Progress in Organic Coatings 170 (2022) 107002

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Progress in Organic Coatings

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

Corrosion and tribocorrosion protection of AZ31B Mg alloy by a

hydrothermally treated PEO/chitosan composite coating
Luyao Xu a, Xiaojing Fu a, Huijuan Su b, Huilai Sun a, Ruichuan Li a, Yong Wan a, c, *
a
School of Mechanical Engineering, Qilu University of Technology, Jinan 250353, PR China
b
School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, PR China
c
State Key laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China

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

Keywords: This study is aimed at the enhancement of the corrosion and tribocorrosion performance of AZ31B magnesium
Tribocorrosion (Mg) alloys after plasma electrolytic oxidization (PEO) treatment. Some PEO-treated Mg samples were coated
Corrosion with chitosan (CS) film by dip-coated method, while others were subjected to hydrothermal treatment (HT)
Plasma electrolytic oxidation
followed by CS film. The microstructure and chemical composition of coatings were investigated via X-ray
Magnesium alloy
Hydrothermal treatment
diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. Corrosion resistance of
Chitosan the specimens was evaluated via electrochemical measurements (open circuit potential and electrochemical
impedance spectroscopy) in simulated body fluid. The tribocorrosion performance was determined by simulta­
neously recording the variation of the friction coefficient and the open circuit potential with the sliding time. The
results indicated that better corrosion and tribocorrosion performance were observed when CS layer is applied on
hydrothermally treated PEO samples than on the bare PEO samples. Thus, fabrication of hydrothermally treated
PEO surface coatings with chitosan is a significant approach to protect the Mg from corrosion and tribocorrosion,
thereby increasing the potential application of Mg alloy as biological implants.

1. Introduction
Compared with traditional biological implants, such as
cobalt‑chromium alloys, titanium alloys, stainless steels, bio-ceramics,
and polymers, the density and Young’s modulus of magnesium (Mg)
alloys are closer to those of natural bones, and the stress shielding effect
can therefore be significantly reduced at the interface between the
implant material and human bones [1]. Good physical and mechanical
properties are suitable for bone repair and the promotion of human bone
growth. Mg and its alloys also have excellent biocompatibility. Mg ions
produced by degradation can participate in many metabolic reactions in
the human body, and are also cofactors of many human enzymes [2].
However, the major challenges of Mg-based implants include their poor
corrosion and wear resistance in the human environment, which easily
results in local alkalization and a reduction in mechanical properties
[3,4]. The plasma electrolytic oxidation (PEO) surface modification
technique has been widely utilized to effectively overcome these ob­
stacles via the rapid formation of a ceramic coating with high hardness
[5–7]. Moreover, the PEO technique has been reported to prominently
reduce the corrosion rate of Mg alloy in simulated body fluid (SBF)
[8–10]. Shi et al. [11] successfully fabricated a PEO coating containing
Ca-P on AZ31B alloy in near-neutral pH solutions and evaluated the
corrosion resistance and biocompatibility in Hank’s solution. Experi­
mental results obtained by Xia et al. [12] indicated that anti-corrosion
properties of PEO treated samples was increased by 1 order of magni­
tude in the SBF, and PEO specimen had excellent mechanical properties.
The HA containing PEO coating fabricated by suitable oxidation times
can effectively protect AZ31 alloy substrate from corrosion by Hank’s
solution [13]. However, PEO coatings are typical in the metallurgical
bonding of their double-layer microstructure, namely a thick porous
outer layer and a fairly compact and thin inner layer, to the substrate
[5,10]. In this case, surface pores and cracks could be free paths for
corrosive media to diffuse to the interface between PEO coatings and the
substrate. Thus, these pores and cracks should be sealed to achieve
better corrosion protection.
Creating a thin organic/inorganic layer on a PEO coating is one of the
most attractive methods which has been considered by many re­
searchers. A variety of composite coatings were prepared on Mg alloy.
The properties of these typical composite coatings along with the
method of preparation are presented in Table 1 [14–23]. Toorani et al.

* Corresponding author at: School of Mechanical Engineering, Qilu University of Technology, Jinan 250353, PR China.
E-mail address: wanyong@qlu.edu.cn (Y. Wan).

https://doi.org/10.1016/j.porgcoat.2022.107002
Received 23 March 2022; Received in revised form 23 June 2022; Accepted 23 June 2022
Available online 2 July 2022
0300-9440/© 2022 Elsevier B.V. All rights reserved.
L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

Table 1
Various composite coatings and results of research conducted on hybrid coatings system.
Substrate PEO Electrolytes Hybrid coatings Coating Results Ref
preparation

AZ31 Na3PO4 + KOH + Ce PEO/silane/ Dip coating The optimal protective performance and great adhesive strength via covalent [14,15]
(NO3)3 epoxy bonding between layers
AZ31 Na3PO4 + KOH + CeO2 PEO/Epoxy-Ce Dip coating Better protective behavior of the epoxy layer due to the presence of CeO2 [16]
AZ31 Na3PO4 + KOH + La PEO/Epoxy-La Dip coating Enhanced protective property of double layer coating due to the deposit of La(OH)3 [17]
(NO3)3
MA8 Na4SiO4 + NaF PEO/PTFE Spray High corrosion-resistant performance and high hydrophobicity [18]
MA8 Na2SiO3 + NaF PEO/PA Spin coating High corrosion resistance and hydrophobicity, excellent wear resistance [19]
MA8 Na4SiO4 + NaF PEO/TFE Dip coating The best anti-corrosion property and wear resistance, lowest wettability [20]
AM50 Na3PO4 + KF + NaOH PEO/sol-gel or Dip coating Enhanced corrosion performance of PEO coating due to the sealing effect of the sol- [21]
epoxy gel or epoxy layer
AZ31 Not specifically PEO/primer Spray The best corrosion resistance due to the synergistic effect of PEO and primer layer [22]
provided
AZ31 NaAlO2 + NaOH PEO/LDHs Hydrothermal Superior corrosion protection due to the synergistic effect of corrosion inhibitors and [23]
hydrothermal treatment

[14–17] fabricated the multiple PEO/Epoxy systems to effectively
enhance the anti-corrosion performance of Mg alloys in corrosive media.
Additionally, some other polymer materials, such as fluoroparaffin (PA),
polytetrafluoroethylene (PTFE), and tetrafluoroethylene (TFE), were
also widely used in the sealing of PEO coatings [18–20]. Especially,
evaluation of the corrosion and wear resistances of composite coatings
reflected a great decrease in corrosion current density (6.3 × 10− 9 A/
cm− 2) and wear rate (4.6 × 10− 5 mm3 N− 1 m− 1) of composite coatings
by 2 orders of magnitude in comparison with the PEO coating [20]. Sol-
gel process is also a proven and simple technique to seal the pores of PEO
coating [21,22]. Moreover, layered double hydroxides (LDHs) were
prepared to improve the anti-corrosion property of PEO coating [23].
More information could also be found in a recently published review
[24].
Given their biological applications, biomedical polymer materials
are employed as an ideal choice to seal PEO-treated samples [25]. Chi­
tosan (CS) has been universally investigated for use in human clinical
materials due to its superb biodegradability, biocompatibility, film-
forming ability, and non-toxicity, among other characteristics [26].
Dou et al. [27] reported that CS coating could seal the pores of PEO
coatings, and exhibited a lower corrosion rate in SBF. Bai et al. [28]
found that a composite PEO/CS coating significantly increased the bio-
corrosion resistance of Mg alloy. Yu et al. [29] investigated the in vitro
degradation behavior of a PEO coating on Mg alloy after being sealed by
a CS coating.
Hydrothermal treatment (HT) is an effective, inexpensive and envi­
ronmentally friendly sealing technique that enhances the corrosion
resistance of PEO coatings. Dey et al. [30] revealed that the anti-
corrosion property of a PEO sample sealed in boiled water was
evidently improved as compared to that of an unsealed PEO sample. An
experimental analysis conducted by Liu et al. [31] revealed that a PEO
coating treated with steam sealing at 453 K for 2 h exhibited the most
remarkable anti-corrosion property. Thus, the corrosion resistance of
PEO-treated Mg is expected to be extended via the combination of HT
treatment with a CS coating. In this study, a CS layer was coated on a
PEO-treated Mg alloy after HT treatment, and the anti-corrosion per­
formance of the resulting composite PEO/HT/CS coating was compared
with that of a PEO/CS coating. Moreover, many joint parts in bio-
implants are often affected by both corrosion and wear. However,
there has been no research on the tribocorrosion behavior of CS coat­
ings. Thus, the second aim of this work is to investigate the tribocorro­
sion protection performance of the composite coatings.
2. Experimental details
2.1. Materials
The used substrate materials are AZ31B Mg alloys with a chemical
composition of 3.20 wt% Al, 1.30 wt% Zn, 0.32 wt% Mn, 0.02 wt% Si,
0.003 wt% Fe, 0.002 wt% Ca, 0.002 wt% Cu, 0.001 wt% Ni and balance
Mg. All Mg alloys were purchased from Lianwei Technology (Dongguan)
Co., Ltd. (China). The alloy sheets were cut into regular pieces with a
dimension of 35 mm × 35 mm × 2 mm. The specimens were ground with
SiC sandpaper to Ra = 0.1 μm.
2.2. Preparation of PEO coatings
All chemical agents were purchased from Sinopharm Chemical Re­
agent Co., Ltd. (China). The alkaline electrolytes solution for the PEO
process was composed of 10 g/L Na2SiO3⋅9H2O, 5 g/L Na2B4O7⋅10H2O
and 1 g/L NaOH. The pH and conductivity values of the electrolytes
solution were 13.2 and 17.3 mS/cm, respectively. The PEO procedure
was performed at a constant current of 1.7 A for 20 min. The aqueous
solution temperature was controlled at around 30 ◦ C. Other parameters
on the PEO instrument panel were also set: 25 % duty cycle, 300 Hz
frequency. The 304 annular tube and clamped Mg alloy sheet were used
as the cathode and the anode respectively. After PEO treatment, the
specimens were thoroughly rinsed with deionized water and dried in air
at room temperature. The samples are denoted as PEO.
2.3. Hydrothermal treatment of PEO coatings
The homogeneous hydrothermal solution consisted of 1.5 mol/L
NaOH. PEO sample was placed in a stainless steel container with built-in
polytetrafluoroethylene reactor, and then completely immersed in the
above 80 mL hydrothermal solution. Subsequently, the reaction
container was heated to 125 ◦ C with a muffle furnace at a heating rate of
5 ◦ C/min, and kept for 18 h. After the hydrothermal treatment, the
sample was slightly rinsed with deionized water several times, and
finally dried in air at room temperature. These samples are marked as
PEO/HT.
2.4. Fabrication of CS coatings
PEO and PEO/HT samples were subjected to CS coating. 1 g chitosan
powder (Mw = 270 kDa, >90 % deacetylated, Aladdin) was dissolved
per 100 mL 0.4 vol% acetic acid solution. The CS solution was
magnetically stirred for 12 h until the chitosan was completely dis­
solved. 1 mol/L NaOH was dropping in the CS solution to change the pH
from about 4.0 to 6.5–7.0 during the process of the next three-hour
stirring. Immediately afterwards, the coated specimen was immersed
perpendicularly in the CS solution for 5 min, then the sample was drawn
out at a constant rate of 2 mm/s with the lifting coating machine. The
above treatment was repeated five times to ensure that micro-pores on
the sample surface were completely sealed. Finally, the specimen was
naturally dried at 25 ◦ C for 120 h. The PEO and PEO/HT coated with CS

2
L. Xu et al.
Table 2
Chemical composition of the SBF (pH 7.4, 1 L).
Reagent NaCl NaHCO3 KCl
Amount (g) 8.035 0.355 0.225
coatings are denoted as PEO/CS and PEO/HT/CS, respectively.
2.5. Characterization of samples
The phase structures of the coatings were analyzed by X-ray
diffraction (XRD; D8 ADVANCE, Bruker, Germany) with Cu Kα radia­
tion, 40 kV tube voltage and 40 mA output current. The chemical
bonding of the specimens was probed using Fourier transform infrared
spectroscopy (FT-IR, INVENIO-R, Bruker, Germany). The scanning
electron microscope (SEM, Merlin-Compact, Germany) was utilized to
investigate the surface and cross-section morphologies of the coatings.
The chemical compositions of the specimens were examined using en­
ergy dispersive X-ray spectrometry (EDS) with 15 kV accelerating
voltage. The water contact angle (CA) was determined utilizing the CA
Fig. 1. The surface morphologies of the (a) PEO, (b) PEO/HT, (d) PEO/CS, and (e) PEO/HT/CS samples with individual enlarged parts.
Progress in Organic Coatings 170 (2022) 107002
K2HPO4⋅3H2O MgCl2⋅6H2O CaCl2 Na2SO4 1 mol/L HCl
0.231 0.311 0.292 0.072 39 mL
goniometer (JC2000D1, China) at the room temperature. The volume of
water droplet was 5 μL.
According to ASTM D3359-09, the adhesion tester (QFH-HD600,
China) was utilized to examine the adhesion strength between the
coating and Mg alloy substrate [32]. The surface roughness of coatings
were detected using portable surface roughness tester (SJ-210, Mitu­
toyo, Japan) with an accuracy of 0.001 μm at a probe sliding rate of 0.25
mm/s. In order to ensure the reliability of the micro-hardness testing,
the rough surface of the PEO-coated specimen was slightly ground with
1200# SiC sandpaper to obtain an average surface roughness of Ra ≈
0.5 μm, and then the hardness testing was carried out by digital Vickers
tester (FUTURE-TECHFM-700, Japan). In the tests of hardness and
roughness, 10 places were randomly investigated to obtain the average
value and standard deviation.
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L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

Table 3
The EDS analysis of the surfaces of different samples (wt%).
Sample (region) O Mg Al Zn Si Na B C N

PEO (#1) 46.41 25.73 0.76 0.46 16.21 1.48 8.95 – –

PEO/HT (#2) 47.38 26.58 0.70 0.34 17.12 1.14 6.74 – –
PEO/CS (#3) 50.25 0.15 0.02 0.05 0.13 7.42 0.06 31.59 10.33
PEO/HT/CS (#4) 50.75 0.12 0.04 0.03 0.10 6.91 0.04 30.88 11.13

2.6. Electrochemical measurements
The open circuit potential (OCP) and electrochemical impedance
spectra (EIS) measurements were utilized as an effective and convenient
method to analyze the corrosion behavior of the coatings on Mg alloys in
the simulated body fluid (SBF) with the chemical components listed in
Table 2 [33]. These electrochemical tests were conducted using a stan­
dardized corrosion testing system (CHI660E, China). The SBF was
buffered at pH 7.4 using tris(hydroxymethyl) aminomethane
((CH2OH)3CNH2) and 1.0 mol/L hydrochloric acid (HCl).
The corrosion testing system consists of a conventional three-
electrode cell with a testing specimen with an exposure area of 4.80
cm2 as the working electrode, an Ag/AgCl electrode as the reference
electrode, a carbon electrode as the auxiliary electrode, respectively.
The testing cell was filled with the SBF of 40 mL in each measurement.
Before EIS measurements, OCP measurements were performed firstly,
and EIS measurements started only when the OCP values kept stable. EIS
measurements were carried out at the OCP in a frequency range of
10− 2–105 Hz with 10 points/10 frequency multiplication, and the signal
amplitude of voltage sinusoidal disturbance was 10 mV RMS. The three-
electrode testing cell was used and the temperature of the SBF was
remained at 36.5 ± 0.5 ◦ C. All the tests were repeated three times and
the value was averaged.
2.7. Tribocorrosion tests
A reciprocating ball-on-disk tribometer (MFT-EC4000, China) was
utilized to evaluate the tribocorrosion performance of the specimens
against a 9.525 mm diameter Al2O3 ball. The working condition of wear
testing was specifically set: normal load of 1 N, track length of 5 mm,
vibration frequency of 1 Hz. The three-electrode cell containing the SBF
was heated to a temperature of 36.5 ± 0.5 ◦ C by the built-in heating
system. The OCP value was detected by the tribo-electrochemical sys­
tem, where the testing specimen, an Ag/AgCl electrode and a carbon
electrode as the working electrode, reference electrode and auxiliary
electrode, respectively. The OCP value was recorded 10 min before, 30
min during and 10 min after the sliding. Topographies and elements
from the wear tracks were analyzed by SEM and EDS. Wear rate of the
specimens was attained by dividing the wear volume by the normal load
and the distance moved [34]. Each testing was repeated three times to
minimize accidental errors.
3. Results and discussion
3.1. Surface and cross-sectional morphologies
Fig. 1 displays the surface morphologies of the samples after different
treatments. The surface of the PEO-treated sample (Fig. 1(a)) reveals the
existence of randomly distributed volcano-like micro-pores of various
sizes and micro-cracks penetrating the pores. The discharge channels,
namely micro-pores, were developed in large quantities due to the
partial spark discharge and gas overflow during the coating growth [31].
In addition, the micro-cracks are supposed to be caused by inhomoge­
neous thermal stress distribution during the molten substance cooling
process [35].
The surface morphological features of the PEO samples after HT, as
illustrated in Fig. 1(b), notably indicate the appearance of hydration as
compared with the PEO samples. Dense, short, hexagonal columnar

Fig. 2. The cross-sectional morphologies and element mappings of Mg, O, Si, and C for (a) PEO, (b) PEO/HT, (c) PEO/CS, and (d) PEO/HT/CS samples.

4
L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

Si-O-Si
5 Mg(AlH4)2 7 Mg3(BO3)2

Mg-OH
3 Al2O3 9 chitosan

N-H
1 Mg

C-O-C
N-H
C-H

C-N
C=O
C-H

Mg-O
2 MgO 4 Mg2SiO4 6 Mg2B2O5 8 Mg(OH)2
5
1
1 PEO
4 6 2 5
4 4 4 7 7 PEO/HT
4

Transmittance (%)
4 44 43 1 4

3695
PEO/CS

O-H

1010
890
Intensity(a.u.)

PEO 1
PEO/HT/CS
1 6 7 7
4 4 84 2 5

515
84 4 4
43 1 4 8 4 5

C-N
PEO/HT 1
chitosan powder
9 4 4 4 1 6 7 7
4 2 1 4 4
5 5
1

1163
1660
PEO/CS

3366

2924

1418
1572
2863
89 4 4 4 18 6 7 7 5

1064
4 2 4 5

1026
1 8 4
PEO/HT/CS
4000 3600 3200 2800 2400 2000 1600 1200 800 400
10 20 30 40 50 60 70 80
-1
2-Theta/degree Wavenumber (cm )

Fig. 3. The XRD patterns of the PEO, PEO/HT, PEO/CS, and PEO/HT/ Fig. 4. The FT-IR spectra of the PEO, PEO/HT, PEO/CS, and PEO/HT/
CS samples. CS samples.

crystals were found to be distributed on the surface of the PEO/HT
coating under high-magnification SEM (see Fig. 1(c)). The hexagonal
crystals precipitated around or inside the micro-pores were character­
ized as Mg(OH)2 crystals [36], which was further confirmed by XRD and
FT-IR analyses, as presented in Section 3.2.
Fig. 1(d) reveals that the porous microstructures of the PEO-treated
samples were completely sealed by the CS layer. In particular, no
obvious defects in the appearance of the samples, such as micro-pores or
micro-cracks, were found. This was also observed for the PEO-HT-
treated samples after being covered with the CS layer (Fig. 1(e)).
The EDS analysis of the different specimens, as presented in Table 3,
reveals that the PEO coatings were mainly composed of O, Mg, Si, and B,
which is not a significantly different composition from that of the PEO/
HT coating. The result also illustrates that the formation of the PEO
coating was associated with both the deposition of electrolyte com­
pounds and the self-oxidation of the alloy substrate [31]. Primarily O, C,
and N were found to exist in the CS layer. Some Na was also observed in
the CS layer, which is ascribed to the addition of NaOH in the CS
solution.
Fig. 2 exhibits the cross-sectional SEM images and element distri­
bution in the cross-sections of the different samples. The thickness of the
PEO coating was found to be approximately 38 μm, which is the same as
that of the PEO/HT coating, demonstrating that the HT process did not
change the thickness of the PEO coating. A hierarchical structure was
obvious in the cross-sectional images of the PEO/CS and PEO/HT/CS
coatings. The CS layer was approximately 15 μm thick. The EDS map­
ping analysis presented in Fig. 2(a) and (b) reveals that Mg, O, and Si
were uniformly dispersed in the PEO and PEO/HT coatings. This result is
consistent with the EDS analysis (see Table 3). However, the B element
was not found due to the unclear EDS mapping image, which may be
related to the relatively low content of B. As clearly shown in Fig. 2(c)
and (d), the discernible and even distribution of C and O provides evi­
dence of the existence of the CS layer on the PEO-treated samples.
The roughness of different samples was also measured. The charac­
teristic surface topography of the PEO specimen led to a higher surface
roughness (Ra ≈ 1.66 μm) as compared to that of the uncoated substrate
(Ra ≈ 0.12 μm). The PEO/HT sample had a relatively low roughness (Ra
≈ 1.32 μm) as compared to the PEO sample, which may have been due to
3.2. Chemical compositions
As is evident from the XRD spectra of the samples obtained using
different treatments shown in Fig. 3, all samples had clear Mg peaks,
which is ascribed to X-rays penetrating the coating to reach the under­
lying Mg alloy substrate [37]. The diffraction patterns of all specimens
demonstrate the common existence of MgO, Mg2SiO4, Mg(AlH4)2,
Mg2B2O5, and Mg3(BO3)2 crystalline phases, excluding the Mg peaks
from the alloy substrate, which were due to the complicated plasma
chemical oxidation reactions during the spark discharge process
[7,38,39]. In the case of the PEO/HT and PEO/HT/CS coatings, the
typical diffraction peaks of Mg(OH)2 at approximately 2θ = 18◦ , 38◦ ,
and 59◦ confirm the formation of Mg(OH)2 crystals during the HT pro­
cess. As can be seen, the XRD spectra of the PEO/CS and PEO/HT/CS
coatings each display a broad peak at about 2θ = 20◦ corresponding to
CS [27,40].
Fig. 4 presents the IR spectra of the samples obtained using different
treatments. For the PEO and PEO/HT coatings, the adsorption peaks at
around 1010 and 890 cm− 1 are respectively ascribed to the asymmetric
and symmetric stretching vibration of Si–O–Si [41,42], which strongly
confirms the existence of Mg2SiO4. A weak absorption band located at
about 515 cm− 1 was due to Mg–O stretching vibration, implying the
growth of MgO in the PEO-treated coating [43]. Additionally, an
adsorption peak at 3695 cm− 1 was detected for the PEO/HT coating,
which corresponds to the high basicity of the O–H groups in Mg(OH)2
[31,44].
Accordingly, the HT process can be described by the following re­
actions [31,43].
Mg2+ (aq) + 2OH− (aq)→Mg(OH)2 (s) (1)
MgO (s) + H2 O (g)→Mg(OH)2 (s) (2)
2+
On the one hand, the Mg derived from compounds in the coating
combines with OH− in the solution to produce Mg(OH)2. On the other
hand, boiled water can transform MgO to Mg(OH)2 due to the hydration
reaction between MgO and H2O.
CS is a linear polysaccharide consisting of β-(1 → 4)-linked N-acetyl-
D-glucosamine (the deacetylated part) and N-acetyl-D-glucosamine (the

the surface sealing effect of Mg(OH)2 crystals. The roughness testing
results also reveal that the mean roughness values (Ra) of the PEO/CS
and PEO/HT/CS samples were respectively 0.72 and 0.64 μm.
acetylated part) [45,46]. The characteristic wide absorption bands
located at 3600–3300 cm− 1 represent the stretching vibration of non-
associated O–H and N–H [47,48]. The shoulder peaks at 2863 and
2924 cm− 1 are associated with the stretching vibration of C–H in
methyl or methenyl [49]. The adsorption band at 1660 cm− 1 is ascribed
to the stretching vibration mode of C– – O (amide I) [50], and the ab­
sorption bands at 1572 (amide II) and 1418 cm− 1 correspond to the

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L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

Fig. 5. The static CA for the (a) Mg substrate, (b) PEO, (c) PEO/HT, (d) PEO/CS and (e) PEO/HT/CS samples.

Fig. 6. The optical images of (a) PEO, (b) PEO/HT, (c) PEO/CS, and (d) PEO/HT/CS samples after the adhesion test.

unique N–H [51]. The characteristic absorption peaks at 1163 and
1026 cm− 1 are associated with the stretching vibration of C–N, and the
absorption band located at 1064 cm− 1 represents the typical anti-
symmetric stretching of the C–O–C bridge [48]. The XRD and FT-IR
analysis results consistently indicate that the CS layer was successfully
deposited on the PEO-treated coating.
3.3. Surface wettability
Fig. 5 exhibits optical images of water droplets on the surfaces of
different samples. The surface of the bare Mg substrate had a CA of 56.5◦
± 1.5◦ (Fig. 5(a)), revealing a hydrophilic nature. As can be seen, the
PEO coating reflects an evidently hydrophilic feature with a static CA of
35◦ ± 0.5◦ (Fig. 5(b)), which is in accordance with that reported in the
existing literature [52,53]. The static CA on the surface of the PEO/HT
sample was 10◦ ± 0.5◦ (Fig. 5(c)), which caused the water droplet to

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L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

-1.25 120000
Substrate
PEO (a) PEO
-1.30 PEO/HT 105000 300
PEO/HT
Potential (V vs.Ag/AgCl)

PEO/CS 250
PEO
PEO/HT PEO/CS
PEO/HT/CS PEO/CS
-1.35 90000 200
PEO/HT/CS PEO/HT/CS

-Z /(ohm cm )
Substrate

2
150
Fit Result Substrate

-Z /(ohm cm )
2
100

-1.40
75000 Fit Result
50

0
60000
-1.45 -50

-100
0 50 100 150 200 250 300 350 400
45000 Z /(ohm cm )
2

-1.50

30000
-1.55
0 200 400 600 800 1000 1200 1400 1600 1800
15000
Time (s)

Fig. 7. OCP variation with time of immersion in SBF for substrate and 0
coated specimens. 0 20000 40000 60000 80000 100000 120000
2
Z /(ohm cm )
diffuse on the surface and rapidly penetrate the coating. As reported by
Jin et al. [54], a super-hydrophilic Mg(OH)2 film prepared on AZ31B Mg 5 (b) PEO
alloy via HT treatment was found to have a static CA of ≤8◦ . It can be 10 PEO/HT
considered that staggered flaked Mg(OH)2 crystals were generated on PEO/CS
PEO/HT/CS
the surface of the PEO coating during HT, giving rise to a more hydro­ 4 (a)
Substrate
10
philic surface with a large number of hydroxyl groups [54]. Regarding 2 Fit Result
Z /ohm cm
the PEO/CS and PEO/HT/CS coatings, the water CA values were
respectively 72◦ ± 1◦ and 72.5◦ ± 0.5◦ , thereby reflecting a hydrophilic 10
3

characteristic.

3.4. Mechanical and adhesion performances 10

2

The micro-hardness values of the coating surfaces were measured.

The micro-hardness of the PEO-treated specimens was significantly
1
10
-2 -1 0 1 2 3 4 5
higher than that of the alloy substrate (55.3 HV0.1). The hardness of the 10 10 10 10 10 10 10 10
Frequency/Hz
PEO/HT coating was about 526.7 HV0.1, which was slightly lower than
that of the PEO coating (552.4 HV0.1). This result also corresponds to the
fact that the staggered growth of Mg(OH)2 crystals in the micro-pores 60 (c)
will cause the overall decrease of the hardness of the PEO coating
[30]. The micro-hardness measurements revealed mean values of 31.8 40
and 32.5 HV0.1 for the PEO/CS and PEO/HT/CS samples, respectively.
-Theta /degree

The adhesion strength of coatings is a critical index of their practical

usage. Fig. 6 presents the surface topographies of all the coated samples
20

after adhesion testing according to the ASTM D3359-09 standard. The

results indicate that the PEO and PEO/HT coatings exhibited no distinct 0 PEO
chipping off at the edge of the square lattice, so the rank of these coat­ PEO/HT
PEO/CS
ings was identified as 5B. The region encircled by the red lines signifies -20 PEO/HT/CS
the peeling areas of the coating. It can be observed in Fig. 6(c) and (d) Substrate
that the peeling ratio of the PEO/CS coating was about 41 % (class 1B), Fit Result
-40
whereas that of the PEO/HT/CS coating was merely about 12 % (class 10
-2
10
-1
10
0
10
1
10
2 3
10 10
4
10
5

3B). This is because Mg(OH)2 grew on the surface of the PEO/HT coating
to form a super-hydrophilic surface with plenty of hydroxyl groups
(Fig. 5(c)), which is beneficial to the diffusion and grafting of the CS
solution into the interior of the coating to form a CS layer with high
adhesion strength. Secondly, due to the high viscosity and poor fluidity
of the CS solution, some micro-pores were observed at the junction be­
tween the CS layer and the PEO-treated coating. Moreover, Mg(OH)2
crystals filled most of the holes to a certain extent, which increased the
contact area between the base material and the CS layer, thereby
improving the adhesion strength.
3.5. Electrochemical measurements
3.5.1. Open circuit potential (OCP) measurements
The variation of open circuit potential during the immersion time
Frequency/Hz
Fig. 8. The EIS and fitting results of the substrate and coated samples: (a)
Nyquist plots; (b) Bode plots of |Z| vs. frequency; (c) bode plots of phase angle
vs. frequency.
can be used to monitor the chemical stability and corrosion process of
specimens during immersion time. Fig. 7 exhibits the evolution of the
OCP during 30 min exposure in SBF. The OCP of bare substrate
approached to the stable value of − 1.51 V vs. Ag/AgCl after showing a
slight increase. The stabilization of the potential demonstrates the for­
mation of corrosion products acting as a barrier layer [55].
If this variation was compared once bare substrate was oxidized, the
PEO coating shifted the potential to the positive direction reflecting an
irregular fluctuation. The OCP value initially rose rapidly and then

7
L. Xu et al.
Fig. 9. Equivalent circuit diagrams of the EIS plots: (a) substrate, (b) PEO, (c) PEO/HT, (d) PEO/CS, and (e) PEO/HT/CS samples in SBF.
decreased sharply, and started to oscillate violently between − 1.36 and
− 1.42 V vs. Ag/AgCl. This may be due to that corrosive ions penetrated
through the loose layer reaching the interface between the inner dense
layer and the outer porous layer [56]. Subsequently, the OCP value
gradually decreased and then stabilized at approximately − 1.41 V vs.
Ag/AgCl. In term of PEO/HT sample, the OCP with lower amplitude
dropped gradually and regularly from around − 1.28 to − 1.37 V vs. Ag/
AgCl. In addition, for PEO and PEO/HT specimens, the slight fluctuation
of stable OCP values occurred during soaking stage, indicating the het­
erogeneous reactions, which may be related to the non-uniform
composition and structure of the outer layer of the PEO-treated
coating [57].
In contrast, both PEO/CS and PEO/HT/CS coatings showed a smooth
evolution of the OCP with immersion time. The OCPs gradually dropped
8
Progress in Organic Coatings 170 (2022) 107002
until potentials remained stable at the values of − 1.49 and − 1.41 V vs.
Ag/AgCl after 10 min, respectively. It could suggest that the composite
coating adsorbed electrolyte, thereby reaching a stable and saturated
state [56]. The above results and corrosion behavior can be testified
further by the following EIS analysis.
3.5.2. Electrochemical impedance spectroscopy (EIS) analysis
EIS was carried out to further analyze the anti-corrosion properties of
the coated specimens. Fig. 8 exhibits the Nyquist and Bode plots of the
Mg substrate and the PEO, PEO/HT, PEO/CS, and PEO/HT/CS speci­
mens immersed in SBF for 30 min. As presented in the Nyquist plots
(Fig. 8(a)), two visible capacitive loops were found at the high- and low-
frequency regions for the coated specimens, which respectively denote
the impedance characteristics of the outer layer and the inner dense
L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

Table 4
EIS fitting parameters of equivalent circuits for the substrate and coated samples.
Samples Rs (Ω cm2) CPEpo-T CPEpo-P Rpo CPEdl-T CPEdl-P Rct RL L
(10− 6 Ω− 1
cm− 2 n
s ) (Ω cm2) (10− 5 Ω− 1
cm− 2 n
s ) (Ω cm2) (Ω cm2) (H cm2)

Substrate 76 – – – 4.85 0.93 236 99 174

PEO 53 1.54 0.74 5702 2.45 0.71 48,632 – –
PEO/HT 41 1.27 0.71 5863 2.03 0.76 65,527 – –
PEO/CS 36 0.82 0.66 5936 1.62 0.73 96,507 – –
PEO/HT/CS 51 0.34 0.69 7863 0.99 0.74 117,550 – –

Fig. 10. Schematic illustrations of the proposed corrosion resistance mechanisms of (a) PEO-treated samples and (b) CS-coated samples.

layer/substrate interface. The two time constants can be observed in the
Bode plots of the coated samples (Fig. 8(c)), which also corroborate with
the characteristics of the Nyquist plots in Fig. 8(a). It is universally
agreed that the anticorrosive properties of the tested specimens can be
evaluated by the axial curvature radius of the low-frequency capacitive
loop [31,58]. The maximum curvature radius of the sample reflects the
most excellent corrosion resistance [58]. As is evident, the PEO/HT/CS
samples had the most remarkable anti-corrosion performance.
The Nyquist plot of the uncoated substrate was magnified for clarity
(see Fig. 8(a)), and a similar corrosion behavior in Mg alloys has pre­
viously been reported [59]. A capacitive loop was found in the high- and
medium-frequency region, which is associated with the charge transfer
behavior of the electric double layer formed between the Mg alloy and
SBF. In addition, a low-frequency inductive loop was distinctively found
to take shape, which is supposed to be caused by the pitting corrosion of
the Mg alloy [31,59,60]. The phase angle of the uncoated Mg alloy was
also found to have a negative value in the low-frequency region, indi­
cating the occurrence of corrosive pitting on the Mg alloy substrate [59].
The value of |Z|f→0 in the Bode plots (Fig. 8(b)) can be used as an
effective indicator to examine the corrosion rate of the coating; the
higher the value of |Z|f→0, the lower the corrosion rate [61]. The order of
the |Z| values of different specimens at 0.01 Hz, from greatest to least,
was found to be as follows: |Z|PEO/HT/CS (108,580 Ω⋅cm2) > |Z| PEO/CS
(76,424 Ω⋅cm2) > |Z| PEO/HT (64,286 Ω⋅cm2) > |Z| PEO (50,162 Ω⋅cm2)
> |Z| substrate (147 Ω⋅cm2). This signifies that the PEO/HT/CS specimens
had the lowest corrosion rate. These results are in good agreement with
the Nyquist plots.
According to the EIS results and the related literature [8,62], the
electric circuit fitting results are shown in Fig. 9, where Rs represents the
SBF resistance between the workpiece and the reference electrode. Rpo
and CPEpo are connected in parallel, and respectively characterize the
outer layer resistance and the dispersed capacitance behavior of the
outer layer within the micro-pores. Moreover, CPEdl corresponds to the
electric double-layer capacitance, and Rct illustrates the charge transfer
resistance of the inner dense layer/substrate interface. For the Mg alloy
substrate, Rct characterizes the charge transfer resistance of the SBF/
substrate interface, which is parallel to CPEdl. RL is the resistance of the
passivation coating formed due to corrosive pitting, which is linked in
series with the inductance L. In particular, CPE belongs to the interface
diffusion constant phase element, which replaces the conventional
capacitance due to the roughness and inhomogeneity of the specimen
surface [63,64].
The corresponding fitting parameters of the EIS spectra based on
equivalent circuits are reported in Table 4. After the PEO samples were
subjected to HT and CS coating, the Rpo value increased slightly, but the
Rct value was much higher than the corresponding Rpo value; thus, the
anti-corrosion effect of the coating was found to be primarily dominated
by the Rct value [8,62]. As exhibited in Table 4, the increase of Rct from
236 to 48,632, 65,527, 96,507, and 117,550 Ω⋅cm2 corroborates that the
PEO/HT/CS specimens most effectively improved the anticorrosive ef­
fect of the Mg alloy substrate. These experimental results are also veri­
fied in other similar reports [29,38].
According to the testing results, the PEO/HT/CS coating can mark­
edly improve the corrosion resistance of the Mg substrate. Fig. 10
schematically illustrates the protective mechanisms of the PEO-treated
and CS-coated coatings based on the preceding analyses. For the PEO
coating, surface pores and cracks could be free paths for a corrosive
medium like Cl− to diffuse to the interface between the PEO coating and
the substrate, as exhibited in Fig. 10(a). The local corrosion of Mg
occurred in accordance with the following reaction [65].
Mg (s) + 2H2 O (g)→Mg(OH)2 (s) + H2 (g)↑ (3)
Because Mg(OH)2 has a larger molar volume than MgO, the contin­
uous generation of Mg(OH)2 will constantly damage the PEO coating
[66]. Regarding the PEO/HT coating, the inherent defects such as pores
and cracks can be sealed due to the superior expansion and sealing effect
of the Mg(OH)2 growth process [43,67]. Thus, the anti-corrosion effect
of the PEO coating was further enhanced by HT. The PEO/HT/CS
coating can effectively prevent the arrival of Cl− ions on the Mg sub­
strate due to the collaborative protection of the PEO/HT coating and the
compact CS layer, as exhibited in Fig. 10(b).

9
L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

-1.15 rupture of the passivation film, which led to the exposure of the fresh
-1.20 (a) PEO substrate to the SBF [68]. Then, the potential stabilized at around − 1.63
-1.25
PEO/HT
V vs. Ag/AgCl and oscillated with the rubbing movement, which is
PEO/CS
-1.30 PEO/HT/CS associated with the dynamic equilibrium of OCP between the mechan­
OCP/(V vs. Ag/AgCl)

-1.35 Untreated ical destruction (de-passivation) and the passive film formation (re-
-1.40 passivation) in the rubbing interface region. After sliding, the OCPs
-1.45
began to increase, but the final potential was slightly lower than that
-1.50
recorded before sliding.
The drop in potential also occurred for the PEO and PEO/HT samples
-1.55
at the onset of rubbing, suggesting the local rupture or wear of the
-1.60
rubbed zone [69]. During the sliding phase, the OCPs of the PEO and
-1.65
PEO/HT samples fluctuated violently at approximately − 1.44 and
-1.70
− 1.39 V vs. Ag/AgCl, respectively. However, unique OCP variation was
-1.75 Soaking Reciprocating sliding Soaking detected for the PEO/CS and PEO/HT/CS specimens. The OCPs did not
decline sharply at the onset of the rubbing motion, but rather progres­
-1.80
0 10 20 30 40 50
Time/min sively decayed with the continuation of the sliding motion. After rub­
bing for ~10 min, the OCPs of the PEO/CS and PEO/HT/CS samples
0.60
PEO
respectively stabilized at − 1.53 and − 1.48 V vs. Ag/AgCl, but that of the
0.55 (b) PEO/HT PEO/CS sample exhibited a slight decreasing trend in the later period.
0.50 PEO/CS Moreover, no intense oscillation of OCP occurred during the sliding,
0.45 PEO/HT/CS suggesting the excellent stability between the mechanical de-passivation
and electrochemical re-passivation [70]. After the sliding ended, the
Untreated
0.40
0.35 OCPs of both samples returned to the initial values.
Fig. 11(b) displays the variation of the COFs. The COFs of the PEO-
COF

0.30
treated specimens were markedly higher than that of the untreated
0.25
substrate, which is ascribed to the holey surface structure obtained by
0.20
the PEO technique. During the entire rubbing process, the COF of the
0.15
PEO/HT sample was more stable and lower than that of the PEO sample,
0.10 but the wear rate was slightly higher than that of the PEO sample (see
0.05
Soaking Reciprocating sliding Soaking
Fig. 11(c)). This is attributed to the slight decrease in the surface
0.00 roughness and hardness of the PEO specimen after HT. The application
0 10 20 30 40 50 of the CS layer clearly decreased the friction and wear rate of the PEO
Time/min and PEO/HT samples. The most remarkable case was that of the PEO/
HT/CS specimen, for which the average COF value was the lowest
18
0.35 (~0.11) and the wear rate was also reduced to the lowest value (~1.83
16
(c) × 10− 5 mm3 N− 1 m− 1) as compared with the untreated substrate (~1.13
× 10− 4 mm3 N− 1 m− 1).
0.30
14
Wear rate/ [10 mm /(N m)]

0.25
Fig. 12 exhibits the SEM morphologies of wear tracks after tribo­
12 corrosion testing. Regarding the uncoated substrate (Fig. 12(a)), a
Average COF
3

10 0.20 typical topography with numerous abrasive furrows at the worn zone
was distinctly observed, which is recognized as a typical abrasive wear
-5

8
6 track was observed, suggesting that the pores and cracks at the wear
4
2
0 0.00
Untreated PEO PEO/HT
Samples
Fig. 11. The evolution of the (a) open circuit potential, (b) coefficient of fric­
tion (COF) with the sliding time, and (c) average COF and wear rate for the
uncoated and coated samples.
3.6. Tribocorrosion tests
The tribocorrosion behavior of all samples was tested by recording
the variation of the OCP in the SBF before, during, and after sliding, and
the results are shown in Fig. 11(a). Before sliding, the samples were
soaked in SBF for 10 min to achieve a steady electrochemical state. The
OCP values of the PEO, PEO/HT, PEO/CS, and PEO/HT/CS samples
remained stable at the values of − 1.41, − 1.37, − 1.49, and − 1.46 V vs.
Ag/AgCl, respectively, and that of the uncoated sample was − 1.51 V vs.
Ag/AgCl.
When the sliding motion began, a sharp drop in potential was
distinctly observed for the uncoated specimen and caused the overall
mechanism [71]. For the PEO and PEO/HT samples, a smooth wear
0.15
0.10 marks were filled and compacted by the delaminated debris [72]. In the
case of the PEO/CS and PEO/HT/CS samples, plenty of micro-cracks and
scratches were clearly detected at the wear tracks. However, the plastic
0.05
deformation was more serious for the PEO/CS sample than for the PEO/
PEO/CS PEO/HT/CS HT/CS sample, and the width of the wear track (662 μm) of the PEO/CS
sample was evidently wider than that of the PEO/HT/CS sample. When
the Al2O3 ball was rubbed against the CS layer, the surface of the CS
layer was prone to propagating crack generation. The high adhesion
strength between the CS layer and PEO/HT sample could limit and
hinder the initiation and propagation of micro-cracks to a great extent,
which also effectively reduced the contact area of the wear scar region.
Accordingly, the COF and wear rate of the PEO/HT/CS sample were
significantly lower than those of the PEO/CS sample.
Fig. 13 exhibits the EDS mapping of the main elements at the various
wear scars. For the Mg alloy, O was visibly detected in the worn zone,
illustrating that the oxidation reaction occurred during the test [72]. In
the case of the PEO and PEO/HT samples, Si was visibly observed at the
wear track regions, which implies that the PEO-treated coatings still
existed after the tribocorrosion tests. In addition, abundant C elements
were also observed at positions #4 and #5, thus directly revealing that
the CS layers did not detach from the substrate.
The schematic diagrams of the tribocorrosion mechanisms are shown
in Fig. 14. Due to the abrasive wear behavior, a deeper wear groove was

10
L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

Fig. 12. SEM topographies of wear tracks after tribocorrosion tests: (a) substrate, (b) PEO, (c) PEO/HT, (d) PEO/CS and (e) PEO/HT/CS samples.

11
L. Xu et al. Progress in Organic Coatings 170 (2022) 107002

O Mg Si C

#1

#2

#3

#4

#5

Fig. 13. The EDS mapping of the main elements at the different positions shown in Fig. 11.

Fig. 14. Schematic illustrations of the proposed tribocorrosion protection mechanisms of (a) PEO-treated samples and (b) CS-coated samples.

formed on the PEO-treated coating. The wear of the coating aggravated and wear rate of the PEO/HT/CS coating may be associated with the
the corrosion of the Mg substrate in the SBF, as revealed in Fig. 14(a). presence of solid lubrication at the interface, which effectively protected
However, the PEO/HT/CS coating was found to have a much smaller the PEO/HT coating from destruction and helped to prevent Cl− ions
wear scar than the PEO-treated coating due to its lower COF and higher from eroding the Mg alloy substrate during tribocorrosion.
anti-wear property, as displayed in Fig. 14(b). The CS coating could
provide convenience to the low-shear-strength film at the surface,
eventually resulting in a change in the wear mechanism. The low COF

12
L. Xu et al.
4. Conclusion
PEO-treated AZ31B Mg alloy is characterized by porousness and
contains plenty of micro-cracks. HT enables the precipitation of Mg
(OH)2 crystals over the PEO sample. The deposition of the CS layer on
the PEO and PEO/HT samples was found to effectively seal the pores and
cracks of the PEO-treated specimens. Based on their anti-corrosion
property in SBF, the anticorrosive effect of the specimens, from great­
est to least, was found to be as follows: PEO/HT/CS > PEO/CS > PEO/
HT > PEO > substrate. Regarding the tribocorrosion behavior, the stable
OCP values, from greatest to least, were found to be as follows: PEO/HT
> PEO > PEO/HT/CS > PEO/CS > substrate. Among them, the PEO/
HT/CS coating exhibited the lowest COF and wear rate. It also displayed
the most stable tribocorrosion performance with an absence of oscilla­
tion in the OCP.
CRediT authorship contribution statement
L. X.: Writing - original draft, Investigation. X. F.: Investigation. H. J.
S. Investigation. H. L. S: Writing - review & editing. Y. W.: Funding
acquisition, Writing - review & editing, Supervision. R. L.: Writing -
review & editing.
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.
Acknowledgments
The authors acknowledge the financial support by National Natural
Science Foundation of China (51975304) and Natural Science Founda­
tion of Shandong Province, China (ZR2019MEE016).
References
[1] J. Nagels, M. Stokdijk, P.M. Rozing, Stress shielding and bone resorption in
shoulder arthroplasty, J. Shoulder Elb. Surg. 12 (2003) 35–39.
[2] A. Hartwig, Role of magnesium in genomic stability, Mutat. Res. Fundam. Mol.
Mech. Mutagen. 475 (2001) 113–121.
[3] M. Ascencio, M. Pekguleryuz, S. Omanovic, An investigation of the corrosion
mechanisms of WE43Mg alloy in a modified simulated body fluid solution: the
effect of electrolyte renewal, Corros. Sci. 91 (2015) 297–310.
[4] W. Yao, W. Liang, G. Huang, B. Jiang, A. Atrens, F. Pan, Superhydrophobic coatings
for corrosion protection of magnesium alloys, J. Mater. Sci. Technol. 52 (2020)
100–118.
[5] T.S. Narayanan, I.S. Park, M.H. Lee, Strategies to improve the corrosion resistance
of microarc oxidation (MAO) coated magnesium alloys for degradable implants:
prospects and challenges, Prog. Mater. Sci. 60 (2014) 1–71.
[6] M. Golabadi, M. Aliofkhazraei, M. Toorani, A.S. Rouhaghdam, Evaluation of La
containing PEO pretreatment on protective performance of epoxy coating on
magnesium, Prog. Org. Coat. 105 (2017) 258–266.
[7] Y. Guo, L. Xu, J. Luan, Y. Wan, R. Li, Effect of carbon nanotubes additive on
tribocorrosion performance of micro-arc oxidized coatings on Ti6Al4V alloy, Surf.
Interfaces 28 (2022), 101626.
[8] Y. Gu, C.F. Chen, S. Bandopadhyay, C. Ning, Y. Zhang, Y. Guo, Corrosion
mechanism and model of pulsed DC microarc oxidation treated AZ31 alloy in
simulated body fluid, Appl. Surf. Sci. 258 (2012) 6116–6126.
[9] R. Chaharmahali, A. Fattah-alhosseini, K. Babaei, Surface characterization and
corrosion behavior of calcium phosphate (Ca-P) base composite layer on Mg and its
alloys using plasma electrolytic oxidation (PEO): a review, J. Alloys Compd. 9
(2021) 21–40.
[10] R. Chaharmahali, A. Fattah-alhosseini, M. Nouri, K. Babaei, Improving surface
characteristics of PEO coatings of mg and its alloys with zirconia nanoparticles: a
review, Appl.Surf.Sci.Adv. 6 (2021), 100131.
[11] X. Shi, Y. Wang, H. Li, S. Zhang, R. Zhao, G. Li, Corrosion resistance and
biocompatibility of calcium-containing coatings developed in near-neutral
solutions containing phytic acid and phosphoric acid on AZ31B alloy, J. Alloys
Compd. 823 (2020), 153721.
[12] Y.H. Xia, B.P. Zhang, C.X. Lu, L. Geng, Improving the corrosion resistance of Mg-
4.0Zn-0.2 Ca alloy by micro-arc oxidation, Mater. Sci. Eng. C-Mater. 33 (2013)
5044–5050.
13
Progress in Organic Coatings 170 (2022) 107002
[13] H. Tang, T. Wu, H. Wang, X. Jian, Y. Wu, Corrosion behavior of HA containing
ceramic coated magnesium alloy in Hank’s solution, J. Alloys Compd. 698 (2017)
643–653.
[14] M. Toorani, M. Aliofkhazraei, M. Mahdavian, R. Naderi, Effective PEO/silane
pretreatment of epoxy coating applied on AZ31B Mg alloy for corrosion protection,
Corros. Sci. 169 (2020), 108608.
[15] M. Toorani, M. Aliofkhazraei, M. Mahdavian, R. Naderi, Superior corrosion
protection and adhesion strength of epoxy coating applied on AZ31 magnesium
alloy pre-treated by PEO/silane with inorganic and organic corrosion inhibitors,
Corros. Sci. 178 (2021), 109065.
[16] M. Toorani, M. Aliofkhazraei, R. Naderi, Ceria-embedded MAO process as
pretreatment for corrosion protection of epoxy films applied on AZ31-magnesium
alloy, J. Alloys Compd. 785 (2019) 669–683.
[17] M. Toorani, M. Aliofkhazraei, R. Naderi, Role of lanthanum nitrate in protective
performance of PEO/epoxy double layer on AZ31 Mg alloy: electrochemical and
thermodynamic investigations, J. Ind. Eng. Chem. 53 (2017) 213–227.
[18] D. Mashtalyar, K. Nadaraia, S. Sinebryukhov, S. Gnedenkov, Polymer-containing
layers formed by PEO and spray-coating method, Mater.TodayProc. 11 (2019)
150–154.
[19] D. Mashtalyar, S. Gnedenkov, S. Sinebryukhov, I. Imshinetskiy, A. Gnedenkov,
V. Bouznik, Composite coatings formed using plasma electrolytic oxidation and
fluoroparaffin materials, J. Alloys Compd. 767 (2018) 353–360.
[20] S. Gnedenkov, S. Sinebryukhov, D. Mashtalyar, Composite coatings formed on the
PEO-layers with the use of solutions of tetrafluoroethylene telomers, Surf. Coat.
Technol. 346 (2018) 53–62.
[21] C. Liu, X. Lu, Y. Li, Influence of post-treatment process on corrosion and wear
properties of PEO coatings on AM50 Mg alloy, J. Alloys Compd. 870 (2021),
159462.
[22] M. Ostapiuk, Corrosion resistance of PEO and primer coatings on magnesium alloy,
J. AsianCeram. Soc. 9 (2021) 40–52.
[23] G. Zhang, E. Jiang, L. Wu, W. Ma, H. Yang, A. Tang, F. Pan, Corrosion protection
properties of different inhibitors containing PEO/LDHs composite coating on
magnesium alloy AZ31, Sci. Rep. 11 (2021) 1–14.
[24] A. Fattah-alhosseini, R. Chaharmahali, K. Babaei, Impressive strides in
amelioration of corrosion and wear behaviors of Mg alloys using applied polymer
coatings on PEO porous coatings: a review, J. Magnes. Alloy. 10 (2022)
1171–1190.
[25] M.J. Anjum, J. Zhao, V.Z. Asl, G. Yasin, W. Wang, S. Wei, W.Q. Khan, In-situ
intercalation of 8-hydroxyquinoline in Mg-Al LDH coating to improve the corrosion
resistance of AZ31, Corros. Sci. 157 (2019) 1–10.
[26] J.K.F. Suh, H.W. Matthew, Application of chitosan-based polysaccharide
biomaterials in cartilage tissue engineering: a review, Biomaterials 21 (2000)
2589–2598.
[27] J. Dou, H. Yu, C. Chen, R.L.W. Ma, M.M.F. Yuen, Preparation and microstructure of
MAO/CS composite coatings on Mg alloy, Mater. Lett. 271 (2020), 127729.
[28] K. Bai, Y. Zhang, Z. Fu, C. Zhang, X. Cui, E. Meng, S. Guan, J. Hu, Fabrication of
chitosan/magnesium phosphate composite coating and the in vitro degradation
properties of coated magnesium alloy, Mater. Lett. 73 (2012) 59–61.
[29] C. Yu, L.Y. Cui, Y.F. Zhou, Z.Z. Han, X.B. Chen, R.C. Zeng, S.K. Guan, Self-
degradation of micro-arc oxidation/chitosan composite coating on Mg-4Li-1Ca
alloy, Surf. Coat. Technol. 344 (2018) 1–11.
[30] A. Dey, R. Umarani, H.K. Thota, P. Bandyopadhyay, A. Rajendra, A.K. Sharma, A.
K. Mukhopadhyay, Corrosion and nanoindentation studies of MAO coatings, Surf.
Eng. 30 (2014) 913–919.
[31] S. Liu, Y. Qi, Z. Peng, J. Liang, A chemical-free sealing method for micro-arc
oxidation coatings on AZ31 Mg alloy, Surf. Coat. Technol. 406 (2021), 126655.
[32] ASTM D3359, Standard Test Methods for Measuring Adhesion by Tape Test, 2009.
[33] T. Kokubo, H. Takadama, How useful is SBF in predicting in vivo bone bioactivity?
Biomaterials 27 (2006) 2907–2915.
[34] Y. Yürektürk, F. Muhaffel, M. Baydoğan, Characterization of micro arc oxidized
6082 aluminum alloy in an electrolyte containing carbon nanotubes, Surf. Coat.
Technol. 269 (2015) 83–90.
[35] X. Lv, L. Cao, Y. Wan, T. Xu, Effect of different electrolytes in micro-arc oxidation
on corrosion and tribological performance of 7075 aluminum alloy, Mater. Res.
Express 6 (2019), 086421.
[36] L. Xiang, Y.C. Jin, Y. Jin, Hydrothermal modification of Mg(OH)2 particles in
NaOH solution, <sb:contribution><sb:title>Chin. J.</sb:title> </sb:
contribution><sb:host><sb:issue><sb:series><sb:title>Process. Eng.</sb:
title></sb:series></sb:issue></sb:host> 3 (2003) 116–120.
[37] A. Ghasemi, V.S. Raja, C. Blawert, W. Dietzel, K.U. Kainer, Study of the structure
and corrosion behavior of PEO coatings on AM50 magnesium alloy by
electrochemical impedance spectroscopy, Surf. Coat. Technol. 202 (2008)
3513–3518.
[38] J. Dou, J. Wang, Y. Lu, C. Chen, H. Yu, R.L.W. Ma, Bioactive MAO/CS composite
coatings on Mg-Zn-Ca alloy for orthopedic applications, Prog. Org. Coat. 152
(2021), 106112.
[39] L.Y. Cui, R.C. Zeng, S.K. Guan, W.C. Qi, F. Zhang, S.Q. Li, E.H. Han, Degradation
mechanism of micro-arc oxidation coatings on biodegradable Mg-Ca alloys: the
influence of porosity, J. Alloys Compd. 695 (2017) 2464–2476.
[40] B.D. Hahn, D.S. Park, J.J. Choi, J. Ryu, W.H. Yoon, J.H. Choi, S.G. Kim, Aerosol
deposition of hydroxyapatite-chitosan composite coatings on biodegradable
magnesium alloy, Surf. Coat. Technol. 205 (2011) 3112–3118.
[41] M. Toorani, M. Aliofkhazraei, A.S. Rouhaghdam, Microstructural, protective,
inhibitory and semiconducting properties of PEO coatings containing CeO2
nanoparticles formed on AZ31 Mg alloy, Surf. Coat. Technol. 352 (2018) 561–580.
L. Xu et al.
[42] G. Zhang, L. Wu, A. Tang, B. Weng, A. Atrens, S. Ma, F. Pan, Sealing of anodized
magnesium alloy AZ31 with MgAl layered double hydroxides layers, RSC Adv. 8
(2018) 2248–2259.
[43] C.Y. Li, X.L. Fan, R.C. Zeng, L.Y. Cui, S.Q. Li, F. Zhang, S.K. Guan, Corrosion
resistance of in-situ growth of nano-sized Mg(OH)2 on micro-arc oxidized
magnesium alloy AZ31-influence of EDTA, J. Mater. Sci. Technol. 25 (2019)
1088–1098.
[44] T. Ishizaki, S. Chiba, K. Watanabe, H. Suzuki, Corrosion resistance of Mg-Al layered
double hydroxide container-containing magnesium hydroxide films formed
directly on magnesium alloy by chemical-free steam coating, J. Mater. Chem. A 1
(2013) 8968–8977.
[45] A. Di Martino, M. Sittinger, M.V. Risbud, Chitosan: a versatile biopolymer for
orthopaedic tissue-engineering, Biomaterials 26 (2005) 5983–5990.
[46] J.I. Kadokawa, R. Shimohigoshi, K. Yamashita, K. Yamamoto, Synthesis of chitin
and chitosan stereoisomers by thermostable α-glucan phosphorylase-catalyzed
enzymatic polymerization of α-D-glucosamine 1-phosphate, Org. Biomol. Chem. 13
(2015) 4336–4343.
[47] C.S. Wu, Y.C. Hsu, H.T. Liao, Y.X. Cai, Antibacterial activity and in vitro evaluation
of the biocompatibility of chitosan-based polysaccharide/polyester membranes,
Carbohydr. Polym. 134 (2015) 438–447.
[48] M.L. Zheludkevich, J. Tedim, C.S.R. Freire, S.C. Fernandes, S. Kallip, A. Lisenkov,
M.G.S. Ferreira, Self-healing protective coatings with “green” chitosan based pre-
layer reservoir of corrosion inhibitor, J. Mater. Chem. 21 (2011) 4805–4812.
[49] T. Sun, C.L. Wu, H. Hao, Y. Dai, J.R. Li, Preparation and preservation properties of
the chitosan coatings modified with the in situ synthesized nano SiOx, Food
Hydrocolloid. 54 (2016) 130–138.
[50] W. Ye, M.F. Leung, J. Xin, T.L. Kwong, D.K.L. Lee, P. Li, Novel core-shell particles
with poly(n-butyl acrylate) cores and chitosan shells as an antibacterial coating for
textiles, Polymer 46 (2005) 10538–10543.
[51] Z. Jia, P. Xiong, Y. Shi, W. Zhou, Y. Cheng, Y. Zheng, S. Wei, Inhibitor
encapsulated, self-healable and cytocompatible chitosan multilayer coating on
biodegradable mg alloy: a pH-responsive design, J. Mater. Chem. B 4 (2016)
2498–2511.
[52] Z. Qiu, J. Sun, R. Wang, Y. Zhang, X. Wu, Magnet-induced fabrication of a
superhydrophobic surface on ZK60 magnesium alloy, Surf. Coat. Technol. 286
(2016) 246–250.
[53] L.Y. Cui, H.P. Liu, W.L. Zhang, Z.Z. Han, M.X. Deng, R.C. Zeng, Z.L. Wang,
Corrosion resistance of a superhydrophobic micro-arc oxidation coating on Mg-4Li-
1Ca alloy, J. Mater. Sci. Technol. 33 (2017) 1263–1271.
[54] Q. Jin, G. Tian, J. Li, Y. Zhao, H. Yan, The study on corrosion resistance of
superhydrophobic magnesium hydroxide coating on AZ31B magnesium alloy,
Colloids Surf. A 577 (2019) 8–16.
[55] L. Wang, B.P. Zhang, T. Shinohara, Corrosion behavior of AZ91 magnesium alloy in
dilute NaCl solutions, Mater. Des. 31 (2010) 857–863.
[56] A. Castellanos, A. Altube, J.M. Vega, E. García-Lecina, J.A. Díez, H.J. Grande,
Effect of different post-treatments on the corrosion resistance and tribological
properties of AZ91D magnesium alloy coated PEO, Surf. Coat. Technol. 278 (2015)
99–107.
14
Progress in Organic Coatings 170 (2022) 107002
[57] H. Duan, K. Du, C. Yan, F. Wang, Electrochemical corrosion behavior of composite
coatings of sealed MAO film on magnesium alloy AZ91D, Electrochim. Acta 51
(2006) 2898–2908.
[58] A. Ghasemi, V.S. Raja, C. Blawert, W. Dietzel, K.U. Kainer, The role of anions in the
formation and corrosion resistance of the plasma electrolytic oxidation coatings,
Surf. Coat. Technol. 204 (2010) 1469–1478.
[59] X.J. Cui, X.Z. Lin, C.H. Liu, R.S. Yang, X.W. Zheng, M. Gong, Fabrication and
corrosion resistance of a hydrophobic micro-arc oxidation coating on AZ31 Mg
alloy, Corros. Sci. 90 (2015) 402–412.
[60] Z. Li, W. Yang, Q. Yu, Y. Wu, D. Wang, J. Liang, F. Zhou, New method for the
corrosion resistance of AZ31 Mg alloy with porous micro-arc oxidation membrane
as an ionic corrosion inhibitor container, Langmuir 35 (2018) 1134–1145.
[61] Y. Zuo, T. Li, P. Yu, Z. Zhao, X. Chen, Y. Zhang, F. Chen, Effect of graphene oxide
additive on tribocorrosion behavior of MAO coatings prepared on Ti6Al4V alloy,
Appl. Surf. Sci. 480 (2019) 26–34.
[62] J. Liang, P.B. Srinivasan, C. Blawert, M. Störmer, W. Dietzel, Electrochemical
corrosion behaviour of plasma electrolytic oxidation coatings on AM50 magnesium
alloy formed in silicate and phosphate based electrolytes, Electrochim. Acta 54
(2009) 3842–3850.
[63] S. Khorsand, K. Raeissi, M.A. Golozar, Effect of oxalate anions on zinc
electrodeposition from an acidic sulphate bath, J. Electrochem. Soc. 158 (2011)
D377.
[64] A.I. Muñoz, J.G. Antón, J.L. Guiñón, V.P. Herranz, The effect of chromate in the
corrosion behavior of duplex stainless steel in LiBr solutions, Corros. Sci. 48 (2006)
4127–4151.
[65] S. Liu, G. Li, Y. Qi, Z. Peng, Y. Ye, J. Liang, Corrosion and tribocorrosion resistance
of MAO-based composite coating on AZ31 magnesium alloy, J. Magnes.Alloy.
(2021), https://doi.org/10.1016/j.jma.2021.04.004. In press.
[66] J. Liang, P.B. Srinivasan, C. Blawert, W. Dietzel, Influence of chloride ion
concentration on the electrochemical corrosion behaviour of plasma electrolytic
oxidation coated AM50 magnesium alloy, Electrochim. Acta 55 (2010) 6802–6811.
[67] F. Cao, M. Miao, P. Yan, Hydration characteristics and expansive mechanism of
MgO expansive agents, Constr. Build. Mater. 183 (2018) 234–242.
[68] M. Fazel, H.R. Salimijazi, M.A. Golozar, A comparison of corrosion, tribocorrosion
and electrochemical impedance properties of pure Ti and Ti6Al4V alloy treated by
micro-arc oxidation process, Appl. Surf. Sci. 324 (2015) 751–756.
[69] M.A. Golozar, K. Raeissi, M. Fazel, Evaluation of corrosion and tribocorrosion of
plasma electrolytic oxidation treated Ti-6Al-4V alloy, Surf. Coat. Technol. 244
(2014) 29–36.
[70] M. Buciumeanu, A. Araujo, O. Carvalho, G. Miranda, J.C.M. Souza, F.S. Silva,
B. Henriques, Study of the tribocorrosion behaviour of Ti6Al4V- HA biocomposites,
Tribol. Int. 107 (2017) 77–84.
[71] E. Matykina, I. Garcia, R. Arrabal, M. Mohedano, B. Mingo, J. Sancho, A. Pardo,
Role of PEO coatings in long-term biodegradation of a Mg alloy, Appl. Surf. Sci.
389 (2016) 810–823.
[72] L. Xu, N. Liu, L. Cao, Y. Wan, Influences of electrolytes on tribocorrosion
performance of MAO coating on AZ31B magnesium alloy in simulated body fluid,
Int. J. Appl. Ceram. Technol. 18 (2021) 1657–1669.