Journal of Alloys and Compounds 885 (2021) 161001

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Journal of Alloys and Compounds

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

Research progress on surface protective coatings of biomedical

degradable magnesium alloys ]]
]]]]]]
]]

⁎ ⁎
Yun Liu a, Yuan Zhang a,b, , Yan-Li Wang b, Ya-Qiang Tian a, Lian-Sheng Chen a,
a
Key Laboratory of the Ministry of Education for Modern Metallurgy Technology, North China University of Science and Technology (NCST), Tangshan 063210, China
b
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing (USTB), Beijing 100083, China

a r t i cl e i nfo a bstr ac t

Article history: Till now, the novel Mg alloys acting as the medical materials have drawn much attention, due to their
Received 22 April 2021 spontaneous degradability, favorable mechanical properties and the excellent biocompatibilities.
Received in revised form 24 June 2021 Unfortunately, they were inevitably affected by flow erosion, corrosion fatigue, stress-interaction and dynamic
Accepted 27 June 2021
wear under the human body conditions, leading to significant mechanical-performance attenuation and
Available online 29 June 2021
premature fracture failure. Thus, how to explore and obtain the biomedical Mg-based alloys with controllable
degradation rate and suitable biocompatibility was the key issue. Surface modification is a typical method to
Keywords:
Surface protective coatings improve the corrosion resistance. It can isolate the Mg-matrix from the electrolyte by establishing the cor­
Conversion coating rosion barrier without changing the microstructure characteristics. Also, it can change the layer structure and
Degradation rate further enhance the degradation behaviors and biological activities of biomedical Mg alloys. In this text, the
Mg alloys latest research progresses of surface modification for Mg alloys were reviewed, and the formation mechanism,
Biocompatibility film layer features as well as the rupture mechanism of conversion coatings were revealed. Besides, the
Deposition layer interaction roles of Mg-matrix/modified-layer and modified-layer/electrolyte were analyzed through the
comparison of film-layer structure, morphology and the establishment of degradation rates for various
modified Mg alloys. Moreover, the internal relationships between the biological biocompatibilities and de­
gradation rates in different corrosive conditions were deeply explored. Finally, the problems of surface
modification on biomedical Mg alloys were proposed and the future development directions were prospected.
© 2021 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 2
2. Conversion coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 2
2.1. Chemical conversion coating . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 2
2.2. Ionic liquid conversion coating . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 4
2.3. Alkali heat treatment (AHT) conversion coatings . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 5
2.4. Plasma electrolytic oxidation coating (PEO). . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 8
3. Deposition coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 11
3.1. PVD coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 11
3.2. Atomic layer deposition (ALD) coating. . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 11
3.3. Electrolytic deposition layer . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 14
3.4. Organic biopolymer coating . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 14
4. Conclusion and future outlook . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 17
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 18

⁎
Corresponding author at: Key Laboratory of the Ministry of Education for Modern
Metallurgy Technology, North China University of Science and Technology (NCST),
Tangshan 063210, China.
⁎
Corresponding author.
E-mail addresses: surpassyuan@126.com (Y. Zhang),
kyckfk@ncst.edu.cn (L.-S. Chen).

https://doi.org/10.1016/j.jallcom.2021.161001
0925-8388/© 2021 Elsevier B.V. All rights reserved.
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1. Introduction
Compared with other biomedical metals (Co, Ni-based, Ti-based,
stainless steel), Mg-based alloys have attracted extensive attention,
due to its high biocompatibilities, excellent degradation and favor­
able mechanical properties [1–4]. As a large-scale bone-repair ma­
terial, Mg-based alloys can effectively reduce the stress shielding
effect and stimulate bone healing [5,6]. As a small thin-walled vas­
cular stent material, Mg-based alloys can maintain support and
positive reconstruction in narrow blood vessels, and then degrade
and disappear by itself [6]. Also, it participated in almost all life
activities, which maintained the stability of nucleic acid structure
and activated the enzymes in the body. Therefore, magnesium alloys
as a new generation of medical implant materials show great ap­
plication potential and development prospects [6–8]. However, the
corrosion rate of magnesium alloys under physiological conditions
was excessive, and the mechanical support effect cannot be
achieved. Besides, the relevant results have been proven by our
previous studies [9–16]. Therefore, the development of high-per­
formance Mg-based alloys with controllable degradation rates and
suitable biocompatibility was the urgent issue.
The key issue of medical Mg alloys is the precise control of its de­
gradation rate. Until now, the methods to modify the corrosion beha­
vior of medical Mg alloys mainly included the heat-treatment [17–19],
high-purity [20–22], micro-alloying [8,23–25], amorphous [3,4],
plastic-deformation [14,19,24] and surface modification [5–7,26,27].
Except for the surface modification, other methods with regarding to
the improving corrosion resistance were at the expense of mechanical
property. Besides, the corrosion contact between the α-Mg matrix and
the electrolyte solution cannot be completely prevented via micro­
structure adjustment, restricting the clinical practice of medical Mg
alloys to some extent. As for surface modification, it can isolate the
matrix from corrosion electrolyte by establishing the corrosion barrier,
change the film layer structure and optimize the biological activity
without adjustment of microstructure. Besides, the preparation process
and theory of degradable biomedical Mg alloys with surface mod­
ification coatings have been rapidly developed in recent years, due to
the preparative technique with booming development [1,5,26,27].
Generally, the surface modification can be divided into four types by
process methods: mechanical, physics, chemical and biological coating.
However, according to the formation mechanism, it can be divided into
conversion coatings (phosphate, fluoride, alkali heat treatment, mi­
croarc oxidation conversion coatings) and deposition coatings (PVD,
ALD, ED, Organic biopolymer coatings), and has played an important
role in actual operations. In this text, the latest studies about the sur­
face modification treatments of degradable Mg alloys were reviewed.
Also, the interactions mechanism between the surface modification
coatings and electrolyte solution was revealed, the formation/rupture
mechanism of modified layer in biological medium were discussed.
Moreover, the relationship between the modified layer characteristics,
degradation rates and biological-activities in vivo was deeply explored.
Finally, the development directions were predicted.
2. Conversion coating
2.1. Chemical conversion coating
Chemical conversion coatings were formed through the interac­
tions of chemical dissolution and precipitation [26,27]. Due to the
simple operation and inexpensive cost, it was widely used in the
2
Journal of Alloys and Compounds 885 (2021) 161001
biomedical field. Especially in highly active metals such as Mg, the
corrosion behavior was mainly controlled by the precipitation of
degradation products. The formation mechanism of chemical con­
version coatings was controlled by the precipitation status of pas­
sivation layer on the metal surface. Following, the treatment can
cause the samples to be converted to the low-active oxides, carbo­
nate, chromate and fluoride. Thus, it can retard the dissolution rates
of these active-metals, offering an excellent corrosion resistance. For
instance, Prabhu et al. [28] investigated the morphological char­
acteristics and degradation behaviors of chemical conversion coating
(CCC) on the surface of Mg-4Zn, which was prepared in saturated
NaHCO3 (9 g/100 ml) solution for different times (1, 2, 4, 8, 16, 24, 48,
96 h) at 30 °C. The results illustrated that the dense coating was
achieved in Mg-4Zn after 24 h incubation (high-degree mineraliza­
tion and complete coverage), with the corrosion rate of
1.099 ml cm−2 day−1. With sustained exposure to SBF solution, the
CCC coating dissolves and gradually cracks to the expose the sub­
strate to corrosion medium. Zai et al. [29] reported the micro­
structure characteristics and degradation behavior of magnesium
phosphate (Mg-P) coating on AZ31 alloy treated by various pH (2.5,
3.0, 3.5, 4.0) and temperature (40, 60, 80 °C). Results indicated that
the modified layer owns the precipitated outer layer and in-situ
grown layer, the dense inner-layer has more corrosion resistance
(Fig. 1). The crystal morphology was controlled by pH, whereas the
thickness was dominated by experimental temperature. Therein, the
superior coating was achieved at 80 °C, pH 3.0, with the current
density of 57 nA/cm2.
Su et al. [30] also analyzed the effects of pH and temperature on
microstructure and corrosion behavior of calcium phosphate con­
version coating (CPCC) on the AZ60. Results indicated that the pH
values and temperature could remarkably affect the coating process
and porosity percentage, thereby altering the corrosion protection
efficiency and corrosion rate. Therein, the CPCC formed at pH 2.8–3.0
and 37 °C can provide the optimum corrosion protection. However,
at the early stage of hydrogen evolution, the production layer was
mainly composed of chips and thin sheets (Eqs. (1)–(4)). Moreover,
the surface layer will produce coarse crystals when the pH is too
high, inducing the loose features, thereby and deteriorate the cor­
rosion resistance.
Mg → Mg2+ + 2e; 2H2O + 2e → 2OH− + H2; Mg + 2H2O → Mg2+
+ 2OH− + H2 (1)
Mg + H2PO4− + OH− + 2H2O → MgHPO4·3H2O (2)
Ca2+ + H2PO4− + OH− + 2H2O → CaHPO4·2H2O (3)
9Ca2+ + Mg2+ + 7H2PO4− + 13OH− → Ca9Mg(HPO4)(PO4)6 + 13H2O
(4)
Zhang et al. [31] investigated the effects of pretreatment pro­
cesses (sand-blasting, grinding and polishing) on the microstructure
and corrosion behaviors of phosphate conversion coating (PCC) on
AZ91D. The alloy was treated for 10 min, 60 °C at the solution bath
consisting of 35 g/L NaH2PO4, 5 g/L (NH4)2HPO4, 2 g/L NaNO3 and
35 g/L MnSO4. Results indicated that the corrosion current densities
were 3290 ± 46.12 μA/cm2, 6.91 ± 1.14 μA/cm2, 6.21 ± 0.91 μA/cm2,
3.85 ± 0.78 μA/cm2, 4.86 ± 0.522 μA/cm2, respectively. The high
corrosion resistance of ground/polished Mg was associated with the
relatively low surface roughness and electrochemical activity, which
facilitated the formation of uniform/protective phosphate conver­
sion coatings. Jayaraj et al. [32] continued to investigate the micro­
structure characteristics and corrosion behaviors of lanthanum
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Fig. 1. Cross-section morphologies of coated samples prepared at 40 °C, 60 °C and 80 °C in conversion solution with different pH values (2.5, 3.0, 3.5 and 4.0) (Scale bar is
100 µm) [29].
based phosphate coating in 3.5% NaCl solution. Herein, the coating
obtained in nitrate bath with water is LaP1, whereas the coating
obtained in ethanol based nitrate solution was LaP2. Electrochemical
results declared that the LaP2 owns the best corrosion resistance,
with the corrosion rate of 0.162 mm/y, due to the formation of var­
ious compact degradation products (Eqs. (5)–(8)). Additionally, the
LaP1 hydroxides coatings using water as solvent after evaporation
were prone to cracking. Moreover, the electrolyte solution could
easily penetrate the Mg substrate, resulting in rapid degradation.
When the ethanol was used as the solvent of nitrate solution, it will
promote the formation of LaPO4 and uniform coating with small
cracks, thereby enhancing the corrosion resistance.
NH4H2PO4 → NH4+ + H2PO4−; Mg → Mg2+ + 2e−
Mg + H2PO4− + 3H2O → MgHPO4·3H2O
La3+ + PO43− → LaPO4; La3+ + 3OH− → La(OH)3
Mg 2+
+ NH4+− +PO4 3−−
+ 6H2O → MgNH4HPO4 · 6H2O
Besides, Maurya et al. [33] reported that the modified-layer
characteristics and corrosion resistance of Mg-9Li-7Al-1Sn (LAT971)/
Fig. 2. SEM images of phosphate chemical conversion (PCC) coated surface (a, c) and cross-section (b, d) of LAT971 and LAT9531; SEM micrograph after corrosion test (e, f)
uncoated LAT971, (g, h) PCC coated LAT971 and LAT9531, respectively [33].
Journal of Alloys and Compounds 885 (2021) 161001
Mg-9Li-5Al-3Sn-1Zn (LAT9531) were remarkably improved by pre­
paration of the environment-friendly phosphate chemical conver­
sion coating. The corrosion rate was reduced from un-coated
(0.82 mA/cm2, 0.34 mA/cm2) to coated (6.74 × 10−7 mA/cm2, 5.39 ×
10−7 mA/cm2), shown in Fig. 2, which offers the protection efficiency
of >99%. The phenomenon was attributed to the intensive and strong
physical barrier, which could retard the formation of degradation
productions and restrict the initiation of pitting, thereby regulating
the degradation rates of coated-LA971/LAT9351. The high corrosion
resistance and low electrical contact resistance of conversion coating
on AZ91D was designed by Duan et al. [34]. EIS measurements in­
dicated that the |Z|0.01HZ of the coated AZ91D (approx. 2900 Ω cm2) is
greater than that of the bare AZ91D (approx. 400 Ω cm2). Due to the
(5)
presence of strong oxidizing agents, it could suppress the hydrogen
(6) reduction reaction, which was associated with its higher redox po­
tentials, thereby retarding the growth of flower-like phosphate
(7) crystals.
(8) Barajas et al. [35] analyzed the degradation behavior of AZ31
treated by fluoride conversion coatings, which were conducted by
immersion in HF under various times and concentrations. The po­
larization results indicated that the degradation behaviors of the
3
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

treated AZ31 decreased firstly and then increased (2.21 × 10−5 →
1.70 × 10−7 → 5.84 × 10−7 → 2.28 × 10−7 → 1.51 × 10−7 A/cm2). This
phenomenon was attributed to the compactness and thickness of
fluoride-coatings. Moreover, the higher contents of the fluorides in
the conversion layer, the thicker of the conversion layer, which is
helpful to reduce the dissolution rates. However, the presence of
intermetallic particles within the AZ31 facilitated the formation of
defects and the growth of corrosion products, leading to the de­
tachment of fluoride-coatings. Panemangalore et al. [36] explored
the corrosion behaviors of Mg-2Zn, Mg-2Zn-2Er, Mg-3Zn-0.5Er with
fluorine-coating in phosphate butter saline solution, which was
fabricated in a 40% HF solution at room temperature for 24 h. Firstly,
it can be seen that the dense, smooth conversion coatings were
covered with tested samples, and these micro-pores were randomly
distributed on the surface, which was associated with hydrogen
evolution. Also, the SEM/EDS characterization revealed that the
distribution of solute elements was uniform along the coating at the
cross-section, indicating the presence of good chemical adhesion
and strong adhesion ability. Degradation behaviors further indicated
the corrosion resistance, with the corrosion rate of 0.013, 0.02,
0.031 mm/y, respectively. Fintová et al. [37] analyzed the
degradation behavior of the unconventional fluoride coatings on
AZ61 via Na[BF4] salt melt. Experimental results indicated that the
inferior corrosion resistance could be appeared with the lower
coating temperature and shorter time. The presence of micro-pores
will lead to the contact with the corrosion solution, thereby dama­
ging the modified-layer structure and causing more pronounced
corrosion attack. Nevertheless, the degradation rates on degradable
Mg alloys can be controlled by regulating/establishing carriers with
optimum mineralization features. However, the nano-scale char­
acterization at the interface was still lacking, particular in the
growth in-situ. Besides, authors summarized the key conditions of
chemical conversion coating under various parameters (Table 1),
which was helpful for readers to select the suitable preparation
procedures on bio-degradation Mg-based implants.
2.2. Ionic liquid conversion coating
Ionic liquid conversion coating (ILC) refers to a room temperature
molten salt or low-silicon salt, which is composed solely of the ca­
tions and anions, and does not contain the neutral molecules. Due to
their wide electrochemical windows, extremely low vapor pressures,

Table 1
The chemical conversion coating formation conditions [28,30,32,33,38–42].

Alloys Coating Conditions pH T/°C Time Ref.

Mg-4Zn CO32− 90 g/L NaHCO3 – 30 – [28]

Mg-8.5Li Zn-P 50 g/L Zn(H2PO4)2 2 45 15 min [30]
20 g/L NaH2PO4
30 g/L Mn(NO3)2
5 g/L C6H8O7
0.2 g/L C18H29NaO3S
AZ31 LA-P MgNH4PO4·6H2O 7.5 55 20 min [32]
MgHPO4·3H2O
NH4H2PO4
20 g/L LaNO3
Ethanol solution
AZ91D Ce-P 5 g/L Ce(NO3)3·6H2O / RT 2h [33]
1 g/L Citric
3 wt% Na3PO4
AZ91D SnO42− 0.2 M Na2SO3·3H2O – 80 0–60 min [38]
0.1 M Na4P2O7·10H2O
0.125 M NaOH
0.08 M CH3COONa·3H2O
ZK60 F 48% HF – – 96 h [39]
Polypropylene
Mg-Zn-Ca F 40% HF – – 24 h [40]
Ca-P 0.042 mol/L Ca(NO3)2·4H2O 5 80 20 min
0.025 mol/L NH4H2PO4
0.1 mol/L NaNO3
JDBM Ca-P (C10H12N2O8)CaNa2 8.2 – – [41]
NaH2PO4
AZ31 Mg-P 0.4 mol/L Mg(NO3)2 2.7 60 20 min [42]
0.2 mol/L H3PO4
Zn-P 0.1 mol/L Zn(NO3)2 [42]
0.2 mol/L H3PO4
Ca-P 0.2 mol/L Ca(NO3)2 [42]
0.2 mol/L H3PO4
ZnMg-P 0.4 mol/L Mg(NO3)2 [42]
0.1 mol/L Zn(NO3)2
0.2 mol/L H3PO4
CaMg-P 0.4 mol/L Mg(NO3)2 [42]
0.2 mol/L Ca(NO3)2
0.2 mol/L H3PO4
ZnCa-P 0.1 mol/L Zn(NO3)2 [42]
0.2 mol/L Ca(NO3)2
0.2 mol/L H3PO4
ZnCaMg-P 0.4 mol/L Mg(NO3)2 [42]
0.1 mol/L Zn(NO3)2
0.2 mol/L Ca(NO3)2
0.2 mol/L H3PO4

4
Y. Liu, Y. Zhang, Y.-L. Wang et al.
good conductivity, high thermal stability and flexible molecular
structure, they were mainly used as the green solvent in electro­
chemical, catalysis and chemical synthesis fields [43]. For instance,
Elsentriecy et al. [44] analyzed the degradation behaviors of am­
monium- phosphate ionic-liquid conversion coatings in 1 wt% NaCl
saturated with Mg(OH)2. Results declared that the corrosion re­
sistance of IL-300 °C was substantially improved than that of the
bare, IL, IL-RT (195.843, 131.638, 13.566, 25.973 μA/cm2), due to
strong passivation behavior.
Besides, the thermal stress of the high temperature preparation
can promote the IL deposition and interaction with the Mg matrix,
thereby enhancing the corrosion resistance with the formation of
conversion layer. Moreover, the IL coating was composed of two-
layer structure, namely that the carbonaceous compounds, metal
phosphates and oxides, with the thickness of 70–80 nm. Finally, the
thermal-stress in the heat-treatment process induced the IL coating
decomposition and the decomposed species can active react with
the Mg2+ to create the phosphates and organic compounds, resulting
in the growth of oxides with dense characteristics. Also, Zhang et al.
[45] evaluated the degradation and cytotoxicity of three phosphate-
based ILs to human coronary artery endothelial cells, due to their
approximate low toxic. The results declared that the formation of IL
coating has proceeded progressively, and treatment time plays an
important role. Compared with other treatment times, the 5 h
treatment on ILs owns the best corrosion resistance, due to more
dense, passive and chemical homogeneous film layer (less corroded,
with the few shallow pits). SECM maps further indicated that the
non-homogeneous corrosion reactivity was occurred on un-treated
AZ31 compliance with the non-uniform distribution of tip-currents.
In addition, the current density at the top was almost 5 times more
than the bottom part. However, the 5 h-ILs owns more homogeneous
surface on SEC map. The scenario was associated with the preference
deposition of ILs around intermetallic particles, making the areas
less susceptible to corrosion. The synthesis, corrosion mechanism of
benzyl triphenyl phosphonium bis (trifluoromethylsulfonyl) amide
([BPP][NTf2]) was analyzed, whilst the theoretical calculations be­
tween [BPP][NTf2] and [P6,6,6,14][NTf2] were evaluated by Su et al.
[46,47]. Compared to initial curves without the inhibitor, the
Rp value increased as the concentrations of [BPP][NTf2] elevated
(659.9 → 2489 → 3203 → 4643 Ω cm2 → 7646 Ω cm2). The H2O
molecules and corrosive ions were inhibited by [BPP][NTf2] isolating
from the substrate, resulting in less active sites of pitting corrosion.
Besides, the adsorption of [BPP][NTf2] on substrate follows with the
Langmuir isotherm model, which was associated with the chemical
adsorption and covalent bond. The NTf2 will occur decomposition
into the small species by cleavages of S-N, S-C, C-F, etc., shown as
following Eqs. (9)–(11).
N(SO2CF3)2− + e → N(SO2CF3)22− → ·NSO2CF3− + SO2CF3−
·NSO2CF3− +e→ NSO2− + CF3−; SO2CF3− +e→ SO2− + CF3−
CF3SO2 NSO2CF3− −
+ e → F + CF2SO2NSO2CF3 −
Compared with conventional ILs, the deep eutectic solvent (DESs)
can be easily prepared at low cost and with high purity. Initially, Guo
et al. [48] conducted the hot corrosion of AZ31B with deep eutectic
solvent membrane (DESs). The wettability results reveal that the CA
value decreased as the temperature increased, which may be at­
tributed to the decrease in viscosity. SEM observations indicated that
the EDS films at ambient pressure would release much more che­
micals to participate the interface reaction than the isothermal
methods in the sealed vessels. Besides, the AZ31B owns the deeper
color corrosion than purity-Mg, which indicated that the porous
structure plays a vital role in creating the blackness in the butterfly
Journal of Alloys and Compounds 885 (2021) 161001
wings, due to the plenty of nano-holes on the surface (Eqs.
(12)–(15)). Electrochemical polarization curves revealed that corro­
sion rate of AZ31B was 1.974, 0.208, 0.137, 0.192 mm/y, respectively,
since the porous nature conversion film could exert the Cl− penetrate
into the substrates.
CO(NH2)2 + 2H2O → 2NH4+ + CO32− (12)
+ −
(CH3)3N (CH2)2OH + OH → N(CH3)3 + CH2]CHOH + H2O (13)
Mg(OH) + 2NH4+ + CO32− → MgCO3 + 2H2O + 2NH3 ↑ (14)
Mg + H2 → MgH2; Mg17Al12 + 17H2 → 17MgH2 + 12Al; 4Al
+ 3O2 → 2Al2O3 (15)
Subsequently, Guo et al. [49] further explored the degradation
behaviors of AZ31 B with/without the EDs-based conversion pre­
treatment. Results revealed that the main composition on the DES-
based conversion coating was MgH2, MgO and MgCO3. The density of
micro-pores on the EDS-based coatings increased as the pretreat­
ment time increased, which provided more anchor points for the
following epoxy resin coating (Fig. 3). However, without the of DES-
conversion pretreatment, the epoxy resin is difficult to be attached
on the substrate during the dip-process. The electrochemical tests
indicated that AZ31B with double layered hybrid coating pretreat­
ment owns the best corrosion resistance, with the current densities
of 0.19 μA/cm2. The improvement in corrosion behavior was attrib­
uted to the unique architecture and component including the hy­
drophobicity of the surface layer, the dense and interlocked epoxy
resin, and the corrosion resistant DES-based conversion pretreat­
ment. Li et al. [50] fabricated the chemical conversion coatings on
degradable Mg alloys through DES methods, and the biocompat­
ibility has also been analyzed. Therein, the LU-AZ has the lowest
corrosion current density (0.29 μA/cm2). It further indicated that the
DES-treatment can effectively improve the corrosion resistance of
degradable Mg alloys in simulated body fluids. The hemolysis per­
centages of the bare Mg, AZ31, LU-Mg/-AZ after 30 min contacting
were 0.89 ± 0.2, 0.62 ± 0.2, 0.36 ± 0.2, 0.13 ± 0.2%, respectively
(Fig. 4). Besides, the cytotoxicity and cytoskeleton staining results
were significantly improved by DES treatment, with visible actin
microfilaments (Fig. 4b). It can be seen that the LU-AZ possesses the
acceptable compatibility and can be considered as an implant ma­
terial. A facile anodic treatment for AZ31B was also fabricated in
choline chloride-ethylene glycol based deep eutectic solvents by
Zhang et al. [51]. The main composition of conversion coating was
composed of MgCO3 and MgO, and the SLIPS-50 owns the best
corrosion resistance, with the corrosion current density of 0.263 μA/
cm2. The immersion tests indicated that the trace amount of pits was
formed on the SLIPS-50 after 24′ immersion. The improvement in
corrosion resistance of the SHS and SLIPS might be attributed to the
(9) less contact area between the conversion films and corrosive solu­
(10) tion supported by trapped air and infused lubricant. So far, the EDS-
based coating still has some limitations (very thin/porous), which
(11) only provides short-term corrosion protection in corrosion medium.
Besides, most of coating applying organic compounds as solvents
was not environment-friendly. Therefore, in order to improve the
corrosion resistance of the DES-based conversion films, the organic
coating was indispensable. Meanwhile, it would be promising that
more effective coatings might be produced on degradable Mg alloys
by adopting different external fields at the IL/substrate interface.
2.3. Alkali heat treatment (AHT) conversion coatings
One surface treatment technique, alkali-heat treatments have
been widely studied as one of the most simple and effective methods
for biodegradable magnesium alloys, due to the formation of
5
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Fig. 3. SEM morphology of Mg/AZ31B substrates with various hot corrosion time at 160 °C: (a) Mg-5; (b) Mg-15; (c) Mg-30; (d) Mg-60; (e) AZ-5; (f) AZ-15; (g) AZ-30; (h) AZ-60;
the reflectance spectra of the pure Mg (i) and AZ31B (j) substrates after hot corrosion [49].
amorphous and densification degradation layer [52]. Also, the nano-
particles can facilitate the nucleation and growth of hydroxyapatite
and Ca-P, thereby enhancing the degradation behavior and opti­
mizing the biocompatibility. For instance, the preliminary studies
using alkaline and alkaline heat treatment indicated that the cor­
rosion rate can be remarkably decreased with no signs of cell
morphology. Initially, the cytotoxicity and corrosion behavior of
alkali-heat-treated purity-Mg in a simulated body fluid were eval­
uated by Li et al. [53]. The static degradation and pH value show that
the AHT-Mg owns the relatively eminent corrosion resistance with
regard to the un-AHTed samples. Besides, no inhibitory on marrow
cells growth and no signs of cellular lysis were detected after cyto­
toxicity tests. Gu et al. [54] further analyzed the degradation beha­
vior and cytotoxicity of Mg-1.4Ca with various alkali-heat-treated
methods (Na2HPO4, Na2CO3, NaHCO3). Herein, the corrosion rates of
untreated, NaHCO3-treated, Na2CO3-treated and Na2HPO4-treated
were 13.27, 2.08, 2.27, 2.29 mm/y. The enhancement in corrosion
resistance was attributed to the integrity and consolidation of the
degradation layer, which was formed as Eqs. (16)–(18). The cyto­
toxicity tests indicated that the AHTed alloys were not toxic to L929,
which may play an important role in osteoblastic differentiation.
6
Journal of Alloys and Compounds 885 (2021) 161001
Tang et al. [55] investigated the film structure and bonding strength
of AZ31 through alkali treatment. It indicated that the bonding
strength of the layer was decreased as the treatment time increased,
and the bonding strength of AHT-3 h between the film and the
substrate was stronger than 60 MPa. Pan et al. [56] explored the
degradation behavior and hydrophilicity of AZ31 treated by self-as­
sembly of 3-phosphonopropionic acid, APTMS and dopamine. Elec­
trochemical tests revealed that the corrosion current density of
AZ31B, MgOH, MgPho, Mg-APTMS, Mg-Dopa was 2.1 × 10−6,
8.2 × 10−6, 2.4 × 10−6, 1.7 × 10−6, 3.3 × 10−6 A cm−2. It can be deduced
that the APTMS has a phosphating effect during the process of self-
assembly, which can contribute to the increased anticorrosion apart
from the covering effect of the molecule. After the observations of
endothelial cell adhesion and proliferation (shown in Fig. 5), it can
deduce that the deposition of protein in culture may offer the sup­
port for cell attachment and growth, leading to more cell attachment
on Mg-APTMS and Mg-Pho. Jiang et al. [57] investigated the effect of
alkali/acid pretreatment on the topography and corrosion behavior
of Ca-P coating on AZ31 alloys. Electrochemical measurements re­
vealed that the HPM10 has the best corrosion resistance, with the
corrosion current density of 0.15 μA cm−2. It was attributed to the
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

Fig. 4. (a) Hemolysis percentages of samples after contacting with the erythrocytes for 30 min/24 h; (b) relative cell growth rates; (c) cytoskeleton staining results pre-osteoblast
cells [50].

proper thickness, which can provide an effective protection for the
substrate and the intact structure, ensuring the coating away from
peeling off from the substrates. On the other hand, the polyelec­
trolyte multilayered coating on Mg substrates was developed by
Kunjukunju using a layer-by-layer (LbL) technique, which can con­
trol the delivery of growth factors and required biomolecules form
the surface of these implants [58]. Besides, the coatings were
surface functionalized by chemical cross-linking and fibronectin
immobilization. Results reveal that these fluoride-pretreated
LbL-coated substrates own high bioactive and less cytotoxic than the
hydroxide-pretreated LbL-coated alloys. Moreover, the synergistic
roles of pulse electro-deposition parameters and alkali treatment on
the porous Mg-Zn scaffold were analyzed by Mirdamadi et al. [59].
The results show that as the temperature increased, the morphology
of coatings changed from the plate structure (250 nm thickness) to a
need-like structure (with the diameter less than 100 nm and length
of 2–3 µm), which was controlled by the diffusion behavior. Also,
with the increment of duty cycle, the crystal structure has been

Fig. 5. The typical fluorescent images of cells and SEM images of endothelial cells on different samples [56].

7
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Fig. 6. The schematic diagram of PEO/MAO device (a); the schematic of growth model (b); the corrosion mechanism of PEO coating: (c) thin coating with through-pores; (d)
thicker coating with complex pores [60].
changed of the deposition layer, and the smaller particles were ob­
tained at the higher duty cycles (1 h). The nucleation rates were
facilitated in finer crystal as the peak current density increased,
which owns the preferential growth. Mentioned above, the optimum
conditions to create high-quality HA coating were at 40 A/cm2, 0.1
duty cycle, 1 h time and 85 °C temperature, with the corrosion rate of
1.5 × 10−4 A/cm2. The detailed formation process of HA/
Ca10(PO4)6(OH)2 on the surface was listed as following
Eqs. (19)–(21). Based on the present researches, although the bio­
logical medical Mg-based alloys in alkali-heat-treatment have made
some progress, there were still many shortcomings. Especially the
existence of porous microstructure and the uniform interfacial ad­
hesion force lead to significant mechanical attenuation and pre­
mature failure of the material under fatigue-loadings.
2.4. Plasma electrolytic oxidation coating (PEO)
Plasma electrolytic oxidation (PEO) is to introduce the working
voltage into the high-voltage discharge area, and then to prepare a
ceramic layer on the substrate using the high-temperature sintering
effect (Fig. 6). Thus, the PEO coatings own the strong binding force
and stable chemical properties, which could remarkably improve the
corrosion resistance of degradable Mg-based alloys in medical-fields
[60,61]. Besides, the PEO coating also has a good wear, stress release
and could be applied into the bone-nail. However, the porous PEO
structure could be used as Cl− diffusion/penetration channel to ac­
celerate corrosion rate of medical Mg-based alloys. It was well
known that the growth process of PEO coating was associated with
the electrical parameters of discharging/cooling process. Ly et al.
[62] analyzed the microstructure characteristics and degradation
behaviors of PEO coating treated by various current models (uni­
polar, bipolar, hybrid models). It could be observed that the PEO
8
Journal of Alloys and Compounds 885 (2021) 161001
coating was micro-porous /rough, which were homogeneously dis­
tributed along the surface and interconnected with each other. The
average size of micro-pores of unipolar, bipolar, hybrid models was
0.62 ± 0.08, 1.09 ± 0.09, 0.94 ± 0.05 µm. Besides, these PEO coatings
have the outer and inner layer, and combined well with the sub­
strate, in which the thickness of various models was 5.6, 6.1, 6.4 µm,
respectively. The electrochemical measurements in Hank’s solution
indicated that the corrosion rate was significantly decreased after
the PEO-treatment (2.09, 0.44, 0.55, 0.37 mm/y), with the Rct value of
662, 2187, 2675, 4677 Ω cm2. The improvement of corrosion re­
sistance under the hybrid models was beneficial to create the dense
HA, with the optimum integrity and hardness, which can be served
on bone-repair and implant materials. The presence of Mg2Ca par­
ticles on PEO coatings and degradation behaviors in Hank’s solution
were further analyzed by Ding et al. [63]. The large amount of micro-
pores with the sizes less than 1 µm and the thickness about 3.46 µm
were generated on the PEO coating (Fig. 7a), whereas the presence of
MgO indicated that the coating forms during MAO treatment bathed
in an electrolyte of NaOH and Na2SiO3. The detailed formation me­
chanism of PEO coating on Mg-1Li-1Ca was illustrated in Fig. 7c1–c4:
a) the formation of thin and dense barrier coating; b) the initiation of
oxides in the depleted Ca after the presence of sparks; c) the growth
of oxides in the horizontal direction; d) the thickening process of
PEO coating. However, these defects such as micro-pores/cracks
provide the paths for corrosion factors, which can be connected with
each other, thereby facilitating the reaction-activities and dissolu­
tion kinetic. As the immersion time increased, the PEO coating
would be subject to stress from substrate pointing to coating, which
originated from the volume expansion in formation of corrosion
precipitations and additional stress of hydrogen bubble evolution.
Nevertheless, the PEO effectively retarded the dissolution rate, de­
creasing from 0.477 to 0.01 mm/y (Fig. 7d). However, due to the high
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Fig. 7. (a) SEM images of MAO coating (a1) and its (a2) EDS result, (a3) cross-sectional view and (a4) EDS scan mapping; morphology of MAO coating obtained (b1) before and
after appearance of arc discharges for (b2) (b3) 5 s, (b4) 10 s; formation mechanism illustration during micro-arc oxidation preparation: (c1) before and (c2) after appearance of
arc discharges (c3) 5 s, (c4) 10 s; corrosion morphologies of Mg-1Li-1Ca (d1) substrate and (d2–d4) MAO coating after immersion of 144 h [63].
difference of Mg2Ca with respect to the matrix, it can undergo the
attack from the solution and stress concentration caused by de­
gradation products.
The relationship between morphology, porosity and corrosion
resistance of PEO coating on extruded Mg-Ca alloys was investigated
by Cui et al. [64]. The formation of micro-pores/cracks could be at­
tributed to the difference of internal stress between the substrate
and coating, which results from the lattice distortion between the
HCP lattice of Mg and cubic lattice of MgO. In this study, as the
number of through-pores increased, the current density was re­
markably enhanced, due to the formation of galvanic-effect. Xia et al.
[65] analyzed the mechanical integrity and degradation behavior of
PEO-treated Mg-4.0Zn-0.2Ca alloys. Experiments indicated that the
O2− and F− precipitated in the arc-discharge in the micro-arc oxi­
dation process and formed dense ceramic like MgO and MgF2.
Electrochemical measurements illustrated that the MAO coated Mg-
4.0Zn-0.2Ca was less reactive to SBF, and the corrosion rates were
decreased from 2.58 × 10−3 to 4.02 × 10−4 mm/y. The tension results
indicated that the PEO treatment was not modified the mechanical
properties. However, the yield strength, ultimate tensile strength
and elongation were 158 MPa, 224 MPa and 8.3%. However, the
mechanical properties of the MAO treated Mg-4.0Zn-0.2Ca alloys are
degraded greatly after 30 day immersion in the SBF, especially in the
elongation. Thus, it was not enough for the bone-fixed application.
This was probably attributed to the surface defects. At the beginning
9
Journal of Alloys and Compounds 885 (2021) 161001
of immersion, PEO coating layer was almost no reaction with SBF;
with the gathering of corrosive ions, it will react with MAO in the
weak micro-zones; Following, the poor quality PEO can directly react
with H2O and corrosive ions. Nashrah et al. [66] investigated the
formation mechanism and degradation behavior of PEO-treated
AZ31 with various surface roughness (FS/GS). Results indicated that
the appearance of micro-discharges on the grooved occurred earlier
than that of the flat surface since the oxidized fragments nucleate
preferentially in the ridges where electrons were heavily con­
centrated under high electric fields. The oxide layer of GS was re­
latively less dense than that of the FS. The scenario was attributed to
the fact that the GS grows easily on the pre-existing coating,
whereas the oxide layer on FS grows uniformly throughout the re­
gions, resulting in higher growth rate of GS. The valleys with higher
surface area would offer preferable nucleation sites for accumulation
of corrosive ions, which accelerated the chemical reactions. Once the
passivation film cannot withstand the high electric-field, the
number of electrons would be injected into the passive film. Polar­
ization tests reveal that the RP of GS was two-order lower than that
of FS, and the corrosion rate in 3.5% NaCl was 5.141 × 10−3 and
1.686 × 10−4 mm/y. The presence large number discharge channels in
GS could provide the convenient path for Cl-. Thus, the surface
roughness will stimulate the discharge behaviors, thereby altering
the structure of oxidation layer. Chen et al. [67] analyzed the de­
gradation, cytotoxicity and antibacterial property of a Cu-containing
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

Table 2
The MAO coating formation conditions [62–64,66–72,].

Alloys Coatings Composition Current Volta Pulse Time (min) Loading Ref.
density (mA) (V) (Hz)

Mg-Zn-Ca MAO 4 g/L NaOH – 300 750 – 1 [62]

20 g/L Na2SiO3
Mg-Li-Ca MAO 10 g/L NaOH 40 – 2000 5 0.3 [63]
18 g/L Na2SiO3
Mg-0.5Ca MAO 10 g/L NaOH 40 – 2000 3 0.35 [64]
18 g/L Na2SiO3
AZ31 MAO 0.1 M KOH 50 – 60 – – [66]
0.05 M Na2SiO3
Mg-Zn-Gd-Zr MAO 1 g/L HA – 360 1000 5 0.4 [67]
1 g/L CuO
8 g/L KF
3 g/L (NaPO3)6
AZ31B MAO 15 g/L Na2CO3·9H2O – – 300 10 0.3 [68]
15 g/L KOH
10 g/L Na2B4O7·5H2O
3 ml/L C3H8O3
Mg-Zn-Sr MAO 10 g/L Na5P3O10 – 350 600 10 – [69]
2 g/L NaOH
10 ml/L C3H8O8
2.5 g/L NaF
9 g/L K2TiF6
2 g/L CH3COOAg
AZ31 MAO 6 g/L C6H18O24P6 83.3 – 500 3 0.2 [70]
10 g/L NaOH
Mg-Zn-Ca MAO 7.5 g/L (C3H7O6P)Ca – 450 680 10 0.8 [71]
15 g/L NaSiO3·9H2O
7 g/L NH4HF2
5 g/L KOH
7.5 ml/L C3H8O3
AZ31B MAO 15 g/L NaAlO2 – 425 – 3 – [72]
2 g/L NaOH
4 g/L EDTA-Ca
1.5 g(NaPO3)6

PEO coating on the extruded Mg-2Zn-1Gd-0.5Zr surface. Mor­ the film layer, and the PEO coated AZ31B exhibits the excellent
phology observations indicated that the Ca3(PO4)2, Mg/MgO and corrosion resistance. The higher anti-corrosion properties of PEO
Ca3(PO4)2 was the primary composition in PEO-treated coating, coating can restrain the electron transfer and diminish the dissolu­
while the Cu3(PO4)2, Ca3(PO4)2, Mg, MgO and Mg3(PO4)2 was formed tion rate. Besides, the other one is glycerol-molecules absorbed on
on the Cu + PEO coating. Polarization tests further verified that the the surface of PEO, which can isolate the corrosion medium form the
Cu + MAO has the lowest corrosion current (0.168 μA/cm2) compared substrate. In a word, the PEO techniques have made some huge
to the uncoated and MAO coated alloys (5.460 μA/cm2, 0.273 μA/ progress, there were still many limitations. The distribution and size
cm2), while the Rct value was 2.79 × 105, 1.91 × 105, 8.72 × 103 Ω cm2. of micro-cracks were not reasonable, which has the difficulty in
Furthermore, the degradation morphology in 3D topography also structure-modifying. Furthermore the preparation of multi­
verified the excellent corrosion resistance in Cu + PEO. This was functional organic composite coating, wear coating, antibacterial
attributed to the inert Cu can stabilize the coating facilitate the coating through PEO treatment was still lack. More importantly,
deposition of Ca-P, thereby inhibiting the dissolution rate. The ex­ authors also summarized the preparation methods of PEO coating
planation can be summarized as Eqs. (22)–(24). Also, the bacteria for degradable Mg alloys, shown in Table 2. Thus, researchers can
could be effectively killed and the Cu-PEO reveals the good anti­ easily select the most suitable modification-coating on degradable
bacterial activity due to the release of Cu2+ (Eqs. (22)–(24)). Ning Mg-based implants for the requirements of different parts of the
et al. [68] investigated the wear and corrosion behavior of PEO- human body.
treated coating on with various diamond-like (DLC), H-DLC, Si-DLC
Mg2+/Ca2+ + CO32− → Mg/CaCO3; MgCO3 + 3H2O → −MgCO3·3H2O
and Cr-DLC. Compared with PEO AZ31B, the DLC-ed could not
(16)
completely seal the surface micro-pores but can reduce the sizes of
micro-pores, having a certain sealing effect. Tribological properties Mg2+ + Na+ + HPO42− + OH− → MgNaPO4 + H2O (17)
inferred that the friction coefficient of PEO coated AZ31B was re­
markably reduced after the DLC film deposition. The excellent fric­ 3Ca2+ + 2HPO42− + 2OH−− → Ca3(PO4)2· + 2H2O (18)
tion coefficient could be attributed to the porous surface with the 2H2PO4− −−
+ 2e → 2HPO42−· + H2 ↑; 2HPO42−− + 2e −−−−
→ 2PO43−· + H2 ↑
intensive/greater hardness and roughness. The polarization test in (19)
3.5% NaCl reveals that the corrosion resistance of duplex-coating
(4.27 × 10−7, 5.20 × 10−6, 3.26 × 10−7, 5.26 × 10−6, 8.52 × 10−5 A/cm2) 10Ca2+ + PO43− + 2OH− → Ca10(PO4)6(OH)2 (20)
was remarkably improved compared to bare AZ31B (2.96 × 10−4
8Ca2+ + 6PO43− + 2H+ + 5H2O → Ca8H2(PO4)6(OH)2·5H2O (21)
A/cm2). The NSS test further indicated that the Cl− can penetrate via
2+ +
micro-pores on the surface coating interface between substrate and Cu + 2H2O → Cu(OH)2· + 2H (22)

10
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

Table 3
The PVD coating formation conditions [73–79].

Alloys Coating Gas Temperature/°C Pressure/Pa Power/W Time/min Bias/V Ref.

Mg-Ca-Zn SiO2 Ar RT 0.24 200 90 −150 [73]

Mg-Ca-Zn-Gd TiO2 Ar 100 0.5 – 150 – [74]
Mg Polymer Ar – 0.057 – 30 – [75]
AZ91 HA Ar – 0.4 400 600 −100 [76]
Mg MgAg Ar – 0.18 200 – – [77]
Mg-Ag Ar – 0.3 50 – – [77]
AZ91D Hf/Si3N4 Ar 300 0.3 250/100 10 0 [78]
AZ31 HA Ar – 0.4 500 – – [79]

corrosive electrolyte can ultimately reach the interface through the

Ca2+ + 4H+ + 2PO43− → Ca10(H2PO4)2 (23)
Mg2+ + 2PO43−− + 4H+ → Mg(H2PO4)2 (24)
3. Deposition coating
3.1. PVD coating
Physical vapor deposition coating (PVD) is a new technology to
solve the high chemical reactivity and low electrode potential of
magnesium substrates. At present, the main processing technology
of PVD is magnetron sputtering technology, and its advantage of
coating produced by magnetron sputtering technology lies in its
uniform distribution and good adhesion, which has a broad devel­
opment prospect [73–79] (Table 3).
Bakhsheshi-Rad et al. [73] investigated the structure, degradation
and antibacterial properties of nano-silica/grapheme oxides coating
on Mg-1Ca-6Zn via the magnetron sputtering deposition. The mi­
crostructure characterization clearly verified that the nano-sized
SiO2 particles own a uniform distribution of bubble-like structure,
and the thickness of compact columnar microstructure was 1 µm
(nano-GO) and 30 µm (GO), respectively. The corrosion current
density of single-layer SiO2 coating was reduced from 239.7 to
33.5 μA/cm2, due to the formation of thin layer containing cracks/
pores, facilitating the penetration of Cl− and dissolution of Mg2+.
Besides, the composite coating SiO2/GO possesses the best anti-
corrosion behavior (5.95 μA/cm2), which was attributed to the che­
mical inertness and impermeable molecules, thereby acting as the
diffusion barrier to against the matrix from corrosion dissolution.
The antimicrobial results measured by disc-diffusion test revealed
that the inhibition zone of bi-layer SiO2/GO was large than single-
layer SiO2, which was promising as the biomaterials. Surmeneva
et al. [76] investigated the microstructure and degradation behavior
of the nano-hydroxyapatite coating on AZ31 through radio frequency
magnetron sputtering. The SEM/AFM results indicated that all the
deposited coatings were homogeneously distributed along the sur­
face and exhibited a regular grain-like shape. Compared with the
un-coated matrix, the contact angle of HA-coated increased can be
explained by hierarchical organization. Besides, the hydrophobic
surface is relatively stable and exerts the better corrosion resistance,
with the current density of 9.2 × 10−7 A/cm2. Wu et al. [75] evaluated
the corrosion behaviors of fluorocarbon polymeric thin film by
magnetron sputtering in 3.5% NaCl solution. AFM tests revealed that
the average roughness was decreased from 5.71 to 4.56 nm after the
magnetron sputtering, with the smooth surface and less protrusions.
In addition, the water contact angle was increased from 61.5° to
107.3°, implying the formation of hydrophobic fluorocarbon film.
Electrochemical tests reported that the corrosion current density
was decreased from 2.14 × 10−5 to 2.80 × 10−8 A/cm2. However, the
defects such as pores and cracks. As the immersion time increased,
the corrosion propagates from the localized corrosion areas with the
formation of cracks and the products precipitations, resulting in the
corrosion failure of coatings. Kania et al. [74] compared the de­
gradation behavior of TiO2 thin films deposited on Mg-Ca-Zn-Gd in
Ringer’s through the magnetron sputtering technology and sol-gel
ways. Polarization measurements indicated that the PVD coated TiO2
owns the best corrosion resistance with regarding to the bare
MgZnCaGd and spin coating, with the corrosion rate of 3.359 mm/y
(un-coated), 2.513 mm/y (sol-gel), 1.737 mm/y (Magnetron sput­
tering), which was attributed to the uniform and nano-sizes film
layer features. Zarka et al. [80] reported the mechanical properties
and biological corrosion behaviors of β-Ti based coating on AZ31
through PVD method. SEM morphology found that the dense co­
lumnar microstructure was formed on the magnetron-sputtered
coatings. The grain structures were regular, the coating layers were
homogeneous, and the grain size was ranging from 20 to 40 nm,
with the porosity of 8.5 ± 1.5%. The hydrophilicity of the Ti-based
PVD coating was better than the uncoated Mg. The scratch test in­
dicated that the adhesive failure was about 12.70 N load, due to the
ductile behavior of the coating. The conformal cracks open away
such as arcs from the direction of scratching in this failure, con­
tinued by spalling and bucking failure, with the full separation was
17 N. The polarization test revealed that the PCD-treated coating
owns the lowest corrosion rate, with the value of 11.3 mm/y. How­
ever, the existence of the discontinuities on the PVD coatings allows
the corrosive ions to penetrate through the layer and has the direct
contact with the base accelerating the corrosion process. Surmeneva
et al. [81] further explored the adhesion of bone marrow stromal
cells (BMSCs) and the degradation of HA coating deposited on the
AZ91. Results found that the thickness of uniform/pore-free hydro­
xyapatite coating was deposited through the RF magnetron sput­
tering with substrate bias −25 V/−100 V. The ratio of Ca/P in coating
can be changed by controlling the fluxes of ions and electrons with
various negative bias Voltage. The fluorescence observations de­
clared that the BMSCs attached on the HA-coated AZ91 reveal the
typical proliferating, with the spindle-like shape morphology. In
addition, the rapid-degradation behavior of the annealed samples
was due to the cracks/gaps created, resulting in different thermal-
stress expansion coefficient between the coating and the substrate.
Therefore, it can conclude that the nano-structure HA coating with
the characteristics of compact and low crystalline offer a positive
effect on the enhancement of coatings quality and can be helpful for
protecting Mg alloys from leaching Mg2+ into tissues.
3.2. Atomic layer deposition (ALD) coating
ALD is a novel surface covering technology, which could be ap­
plied in the fields of biomedicine and corrosion prevention. Also,

11
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Fig. 8. Schematic illustration of MAO/Ta2O5 coating through ALD for (a) 1 and (b) 500 cycles and the reaction equation of Ta2O5; and the schematic illustration of corrosion
resistance mechanism of the MAO/Ta2O5 coating [82].
ALD has many advantages, including the uniformity of the large
areas, compact and non-porous film structure, accurate thickness
control, etc. Thus, the ALD methods have received much more at­
tention. Li et al. [82] researched the in vitro degradation behaviors of
Ta2O5 nano-film on AZ31 by ALD technique. The schematic illustra­
tion of MAO/Ta2O5 coating through ALD was depicted in Fig. 8a, b.
Herein, the Ta[N(CHCH3)2]3[NHC(CH3)3] was as the Ta source and
water vapor was as O source, and the whole reaction could be di­
vided into two steps in Fig. 8a. The first step was listed in Eq. (25),
and the second step was summarized in Eq. (26). Due to the steric
hindrance effect, the O source would first react with –NHC(CH3)3
and then replaced the –N(CHCH3)2 groups. Also, a Ta2O5 film was
obtained in each cycle, and each of the half-reacted precursors could
be adsorbed inside the micro-pores/micro-cracks of coating. Finally,
a dense Ta2O5 coating was obtained after a plurality of cycles of
deposition (Eq. (27)). Therein, SEM morphology indicated that the
uniform deposition of ALD (Ta2O5) effectively sealing the micro­
porous and micro-cracks, with the thickness of 50 nm. The relevant
electrochemical tests manifested the MAO/Ta2O5 coating owns the
best corrosion resistance in Hank’s electrolyte, with the corrosion
current density of 2.23 × 10−9 A/cm2. It can be attributed to the dense
layer can block the micro-cracks. Immersion tests revealed that the
bare AZ13 was corroded seriously, especially in the edge region with
deep etch pits, while the MAO/Ta2O5 was intact even after long-term
soaking. Therefore, the MAO coated samples treated by ALD de­
position could obviously decreased the micro-cracks/porous,
thereby making the film flatter and blocking the Cl− into the sub­
strate. However, as the immersion time increased, the aggressive
ions can penetrate into the Ta2O5 nano-layer-structure. Also, the
hydrogen produced through the chemical reaction between H2O and
α-Mg would eventually lead to local damage of the Ta2O5 nanofilm,
causing the pitting corrosion (shown in Fig. 8c) [82].
Ta[N(CHCH3)2]3[NHC(CH3)3](g) + MAO-OH*(s) → Ta-O-
Ta[N(CHCH3)2]3*(s) + NHC(CH3) 3(g)
H2O(g) + Ta[N(CHCH3)2]3*(s) → Ta-OH*(s) + NH(CHCH3)]2(g)
2Ta[N(CHCH3)2]3[NHC(CH33)3]3(g) + 5H2O → Ta2O5-
6NH(CHCH3)2 + NH2C(CH3)3(g)
On the other hand, Yang et al. [83] analyzed the biocompat­
ibilities and corrosion behaviors of ZrO2 nanofilm on Mg-Sr alloys
through the atomic layer deposited. SEM morphology determined
that the nanoparticles were uniformly on the surface of ZrO2-100
sample. As the deposition circles increased, the size of nanoparticles
Journal of Alloys and Compounds 885 (2021) 161001
was reduced slightly (200 circles). This is because more deposition
circles result in thicker and denser nanoparticles. Polarization
measurements displayed that the ZrO2-treated could effectively
enhance the corrosion resistance, with the current density of
3.065 × 10−4, 1.536 × 10−4, 5.102 × 10−5, 1.318 × 10−5, 4.88 × 10−6 A/cm2
for various deposition circles. In addition, morphology observations
indicated that the obvious cracks and corrosion products were pre­
sent on the surface, due to the chemical reaction and polarization
measurements. The ZrO2100 sample was corroded slightly, and the
ZrO2200 was still maintained the good condition of surface. The
corrosion behavior of ZrO2300 was improved remarkably, and nearly
half of the surface was intact. The MTT results indicated that the cell
viability of the ZrO2400 increased as the incubation time increased,
in which the cell viability ZrO2400 reach to 280% after 14 days’ in­
cubation. In addition, the ZrO2400 can produce much more ALP than
the control and promote the osteogenic differentiation. Moreover,
the combined coating based on AZ31 was developed by Liu et al. [84]
through ALD and the subsequent PLGA method. The detailed for­
mation mechanism and degradation mechanism of ALD coatings
were elaborated in Fig. 9. In Fig. 9 (step 1), a certain amount of di­
methylamino zirconium was introduced to incur the reaction with
the reactive sites such as –OH, which can produce the intermediate
layer, i.e., Zr[N(CH3)2]2 and (CH3)2NH. In step 2, a certain amount of
O source precursor of deionized water was introduced to initiate the
reaction with sites of intermediate layer, i.e., –N(CH3)2 to form the
new active sites and target material of ZrO2. Degradation behavior
indicated that a thicker ZrO2 nanofilm coating on the surface could
retard the dissolution rate of Mg substrate when compared to a
thinner coating. The detailed corrosion mechanism has been listed in
Fig. 9c. Besides, the corrosion resistance could be significantly in­
creased by two or three orders of magnitude, as the ZrO2 deposition
cycles increased from 25 to 100.
On that basis, the corrosion behaviors of ALD Al2O3 film on AZ31
with various surface roughness were evaluated by Xu et al. [85].
(25) Neutral salt spray test pointed out the uncoated alloy reveals the
serious corrosion morphology with large number of cracks. The
(26) surface of the coated-AZ31 was relatively compact and potholed,
showing a uniform degradation. Potentio-dynamic polarization be­
havior showed that the corrosion rate of the un-coated AZ31 was
(27) decreased from 1.41 to 0.05 mm/y, and the degradation rate of the
smooth surface was decreased from 0.12 to 0.01 mm/y. This phe­
nomenon was mainly related to the film thickness. Staišiūnas et al.
[86] evaluated the corrosion resistance of amorphous hafnium
oxides on the AZ31 through ALD methods. SEM corrosion mor­
phology indicated that the bare sample was corroded seriously with
the large number of corrosion-pits, and the ALD-treated AZ31
12
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

Fig. 9. Schematic illustration of formation mechanism of ZrO2 coating deposited through ALD and PLGA (a); the illustration of corrosion mechanism of PLGA/ZrO2
coated AZ31 (b) [84].

13
Y. Liu, Y. Zhang, Y.-L. Wang et al.
reveals the higher stability. Interestingly, Peron et al. [87] compared
the corrosion of AZ31 treated by ALD and sputter coated TiO2.
Electrochemical test indicated that the sputtering and ALD possess
the lower corrosion rate (5.027 mm/y, 1.919 mm/y) with regard to
the bared AZ31 (31.99 mm/y). Besides, the morphology of bare 3D
AZ31 was highly corroded after 1 day immersion in SBF, and it was
difficult to recognize the original shape. The lower amount of cor­
rosion products was detected on sputter AZ31/ALD31, and the ori­
ginal structure could also be characterized. It was attributed to the
defects and the line-of-sight limitation. Much more defects such as
cracks and pores could provide convenient access for medium to
attack the matrix. As a result, ALD method can be recognized as
feasible method for the fabrication of next generation biomedical
implant materials with the prolonged durability inside the human
body. Peron et al. [88] further conducted the stress corrosion
cracking (SCC) susceptibility of ZrO2-ALD AZ31 under strain rate of
2.6 × 10−6 s−1. Results indicated that the excellent mechanics com­
bination of strength and ductility were obtained in bare and coated
samples under air condition. Whereas the elongation of ALD-coated
AZ31 (19.7%) was higher than the former (6.1%) under the SBF
electrolyte, with the Ic of 75.1 and 18.3, respectively. Then, Peron
et al. [89] explored the SCC behavior of ALD conformal thin TiO2/
ZrO2 on AZ31, with the strain rate of 3.5 × 10−6 s−1. The SCC sus­
ceptibility index IUTS was reduced by 6% and 40% and the Iε was
reduced by more than 70% and 76% with TiO2 and ZrO2 coating,
respectively. The difference in SCC was associated with four aspects,
such as the different cohesive energies, wettabilities, defect densities
and mechanical properties.
3.3. Electrolytic deposition layer
As a novel surface modification technique, electrolytic deposition
layer (ED) can be utilized into the various metals/alloys. ED mainly
refers to the deposition of these inorganic phases on the bare and
pre-coated surface under the action of electric field. Unlike the
chemical conversion, electrolytic deposition layer can create the
thicker, harder and more durable layer. Initially, Wang et al. [90]
investigated the corrosion behavior of electrolytic MgO/ZrO2 duplex-
layer coating on AZ91D. Results indicated that duplex-layer MgO/
ZrO2 exhibits relatively high corrosion resistance and superior sta­
bility. Since the adhesion strength, thickness and densification of
layer on the substrate were significantly enhanced by the inter­
mediate ZrO2, which can prevent the formation of Mg2(OH)3Cl4H2O
products. Liu et al. [91] conducted the electrochemical corrosion
behavior of Al2O3-ZrO2 coating on WE43 by cathodic plasma elec­
trolytic deposition (CPED) technique. SEM morphology demon­
strated that some macro-pores were distributed on the surface,
consisting of t-ZrO2, α-Al2O3, γ-Al2O3, which were formed on the
residual plasma discharge channels and the trapping of gas bubbles
in the growing oxide layer. Electrochemical tests in SBF reveal that
the corrosion potentials were increased from −1.681 to −1.354 V, the
degradation rate was decreased from 13.027 to 0.239 mm/y. It in­
dicated that the coated-WE43 owns higher corrosion resistance and
more practicability. Following, the corrosion resistance of cerium
oxide coatings on the AZ31 was analyzed by Ji et al. [92] via the CPED
method. Results reveal that the CPED without glycerol produce the
crack surface, and the CPED with glycerol can form the uniform and
intact layer, though there were some small flaws and cracks. In ad­
dition, the thickness of ED layer with and without glycerol was 5.3
and 1.1 µm. The dense and thick ED layer can offer better protection
of substrate, thereby preventing the further corrosion of the Mg-
matrix. The corrosion resistance of the alloys was not only associated
with the density and thickness of the surface layer, but also related
14
Journal of Alloys and Compounds 885 (2021) 161001
with the properties of glycerol. On the one hand, glycerol acting as
the carbon source, the addition of glycerol increased the con­
ductivity, so that the coating was not easily decomposed. On the
other hand, the addition of glycerol can restrain the point discharge,
resulting in the inhomogeneous thickness of oxide film. Besides, it
can also increase the viscosity of electrolytes, making it difficult for
H2 release. The dual layer (PEO/CaP) was fabricated on pure Mg by
electrodeposition method, which can delay the degradation beha­
vior for bone fixation implants [93]. Polarization tests indicated that
the corrosion rate of pure-Mg, PEO, ED-PEO was 0.53, 0.19,
0.019 mm/y, respectively. Moreover, no obvious degradation beha­
vior was occurred at the PEO-CaP coated Mg, which was associated
with the thick and dense film layer. In addition, these defects of the
film was modified and decreased. Xu et al. [94] analyzed the cor­
rosion behavior of Mg(OH)2/GO composite coating, which was fab­
ricated by electric deposition (ED) under the constant potentials.
Results indicated that more particles and cracks were present on the
uneven surface since only the Mg(OH)2 was present. It can be uti­
lized as diffusion channels to accelerate dissolution rate. With the
addition of GO, although there were still some pores in the film layer,
and the films become more uniform and these particles disappear.
Polarization tests displayed that the corrosion rate of bare AZ91D,
Mg(OH)2, and Mg(OH)2/GO was 0.987, 0.122, 0.0058 mm/y, which
was attributed to the dense composite structure and isolation role
with GO addition. Singh et al. [95] also examined the characteristics
and degradation behaviors of HA/Fe3O4/CS composite coatings on
AZ91 through the electrophoretic deposition method. It can be seen
that the coating was non-cracks in the HA and Fe coating. Ad­
ditionally, the sizes of HA-agglomerates decreased and the compo­
sites coatings appeared to be more uniform and dense as the Fe3O4
contents in increased. Surface roughness results indicated that the
lowest value was obtained in the HA-coated sample. The values of
Fe-containing and HA-1Fe were near to each other. Surface wett­
ability revealed that the best performance was obtained in HA/Fe3O4
composite coating due to its nature of HA and polymer chitosan.
Besides, the electrochemical tests indicated that the best corrosion
resistance was obtained in HA- 1Fe, with the current density of
3.8 × 10−6 μA/cm2. Degradation behavior indicated that the minimum
weight loss was captured on HA-1Fe after 21 days’ immersion, which
can be associated with dense and integrity composite structure. In
addition, the addition of Fe in HA can reinforce the HA composite
coatings with good crystallinity. Therefore, it was proposed that the
HA/Fe3O4/CS composite coating was favorable candidate for appli­
cation of biodegradable implant materials.
3.4. Organic biopolymer coating
Organic coatings can be obtained by dipping or soaking. In ad­
dition to typical organic coating of polylactic acid/chitosan, the effect
of silane, dopamine and stearic acid (SA) on biomedical magnesium
aluminate were also obvious. Due to its low cost, versatility and
unique esthetic properties, organic coating has been widely used as a
new anti-corrosion properties technology. The typical preparation
methods were listed in Table 4, which can facilitate the authors’
selection according to the specific requirements. For instance, the
adhesion, toughness and degradation behavior of PLA deposition
coating were examined by Muñoz et al. [96]. SEM observations in­
dicated that the PLA layer can smooth the linear channel mor­
phology, while the bubbles, scratches and PLA flakes were mainly
composed of 44.6% C and 20.4% O. The AZ31/PLA layer at cross-
section was homogeneous, with the thickness of 10 ± 1 µm in AZ31/
PLA/C4. Electrochemical measurements indicated that the corrosion
rate was 0.046, 0.016, 1.485 × 10−3, 3.885 × 10−4 mm/y for AZ31, AZ31/
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

Table 4
The condition of formation organic biopolymer coating [96–102].

Alloys Coating Tem Time (h) Solution pH ST WT CR (cm/min) CT Time Ref.

(°C) (min) (°C) (°C) (h)

AZ31 PLA – – 6 wt% CHCl3 – 1 RT 75 70 2 [96]

AZ31 PLA – – 10 wt% CHCl3 – 2 – 2 40 24 [97]
AZ31B SA 37 72 3 vol% Triethoxy(octyl)silane solution – 10 – – 150 1 [98]
ethanol and water
75:25
AZ31 SA 25 8 APTMS and enthanol and water – 15 30 – – – [99]
3:22:75
– PP 125 – Polypropylene and malefic anhydride – 5 – – 100 2 /
grafted polypropylene and xylene
0.2:1.6:100
AZ31B SA 25 24 Water and ethanol and silanes 4.5 0.5 – – 120 3 [100]
0.56:0.14:0.3
AZ31 PDA – – 2 g/L Dopamine solution 8.5 1440 – – – – [101]
– HYA – – 2 g/L Hyaluronic solution – 720 – – – – /
AZ31 epoxy resin – – Water-based epoxy resin 8.5 10 150 – – – [102]
– polydopamine – – 2 mg/ml of dopamine hydrochloride and – 1440 – – 150 1/6 /
10 mM of Trizma-base

PLA, AZ31/PEO, AZ31/PEO/PLA, respectively. It was further indicated
the AZ31/PEO/PLA possesses the best corrosion resistance, which
was attributed to the modification and thickness. In addition, the
voids and cavities can be filled with treatment of PEO/PLA, offering a
positive effect on sealing and mechanical consolidation. As expected,
the average thickness of AZ31/PLA was relatively smaller than that of
AZ31/PEO/PLA, due to the roughness of the substrates and high
viscosity of the solution, with the value of 27 µm and 59 µm. Also,
the porous morphology on PEO coating was beneficial to penetrate
for PLA in its pores, thereby facilitating the deposition rate on the
surface of samples. Adhesion strength results displayed that the
values were ranked as: AZ31/PLA＞AZ31/PEO＞AZ31/PEO/PLA, since
no high enough electrostatic biocompatibility between PEO and PLA
and strong chemical interactions were formed.
Shi et al. [97] further prepared the PLA and PLA/MAO composite
coating on AZ31 via dipping method. SEM observations indicated
that the original MAO coating was present some micropores/micro-
cracks, with the average sizes of 0.5–2 µm, which was randomly
distributed on the surface. However, the PLA coating can cover and
seal the micro-cracks, leaving the smooth and uniform without any
tiny cracks morphology. In addition, the addition of PLA can improve
the adhesion strength and bonding between PLA and AZ31 substrate.
Polarization tests indicated that the Rp value was increased and the
transfer corrosive ions were inhibited in the simulated body fluid
due to the covering and blocking effect of PLA layer. Compared with
untreated AZ31 (13.978 mm/y) and MAO-treated AZ31 (1.515 mm/y),
the degradation rate of composite coating alloy was significantly
reduced (0.042 mm/y). Degradation tests further examined the PLA/
MAO coating could provide a longer time anti-corrosion effect for
AZ31. Gu et al. [98] also analyzed the degradation behavior, hemo­
lysis and cytotoxicity of Triethoxy(octyl)silane coating on AZ31B
alloys. SEM morphology indicated that the coating become more
compact as the deposition potentials improved from −1.8, 2.0 V.
However, the thickness reaches to 3.4 µm, with the potentials of
−2.2 V, leaving some micropores on the surface. The contact angles
of increased from 49.0° to 98.9–102.3°, implying the formation of
hydrophobicity layer. Zhang et al. [99] examined the corrosion be­
haviors of self-cleaning silane/polypropylene composite coating on
AZ31. FE-SEM pictures revealed that some white and bulges spots
were present on the transparent film surface due to the self-con­
densation of silanol to oligomer. Also, no cracks and damage were
occurred on the surface after 100 s of water impingement, indicating
an excellent stability. In addition, the PAPRMS/PP coating possessed
the superhydrophobic properties, due to the low surface energy and
spherical microstructure. Electrochemical polarization displayed
that the PAPRMS/PP possessed excellent corrosion resistance
(9.08 × 10−8 A/cm2) compared to the PAPTMS (1.95 × 10−6 A/cm2). The
formation mechanism was mainly listed as Eqs. (28)–(31):
X-Si(OH)3 + X-Si(OH)3 → 3X-Si-O-Si-X + 3H2O (28)
RCOO-OCR + H2N-Si-O-Mg → RCONH-Si-O-Mg + COOH (29)
RCOO-OCR + H2N-Si-O-Mg → R(CO)2N-Si-O-Mg + H2O (30)
RCOOH + H2N-Si-O-Mg → RCONH-Si-O-Mg + H2O (31)
Moreover, Toorani et al. [100] examined degradation behaviors of
epoxy coated AZ31B treated by PEO/Silane pretreatment. Herein, the
cerium nitrate was selected as the inhibitor in PEO coating with
various contents and γ-amino propyltriethoxysilane (APTES). The
morphology of PEO coating was porous pancake-like, whereas the
morphology after silane treatment was covered with the entire
surface. The number of cracks in silane structure and covering ability
in silane layer decreased as the APTES content increased. As a result,
the silane layer can seal the film layer and enhance the corrosion
resistance by reducing the penetration of corrosive agents into the
film structure. The volume ratio of APTES increased to 50% in silane
can improve the corrosion resistance and the adhesion abilities. It
was associated with the APTES silane layer with the organic-func­
tional group, forming in the chemical bond with active regions and
covalent bond with the reactive groups of epoxy molecules. Zhou
et al. [101] analyzed the corrosion behavior and biocompatibility of
polydopamine/hyaluronic acid composite coating on AZ31. Many
microcracks were observed on the PDA, which may be potential risk
to weak corrosion resistance, while the smooth and sealed coatings
were formed on the PDA/HYA composite coating. Electrochemical
polarization displayed that the open circuit potentials of samples
were PDA/HYA > PDA > AZ31, and the corrosion rate was ranked as
following: AZ31(1.938 mm/y) > PDA(1.536 mm/y) > PDA/HYA(0.13
mm/y). Similarly, the large pits and cracks were present on the
surface of bare AZ31 after 7d’ immersion, whereas the coated AZ31
exhibits relative uniform surface. Combined with EDX analysis, the
formation of Ca-P facilitated the recovery of the new bone. Cyto­
compatibility evaluation found that all alloys possess better pro­
liferation-abilities, which was promising to act as the orthopedic

15
Y. Liu, Y. Zhang, Y.-L. Wang et al. Journal of Alloys and Compounds 885 (2021) 161001

implants. Carangelo et al. [102] compared and analyzed the de­

gradation behavior of AZ31 alloys containing the PDOPA, epoxy, and
the composite PDOPA/epoxy in Hank’s solution. Electrochemical
results indicated that both the AZ and AZD showed the low corrosion
resistance, indicating it does not possess the obvious enhancement
in anti-corrosion. In addition, the AZDE showed the best perfor­
mance among the tested samples, since the polydopamine acting as
the intermediate layer collaboration with organic coating can be
effective to inhibit the corrosion rate. The corrosion and adhesion
strength of AZ31 pretreated by PEO/silane with inorganic/organic
inhibitors were investigated by Toorani et al. [103]. SEM observation
displayed that the more porous structure was formed on the coating,
due to the micro-channels of electrical discharge. The hydrolysis and
condensation reactions occurred between silanol group and –OH
groups. The presence of amine groups in the silane-treated layer
results in the covalent bonding between the epoxy and silane layers
and increased adhesion strength. However, the adhesion strength
was lowest in the 8-HQ in the wet conditions. Zhou et al. [104]
analyzed the degradation behavior and biocompatibility in vitro and
in vivo of 5β-TCP/Mg-3Zn scaffold coated with dopamine-gelatin
composite. SEM observation indicated that the neat and flat gelatin
and PDA/G organic coating were formed on the G and PDA/G sam­
ples, while the porous and loose structure was created on the PDA
via cross-section observation. The electrochemical tests in Hank’s
solution revealed that the degradation rate of the alloys was con­
tinuously decreased (119.734 → 85.002 → 67.408 → 32.419 mm/y).
Fig. 11. Post-op X-ray images after implantation for (a1, b1) 1 week, (a2, b2) 2 weeks
The indirect cytotoxicity tests showed that the uncoated/coated 5β- and 4 (a3, b3) weeks of the bare sample and PDA/G coated sample. White arrow:
TCP/Mg-3Zn was no cytotoxicity to BMSCs, HOS and MG63. After Hydrogen gas bubble; red arrow: scaffold [104].
culturing in extraction medium for various cycles, BMSC reveals
healthy morphology with cell bodies and pseudopodia, as shown in
Fig. 10. On the other hand, the in vivo biocompatibilities tests in­ of paclitaxel eluting MPPS Mg-Zn-Y-Nd alloy stent in vitro/vivo. It
dicated that the morphology with no degeneration, necrosis and can be seen that the surface was completely covered by PLLA by
inflammatory occurred in the tissues, indicating the all the samples dipping method, which can delay the corrosion dissolution of Mg.
were highly biocompatible. Bone tissues slices with 4 weeks im­ After 5d’ immersion tests, the morphology PLLA/paclitaxel stent was
plantation can stimulate the formation of more capillary vessels, smooth and tight, with the high integrity and no damage and cracks.
fiber connective tissue and osteoblasts. X-ray results displayed that After coat-treatment, the corrosion resistance was obviously im­
the rapid degradation rate was obtained in the uncoated alloy, with proved, decreasing from 4.4 × 10−4 to 0.835 × 10−6 A/cm2. The histo­
the massive subcutaneous emphysema after 1-week post-surgery pathological examination revealed that no recurrence of intestinal
(Fig. 11a). However, the coated 5β-TCP/Mg-3Zn exhibits the relatively stricture or obvious inflammatory was occurred after the implanta­
small gas cavity and disappeared at 4 weeks (Fig. 11b). It provided tion of MPPS Mg-Zn-Y-Nd stents. However, the MPPS stents degrade
the theoretical support for the clinical application of the Mg-based too fast to meet clinical requirements. Therefore, it is necessary to
alloys. Interestingly, Wang et al. [105] examined the biocompatibility study new strategy to inhibit the dissolution rate of alloys under the

Fig. 10. Fluorescence images of BMSC cells cultured with extraction media of the bare sample, G, PDA and PDA/G after 1, 3 and 5 days [104].

16
Y. Liu, Y. Zhang, Y.-L. Wang et al.
Fig. 12. Degradation rate images of different coated magnesium alloys under (a) SBF [28,30,37,45,54,73,89,91,93,97,101,105–109], (b) NaCl [32,33,44,46,48,76,81,85,99,110,111], (c)
Hank’s [35,62–64,67,82,96,98,112] and (d) other corrosive media[5,36,75,113–117].
complex environment. Besides, authors also summarized the cor­
rosion rates of modified coatings on Mg alloys under different cor­
rosion mediums, as shown in Fig. 12. The data can facilitate the
scientific researchers to complete the evaluation of each modifica­
tion process in a short time. Also, the mapping of the relationship
between the coating and the degradation rate enables readers to
clearly understand and compare the conversion coating features.
Thus, researchers can easily select the most suitable modification-
coating on degradable Mg-based implants for the requirements of
different parts of the human body.
4. Conclusion and future outlook
Acting as a new generation of biodegradable metallics (BMs), Mg-
based alloys were inevitably affected by corrosion fatigue under the
physiological environments, resulting in significant mechanical at­
tenuation and premature fracture failure. Therein, excessive corro­
sion rate was essential reason for the above phenomenon. In this
text, the latest studies about the surface modification coatings on
degradable Mg alloys were reviewed. Besides, the interactions me­
chanism between the modified layer and electrolyte solution, the
rupture mechanism of modified layer in biological medium were
17
Journal of Alloys and Compounds 885 (2021) 161001
discussed. In conclusion, the great progress has been made in the
improvement of corrosion resistance by surface modification, but
there were still many limitations and challenges:
(1) The development of multi-functional coatings was needed. The
ideal coatings on biomedical Mg implants for clinical application
may be high corrosion resistant, self-degradable, drug-lading
and bio-safety. However, it is almost impossible to make men­
tioned properties, especially for Mg alloys with very poor cor­
rosion resistance.
(2) Surface modification coatings with special anodic gradients
might be choice for the degradable Mg-based implants. Thus, the
outer anodic coating preferentially degraded and its inner
coating/the substrates still kept passivated, which can maintain
the integrity of mechanical properties and film layers structure.
(3) The nano-scale characterization at the interface was still lacking,
particular in the deposition/growth in-situ. Besides, the pre­
paration of multifunctional composite coating, wear coating,
antibacterial coating through PEO treatment was still lack.
(4) At present, the degradation model of biomedical Mg-based al­
loys was mainly in vitro and static measurements. It is neither
scientific nor sufficient for its practical application. Thus, more in
Y. Liu, Y. Zhang, Y.-L. Wang et al.
vivo degradation models should be established, especially the
fatigue damage mechanism and crack growth rate (CRK) of the
modified-coatings under the interaction of corrosive ions and
the nonlinear mechanical-loading.
Declaration of Competing Interest
The authors declare that they have no financial interests or
personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgments
The research is supported by the financial support of the Science
and Technology Program of Hebei (E2020209153), Basic Scientific
Research Business Expenses of the Universities in Hebei Province
(JYG2019001), Science and Technology Project of Tangshan
(20130205b), State Key Lab of Advanced Metals and Materials
(2020-Z12).
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