2 B4 O7 ·10H2 O (g L-1 ) 0 1.5 3.0 4.5 6.0
Frequency (Hz) 1000
Duty cycle (%) 25
Ton + 250/(250 + 200
(␮s)/(Ton + + Toff + + Ton – + Toff –) + 200 + 350)
(␮s)
Breakdown voltage (V) 416.34 420.53 422.28 423.92 435.79
Time to reach breakdown 25.5 29.5 34.0 39.0 40.0
voltage (s)
Electrolyte conductivity 14.03 ± 0.01 13.32 ± 0.01 12.61 ± 0.02 11.97 ± 0.02 11.38 ± 0.01
(mS/cm)
pH value 12.47 12.36 12.34 12.22 11.98

to investigate the corrosion performance of PEO coating, the

Fig. 1 – Schematic plot of voltage versus time (V–t) for PEO
treatment under bipolar pulsed mode.
potentiodynamic polarization experiments and electrochem-
ical impedance spectroscopy (EIS) in 3.5 wt% NaCl aqueous
solutions were conducted using an electrochemical worksta-
tion (BioLogic, SP-200, France). The corrosion property of pure
aluminum substrate was also studied as a reference. A stan-
dard three-electrode cell arrangement including a saturated
calomel reference electrode (SCE), a platinum plate as counter
electrode and a working electrode of PEO sample were used.
EIS measurement was started after the sample was stabi-
lized at the corrosion potential (Ecorr ) for 6 h immersion. An
AC (alternative current) potential amplitude of 10 mV versus
the Ecorr was used to the working electrode at its corrosion
potential. The impedance spectra were acquired in the fre-
quency range from 100 kHz to 0.01 Hz. The software of BioLogic
was adopted to fit the equivalent electrical circuits from the
impedance data of each EIS test.

3. Results and discussion

2.2. Characterization of PEO coatings 3.1. Voltage–time curve characteristics of coatings

The electrical conductivity of each electrolyte was measured
by a portable electrical conductivity meter (HANNA Instru-
ments HI 991300 pH EC Electrical Conductivity, UK). The pH
value of each electrolyte was measured by the pH meter
(HORIBA pH meter F-71, Japan). The crystal structure of the
coatings was studied by a grazing incidence X-ray diffraction
(GAXRD, PANalytical, X’pert, Holland) operated at 30 kV and
40 mA, by the radiation source of Cu K␣ with an incident angle
of 2◦ . The field emission electron probe microanalyzer (FE-
EPMA, JXA-8500F, JEOL, Japan) was employed to analyze the
elemental compositions of the coatings. Moreover, the oxide
layer thickness, surface and the cross-sectional microstruc-
ture of each PEO coating were studied by a scanning electron
microscope (SEM, S3400N, Hitachi, Japan). The average oxide
layer thickness and standard derivation of each sample were
calculated from twenty measurements. The average pore size
and the percentage of porosity were measured according to
the SEM surface images and calculated by ImageJ software.
The surface roughness of the coatings was measured by a sur-
face profilometer (Surfcorder ET3000, Kosaka, Japan). In order
Fig. 2(a) shows the voltage–time (V–t) characteristic curves for
five PEO treatments using different concentrations of borax
in the electrolyte. The V–t curve showed an initial abrupt
increase of voltage and followed by a quick decrease in the
slope, which represented the onset of micro-discharges on the
aluminum surface. The corresponding voltage is referred to
the breakdown voltage and listed in Table 1. Figs. 2(b) and (c)
represent the enlarged V–t curves of the anodic and cathodic
regions from 10 to 80 s. It can be found that the breakdown
voltage and the corresponding time increased from 416.34 to
435.79 V and from 25.5 to 40 s, respectively, as the concentra-
tion of borax increased from 0 to 6 g L−1 in the electrolyte.
In addition, as shown in Fig. 2(c), the cathodic voltage-time
behavior is also different when different concentrations of
borax were added in electrolyte. The significant difference in
shape and values of the cathodic V–t curves can be found. The
voltage of the PEO process further increased gradually with
time due to the formation of a dense oxide layer after the
breakdown voltage. It has been reported that the breakdown
voltage strongly depends on the compositions and concentra-
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779
Fig. 2 – (a) Voltage-time (V–t) characteristic curve of the PEO process with different concentrations of borax addition in the
electrolyte solution. (b) Enlarged plots of the anodic region of the voltage-time (V–t) characteristic curve. (c) Enlarged plots of
the cathodic region of the voltage–time (V–t) characteristic curve.
tions of electrolyte in the PEO process, which are responsible
for the development of micro sparks on the substrate surface
[44,45]. Dehnavi et al. [46] also discovered that the PEO pro-
cess condition and the substrate material strongly affected
the breakdown voltage values. Ono et al. [47] reported that
a direct relationship was found between the concentration of
phosphoric acid in the electrolyte and the value of breakdown
voltage.
To address the electrolyte conductivity in the PEO process,
it can be found that electrolyte conductivity decreases with
increasing borax concentration as listed in Table 1. The high-
est electrolyte conductivity of 14.03 mS/cm can be seen for
the electrolyte without any borax addition. Whereas, the low-
est electrolyte conductivity of 11.38 mS/cm is obtained for the
electrolyte containing 6 g L−1 of borax. The possible reason for
the lower electrical conductivity of the PEO electrolyte induced
by the addition of borax has been explained by Zhang and
coworkers [40], and Molaei et al. [48]. We believe that the key
point is the ion mobility of OH− , which is much faster than
that of Na+ . Therefore, although the total ion concentration
increased, the electrical conductivity of the PEO electrolyte
still decreased while the OH− concentration was diluted due to
more amount of borax addition. Addition of 1.5 g L−1 borax in
the electrolyte can increase the Na+ and BO2 − ions in the alka-
line electrolyte and thus decreases the pH value from 12.47
8769
(electrolyte without borax, B0) to 12.36 (electrolyte with borax,
B1.5). The value of pH decreased with increasing borax con-
centration. The pH value of the electrolyte containing 6 g L−1
borax addition was 11.98. This decreasing of pH value is related
to the formation of weak acid, HBO2 produced after the addi-
tion of borax in the electrolyte. Bordbar-Khiabani et al. [49]
reported that the pH value of electrolyte reduced from 12.64
to 8.53 by adding boric acid due to the formation result of H+
and BO3 3− ions which disturbed the ionic equilibrium in the
alkaline electrolyte. Based on the data listed in in Table 1, the
breakdown voltage increased with increasing concentration
of borax, whereas, the pH value and electrolyte conductivity
decreased with increasing borax concentration. The decreas-
ing tendency of the electrolyte conductivity and pH value
with the addition of different concentrations of borax in the
electrolyte solution resulted in an increase in the breakdown
voltage. According to the theoretical model of Ikonopisov [44],
the relationship between electrolyte conductivity and break-
down voltage can be presented as follows:
1
VBD = aB + bB log (1)
K
where aB and bB are constant values for a given metal and
electrolyte composition, and VBD and K are breakdown volt-
age and electrolyte conductivity, respectively. Therefore, an
8770 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779
Fig. 3 – XRD patterns of pure aluminum and PEO coatings.
inverse relationship between the electrolyte conductivity and
breakdown voltage was thus obtained in this work.
3.2. Phase and chemical composition analysis
The XRD patterns of untreated pure aluminum and PEO coat-
ings are depicted in Fig. 3. The dominant phase for all PEO
coatings is ␥-Al2 O3 , which has been reported elsewhere [17].
The diffraction peaks of the Al substrate was also found
because of the penetration power of X-rays into the PEO coat-
ings [50]. The chemical compositions of each PEO layer carried
out on the cross-sectional region are listed in Table 2. The
major concentrations of the PEO layer are Al and O imply-
ing the formation of ␥-Al2 O3 phase. However, it is noticeable
that the O/Al ratio for each PEO layer is ranging from 1.6
to 2.0, suggesting that an over-stoichiometric alumina phase
containing more defects was produced on the PEO layer. The
contents of Na, Si, K, P, and B elements are all obtained from
the electrolyte. It is obvious that the boron content of the coat-
ing increased from 0 to 2.04 at.% as the borax concentration
increased from 0 to 6 g L−1 in the electrolyte. On the basis of
XRD results and the chemical composition analysis in Table 2,
we can confirm that there is not any Na, Si, K, P, and B related
crystalline phase observed in Fig. 3 possibly due to the solid
solution effect of these elements in the ␥-Al2 O3 structure.
3.3. Surface morphology analysis of PEO coatings
The surface morphologies of the PEO coatings grown using
different concentrations of borax in the electrolyte are shown
in Fig. 4. The typical pancake-form microstructure consist-
ing of craters and pores are visible, which were produced by
molten oxide and gas bubbles throughout the micro-arc dis-
charge channels in the PEO layer [51,52]. It is also noticeable
that some micro-cracks were formed on the B0 oxide layer,
which was grown without the addition of borax, due to the
thermal stress generated through quick solidification of the
molten oxide by the chilling of cold electrolyte [40,53,54].
To understand the surface microstructural change at differ-
ent PEO treatment time periods, the surface morphologies of
B0 and B6 coatings treated for 30, 80 and 300 s at low and high
magnifications are shown in Figs. 5(a) and (b), respectively.
It has been reported that the porous characteristics strongly
depends on the nature of discharge properties involved in
the PEO mechanism [55]. Comparing the images of B0 and
B6 coatings at early plasma oxidation stage (at 30 s), the large
amount of micropores can be seen on B0, whereas the ran-
domly distributed micropores are observed on B6. For the
coatings treated for 80 s, B6 shows a less porosity, denser and
more compact surface microstructures than that of B0. Finally,
after the PEO treatment for 300 s, the B0 coating exhibits a
surface full of larger size micropores and cracks. Meanwhile,
a surface with less porosity, denser and more compact mor-
phology can be seen for B6 coating. It is obvious that, due to
the absence of borax in B0, the number and size of micropores
quickly increase with increasing PEO treatment time.
The calculated average pore sizes and porosity ratios of PEO
coatings based on the surface morphologies in Fig. 4 are listed
in Table 3. The average pore size and porosity on the PEO coat-
ing decreased with increasing concentration of borax added
in the electrolyte. The lowest average pore size of 0.13 ␮m and
the lowest porosity of 1.34% can be found for B6 coating grown
with the highest borax concentration in the electrolyte. Mean-
while, the largest average pore size of 0.29 ␮m and the highest
porosity of 4.04% are found for the B0 coatings without borax
addition. It has been reported that the addition of borax can
reduce the spark of the micro discharge on PEO coating [40].
The larger sparks on the surface can produce bigger micro-
pores, while shorter sparks can form a smaller amount of
micro-pores with reduced sizes [56,57]. Due to the decreasing
amount of micro discharge sparks during the PEO treatment
by the addition of 6 g L−1 concentration of borax (B6), a more
compact surface microstructure with small pore sizes, fewer
defects and cracks can be observed in our investigation.
In Table 2, the chemical composition analysis of each PEO
layer shows the existence of the boron element in the coating,
indicating the incorporation of borax in the reaction process of
PEO coating. The chemical reaction of borax and metal oxide
in the electrolyte can be expressed as follows
Na2 B4 O7 + MO
= 2NaBO2 + M (BO2 )2 (M represents the metal cation) (2)
The possible reason for the improvement of the PEO reac-
tion is due to the increasing amount of anions. With the
addition of borax in the electrolyte, we observed that the
PEO electrical discharge reaction changes dramatically as
illustrated in Fig. 2. Therefore, the addition of borax in the
electrolyte can significantly affect the surface morphology of
PEO coating [58].
The average surface roughness of PEO coatings are also
listed in Table 3. The surface roughness of the PEO coating
showed an increasing tendency with respect to the concentra-
tion of borax. The PEO coating without the addition of borax
(B0) has an average surface roughness of 0.521 ␮m, while a
high surface roughness of 0.923 ␮m was obtained for the coat-
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779 8771

Table 2 – The chemical compositions of PEO coatings (unit: at.%).

Sample Na Si O K P Al B

B0 0.31 0.94 61.39 0.04 0.57 36.75 0

B1.5 0.53 0.98 60.11 0.12 2.45 35.41 0.39
B3 0.06 0.12 61.78 0.03 6.97 30.16 0.88
B4.5 0.04 0.14 60.72 0.02 6.18 31.59 1.30
B6 0.01 0.14 60.10 0.01 0.02 37.68 2.04

Fig. 4 – Surface morphologies of the PEO coatings grown by different borax concentrations.

Table 3 – Pore size, porosity, surface roughness and oxide layer thickness of PEO coatings.
Sample No. B0 B1.5 B3 B4.5 B6

Pore size (␮m) 0.29 ± 0.03 0.23 ± 0.02 0.21 ± 0.03 0.19 ± 0.03 0.13 ± 0.03
Porosity (%) 4.04 ± 0.03 3.55 ± 0.03 1.73 ± 0.03 1.55 ± 0.02 1.34 ± 0.02
Surface roughness, Ra (␮m) 0.52 ± 0.02 0.61 ± 0.02 0.83 ± 0.03 0.86 ± 0.05 0.92 ± 0.03
Oxide layer thickness (␮m) 2.67 ± 0.12 3.58 ± 0.21 4.40 ± 0.25 3.67 ± 0.22 3.43 ± 0.20

ing grown using the highest borax concentration (B6). With the
addition of borax in the electrolytic solution, the PEO coatings
developed a rough surface [40]. Similar results on the increase
of surface roughness of PEO coating by adding higher concen-
trations of Na3 PO4 [59] and NaAlO2 [60] in electrolytes were
also reported. For the PEO coating using lower concentration of
borax addition, the lower surface roughness was achieved due
to the uniform distribution of discharge channels on surface.
Fig. 6 depicts the cross-sectional morphologies of PEO coat-
ings. Some cracks and large amounts of pores underneath the
PEO layer can be seen for B0, B1.5, and B3 coatings. The cross-
sectional morphology of B6 coating exhibits a relatively dense
microstructure, less microcracks and pores as compared with
other PEO coatings.
The oxide layer thickness of each coating is listed in Table 3.
The PEO layer thickness increased from 2.67 to 4.45 ␮m and
then decreased to 3.43 ␮m as the borax content increased from
0 to 3 g L−1 and then increased to 6 g L−1 . We believe that the
decreased thickness of PEO layers for B4.5 and B6 coatings
is possibly due to the formation of more compact and dense
oxide layers with less amounts of defects. Also, due to lower
electrical conductivity of electrolyte, the oxide layer thickness
of B6 is thinner than the other PEO coatings. Since the previous
investigation suggested that the addition of Na2 B4 O7 in the
electrolyte can lower the electrical conductivity and obtained
a thinner oxide layer [48], similar result is also found in this
work.
3.4. Corrosion resistance evaluation
The potentiodynamic polarization curves of PEO coatings and
untreated pure Al substrate in 3.5% NaCl aqueous solution
are shown in Fig. 7. The polarization resistance (Rp ), corrosion
potential (Ecorr ) and corrosion current density (Icorr ), anodic
Tafel slope (ˇa ) and cathodic Tafel slope (ˇc ) of each sam-
ple obtained from the potentiodynamic polarization curve are
listed in Table 4. It is obvious that the Ecorr values of all PEO
coatings, ranging from −759.567 to −471.097 mV, are higher
than that of the untreated pure Al substrate, −768.931 mV. All
PEO coatings have lower Icorr values. In particular, the high-
est Ecorr of −471.097 mV, the lowest Icorr of 9.00 × 10−11 A cm−2
and the highest Rp of 3.13 × 108 ohm cm2 can be found for B6
8772 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779

Fig. 5 – Surface morphologies of the B0 and B6 coatings grown after 30, 80 and 300 s PEO treating time at (a) low and (b) high
magnifications.

Table 4 – Potentiodynamic polarization analysis results of pure aluminum and PEO treated samples with different
concentrations of borax.
Sample no. Untreated Al B0 B1.5 B3 B4.5 B6

Ecorr (mV) –768.9 –759.6 –729.7 –699.1 –530.2 –471.1

Icorr (A cm-2 ) 1.81 × 10–7 1.80 × 10–8 1.00 × 10–9 4.89 × 10–10 1.80 × 10–10 9.00 × 10–11
ˇa (mV) 36.9 19.8 59.5 146.7 80.2 188.7
ˇc (mV) 90.4 313.3 87.4 172.9 63.9 98.5
Rp (ohm cm2 ) 6.29 × 104 4.49 × 105 1.54 × 107 7.06 × 107 8.59 × 107 3.13 × 108
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779
Fig. 6 – The cross-sectional SEM images of PEO coatings.
Fig. 7 – Potentiodynamic polarization curve of the uncoated
pure aluminum and PEO coatings with different borax
concentration.
coating, which shows the best corrosion resistance than other
PEO coatings and Al substrate.
The polarization resistance (Rp ) of PEO coating was calcu-
lated using Stern and Geary’s equations [61]:
B layer, the corrosion resistance of the PEO coatings are mostly
Icorr
Rp
ˇa ˇc
B=
2.3(ˇa + ˇc )
According to the data listed in Table 4, the Rp value
increases with increasing borax concentration in electrolyte.
Meanwhile, the Icorr value of PEO layer decreases with
increasing borax content. Therefore, increasing the borax
concentration in the electrolyte can grow a PEO layer with
significantly improved corrosion resistance on the surface of
8773
pure aluminum. We also found out that through the addi-
tion of 6 g L−1 borax in the electrolyte, the calculated corrosion
resistance of Al substrate can be improved around 4976 times
higher after the PEO treatment.
Nyquist plots of the pure aluminum and PEO coatings are
shown in Fig. 8(a). The enlarged plots of the dashed region
(Nyquist plot) are further depicted in Fig. 8(b). The Nyquist plot
of the untreated Al sample is difficult to identify due to its rel-
atively smaller semicircle, which indicates its poor corrosion
resistance behavior. It is clear to observe that the diameter of
the semicircle for PEO coating increases with an increasing
borax concentration in the electrolyte. The largest semicir-
cle for the B6 coating sample can be found due to its highest
corrosion resistance. The PEO coatings exhibit different EIS
performances, and their difference can be characterized in the
low frequency (LF) range of EIS Bode modulus and phase plots
as shown in Fig. 8(c) and (d) respectively.
It has been reported that the corrosion behavior of outer
layer can be reflected by the impedance at high-frequency (HF)
range, whereas the anti-corrosion property of inner layer of
the coating can be determined by the low frequency (LF) range
[62,63]. The difference of EIS Bode plots between five PEO coat-
ings at the LF range indicates that the diversity in corrosion
resistance between these PEO coatings may be essentially due
to the different nature of their inner barrier layers. Since the
inner barrier layer of PEO coatings possessed a compact struc-
ture with better corrosion resistance than the outer porous
(3)
determined by the inner barrier layer [64]. It is reported that
the external porous layer has very limited effect on the anti-
(4) corrosion property of PEO coating [65]. According to the EIS
Bode plots in Fig. 8(c), B6 coating has the highest corrosion
resistance in the LF range than the other PEO coatings, imply-
ing its best anti-corrosion nature. From to the EIS Bode figure,
it is clearly to be seen that the corrosion resistance of PEO coat-
ings increases with increasing borax concentration due to its
effective blockage for the penetration of corrosive agent and
protecting the coating without severe destructive failure. We
8774 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779
Fig. 8 – EIS plots of the pure aluminum and PEO coatings in 3.5% NaCl solution for 6 h immersion time. (a) Nyquist plots, (b)
the enlarged plots of Nyquist plots, in the lower-left region, (c) Bode modulus, and (d) Bode phase plots.
believe that the addition of borax can ensure a PEO outer coat-
ing with less porosity, which can reduce the rapid penetration
of corrosive solution through the cracks and pores on surface.
The equivalent electrical circuits of EIS data obtained from
pure Al and PEO coatings are shown in Figs. 9(a) and (b),
respectively. The physical model and electrical equivalent
circuit for the PEO coating on Al substrate can be further
depicted in Fig.10.The parameters of EIS fitting, i.e. capaci-
tance, resistance, corrosion reaction, electrolyte interface, and
diffusion-reaction, etc., of all PEO coatings were found from
the equivalent electrical circuits in literature [66,67]. In this
equivalent electrical circuit model of pure Al, R1 is the resis-
tance of the electrolyte, R2 is the resistance due to the porous
surface layer, and Q1 is the capacitance of the porous layer,
representing the response from porous layer in coating at high
frequency. Furthermore, for the equivalent electrical circuit
model of PEO coating, R1 is the resistance of the electrolyte, R2
is the resistance in the defects and pores of outer layer, which
is parallelly connected with a constant phase element (CPE)
(Q1 ). The resistance of the barrier layer, R3 , is connected with
a CPE of barrier layer (Q2 ). The resistance of charge transfer,
R4 , is parallelly connected with a CPE (Q3 ) corresponding to
low frequency. A Warburg impedance associated with the dif-
fusion process is also connected with R4 , which is related to
the corrosion products at the interface between coating and
Al substrate demonstrating the semi-infinite length diffusion
and has a higher effect at lower frequency [68]. Toorani et al.
[69] reported that after some period of immersion, component
of Warburg occurred at low frequency in the equivalent circuit
is credited to the limited mass transfer. The higher amounts
of resistance of the porous layer of the samples are due to less
penetration of corrosive agents through the external porous
layer and higher density of a barrier layer [70]. The solid lines
in Fig. 8 are the fitted results in the Nyquist plot and Bode plots,
which show very good fitting with experimental data points.
According to the equivalent circuit model, the results of these
parameters are listed in Table 5.
To better define the interfacial heterogeneities of the PEO
coatings, the general constant phase element (CPE) is used
instead of a rigid capacitive element. The CPE is describe by:
[71]
n
ZCPE = 1/[Y(jω) ] (5)
where j is the imaginary unit, ω is the angular frequency, and n
and Y are the CPE parameters. The n values are ranging from 0
to 1. For n = 0, the CPE describes an ideal resistor, and for n = 1,
the CPE describes an ideal capacitor.
According to the fitting data of all coatings and untreated
Al as listed in Table 5, the corrosion value R3 increases from
3.40 × 103  cm2 for untreated Al substrate to 6.51 × 107  cm2
for the B6 coatings. On the other hand, the sum of R3 and
R4 increased with increasing borax concentration. The R3 + R4
value increases from 1.61 × 106 to 7.84 × 107  cm2 as the borax
addition increases from 0 to 6 g L−1 . Apparently, the resistance
value of PEO coating increased with increasing borax contents
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779 8775

Fig. 9 – The equivalent circuits for fitting the impedance data of (a) bare pure aluminum and (b) PEO coated samples.

Table 5 – Impedance values using the equivalent circuit for fitting.

Parameter Al B0 B1.5 B3 B4.5 B6

R1 ( cm2 ) 25.36 22.56 37.26 35.23 35.59 20.36

Q1 (S·sn1) ) 5.13 × 10–5 1.01 × 10–7 1.93 × 10–8 2.04 × 10–8 3.94 × 10–8 3.82 × 10–8
n1 0.84 0.83 0.97 0.95 0.93 0.95
R2 ( cm2 ) 3.40 × 103 2.38 × 104 2.94 × 104 3.45 × 104 4.03 × 104 6.29 × 104
Q2 (S sn2 ) – 2.79 × 10–7 1.36 × 10–8 6.54 × 10–8 7.07 × 10–8 6.61 × 10–7
n2 – 0.75 0.65 0.67 0.51 0.79
R3 ( cm2 ) – 3.36 × 105 3.36 × 106 5.64 × 106 7.19 × 106 6.51 × 107
Q3 (S sn3 ) – 5.19 × 10−5 4.14 × 10–6 4.85 × 10–8 8.05 × 10–8 1.87 × 10–8
n3 – 0.74 0.85 0.66 0.76 0.70
R4 ( cm2 ) – 1.27 × 106 2.94 × 106 6.12 × 106 7.09 × 106 1.33 × 107
W ( s–1/2 ) – 2.39 × 104 3.88 × 105 8.91 × 105 9.76 × 105 1.09 × 102

Table 6 – Surface porosity values of PEO coatings

calculated from EIS results.
Sample no. B0 B1.5 B3 B4.5 B6

Porosity (%) 2.117 4.235 4.289 4.233 2.735

delamination of the PEO layer are indicated by white arrows

Fig. 10 – The physical model and electrical equivalent
circuit of the PEO coating on pure aluminum immersed in
3.5 wt% NaCl solution.
on the corroded surfaces. A large delaminated oxide region
can be seen for B0 coating. Whereas very limited numbers of
corrosion pits and cracks on the B6 coating imply its good cor-
rosion resistance. Since the corrosion resistance of the PEO
coating is strictly associated with its porosity density [72,73],
the deep penetrating pores become the shortcuts for the cor-
rosive solution penetrating into the metal substrate and thus
degrades its anticorrosion performance [2,74].
In addition to the porosity measurement by the direct cal-
culation on the surface morphologies in Fig. 4, the surface
porosity of the PEO coating was also measured from the EIS
values [75]. The surface porosity of oxide coating can be cal-
culated using the following Equation [75]:
/AB /
P= (6)
/AC /

where P is the percentage of porosity, |AC | is the absolute value

in the electrolyte. After calculating the ratio between (R3 + R4 )
of B6 and R2 of pure Al, the corrosion resistance of Al substrate
was increased 23058 times higher after the B6 PEO treatment
using an electrolyte containing 6 g L−1 borax. The increment
in corrosion resistance indicates that the borax addition dur-
ing PEO treatment can effectively provide a protective oxide
layer on the surface of Al substrate. The anti-corrosion per-
formance also increases with increasing borax addition due
to the formation of a denser and less defect microstructure.
The surface morphologies of PEO coatings after potentiody-
namic polarization tests are shown in Fig. 11. Some cracks and
of the area of PEO coated sample under Nyquist admittance
curve and |AB | is absolute value of area of non-treated bare
pure aluminum under Nyquist admittance curve. The calcu-
lated surface porosity values from the EIS results are listed
in Table 6. However, the porosity results are not compatible
with these obtained from the direct image analysis method
as listed in Table 3. In Table 6, the calculated porosity value
of B0 has the lowest porosity, 2.117% than other PEO coatings,
which is contrary to its poor corrosion resistance. The differ-
ence between the data shown in Tables 3 and 6 still needs
further investigation in the near future.
8776 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779
Fig. 11 – SEM image of the PEO coated sample after the potentiodynamic polarization test.
Through the observations of microstructure, surface poros-
ity, cross-sectional morphology, and corroded surface images
after corrosion test analysis, the effectiveness of borax addi-
tion in the PEO electrolyte on the formation of dense and less
defect microstructure of PEO coating on Al substrate can be
confirmed in this work. It has been reported that the corro-
sion resistance of the PEO coating is strongly influenced by the
surface morphology and the electrolyte concentrations [76,77].
The better corrosion resistance of PEO coating on Mg substrate
by the addition of borate and NaAlO2 in electrolytes was also
revealed due to its ability to produce a compact microstruc-
ture and a less defect structure [42]. In this work, it has been
observed that the thickness of the PEO layer has less influence
than the dense microstructure on the corrosion resistance of
Al substrate, which has a strong agreement with previously
reported literature [78].
Finally, we can conclude that the borax concentration in the
electrolyte plays a major influential role on the electrical con-
ductivity, discharge characteristics, and breakdown voltage,
which ultimately affects the density of porosity, microstruc-
ture, oxide layer thickness, and corrosion resistance of PEO
coating on pure Al. A dense PEO oxide layer with less surface
defects and an excellent corrosion resistance can be obtained
on the Al substrate when the borax concentration of 6 g L−1
was added in the electrolyte.
4. Conclusions
In this study, we investigated the influence of borax con-
centrations on the PEO process discharge characteristics,
microstructure and corrosion behavior of PEO coating on
pure aluminum. The electrolyte conductivity decreased with
increasing borax concentration. The breakdown voltage and
corresponding time increased with increasing borax con-
centration in the electrolyte. An over-stoichiometric ␥-Al2 O3
phase was produced on each PEO layer. The boron content
of the PEO coating increased with increasing borax concen-
tration in the electrolyte. Meanwhile, the average pore size
and porosity on the PEO coating decreased with increasing
borax concentration. Due to the decreasing amount of micro-
discharge sparks during the PEO treatment by the addition
of 6 g L−1 borax, a more compact surface microstructure with
smaller pore size, less defects and cracks was obtained for
the B6 coating. Through the potentiodynamic polarization test
and EIS measurements, the corrosion resistance of the PEO
layer was greatly enhanced by the increasing amount of borax
in the electrolyte due to the development of denser and less
defect PEO oxide layer. The improvement of corrosion resis-
tance of Al substrate in 3.5 wt% NaCl aqueous solution up to
23,058 times higher was achieved by the PEO treatment using
an electrolyte containing 6 g L−1 borax addition. The result
obtained in this work can be further used to improve the cor-
rosion resistance of aluminum in various environments.
Conflicts of Interest
The author declares no conflicts of interest.
Intellectual property
We confirm that we have given due consideration to the pro-
tection of intellectual property associated with this work and
that there are no impediments to publication, including the
timing of publication, with respect to intellectual property. In
so doing we confirm that we have followed the regulations of
our institutions concerning intellectual property.
Acknowledgments
The authors would like to thank the financial support by the
Ministry of Science and Technology (MOST) in Taiwan under
the Project numbers of MOST 107-2218-E-131-001 and MOST
107-2221-E-131- 002-MY3.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(x x):8766–8779 8777

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