BaratiDarbandetal. 2017 PlasmaelectrolyticoxidationofmagnesiumanditsalloysMechanismpropertiesandapplications PDF

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Plasma electrolytic oxidation of magnesium and its alloys: Mechanism,

properties and applications
Article · March 2017

DOI: 10.1016/j.jma.2017.02.004
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Journal of Magnesium and Alloys ■■ (2017) ■■–■■
www.elsevier.com/journals/journal-of-magnesium-and-alloys/2213-9567
Review
Plasma electrolytic oxidation of magnesium and its alloys: Mechanism,
properties and applications
Gh. Barati Darband, M. Aliofkhazraei *, P. Hamghalam, N. Valizade
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, P.O. Box: 14115-143, Tehran, Iran
Received 11 February 2017; accepted 26 February 2017
Available online
Abstract
Plasma Electrolyte Oxidation (PEO) process has increasingly been employed to improve magnesium surface properties by fabrication of an
MgO-based coating. Originating from conventional anodizing procedures, this high-voltage process produces an adhesive ceramic film on the
surface. The present article provides a comprehensive review around mechanisms of PEO coatings fabrication and their different properties. Due
to complexity of PEO coatings formation, a complete explanation regarding fabrication mechanisms of PEO coatings has not yet been proposed;
however, the most important advancements in the field of fabrication mechanisms of PEO coatings were gathered in this work. Mechanisms of PEO
coatings fabrication on magnesium were reviewed considering voltage–time plots, optical spectrometry, acoustic emission spectrometry and
electronic properties of the ceramic film. Afterwards, the coatings properties, affecting parameters and improvement strategies were discussed. In
addition, corrosion resistance of coatings, important factors in corrosion resistance and methods for corrosion resistance improvement were
considered. Tribological properties (important factors and improvement methods) of coatings were also studied. Since magnesium and its alloys
are broadly used in biological applications, the biological properties of PEO coatings, important factors in their biological performance and
existing methods for improvement of coatings were explained. Addition of ceramic based nanoparticles and formation of nanocomposite coatings
may considerably influence properties of plasma electrolyte oxidation coatings. Nanocomposite coatings properties and nanoparticles adsorption
mechanisms were included in a separate sector. Another method to improve coatings properties is formation of hybrid coatings on PEO coatings
which was discussed in the end.
© 2017 Production and hosting by Elsevier B.V. on behalf of Chongqing University. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: Plasma electrolytic oxidation; Magnesium; Tribological properties; Biomedical properties; Nanocomposite coatings
1. Introduction corrosive media [7–14]. A proper surface treatment may

improve wear and corrosion resistance of the substrate. There
Magnesium and its alloys are among the lightest group of
are some surface treatment techniques established for protec-
engineering metals. Magnesium also has very good properties
tion of magnesium and its alloys. These techniques include
such as low density, high strength to weight ratio, tremendous
chemical conversion plating, electrodeposition, anodizing, gas-
dimensional durability [1–5], good electromagnetic shielding,
phase deposition, organic coatings and sol-gel technique
higher damping capacity and high machinability. Hence, mag-
[15,16]. A popular technique for surface treatment of magne-
nesium and its alloys have found many applications in various
sium and its alloys is plasma electrolyte oxidation which is
industries including automobile, aerospace and communica-
likewise recognized as micro-arc oxidation [17,18], micro-
tions [6]. However, high activity of magnesium weakens corro-
plasma oxidation [19] and anodic spark deposition [20]. Origi-
sion and wear resistance of this metal and its alloys especially in
nating from traditional anodizing process, PEO is a rather
inexpensive and environmentally friendly technique [21,22]. It
is a high-voltage process that is broadly used for surface treat-
* Corresponding author. Department of Materials Engineering, Faculty of ment of magnesium and its alloys [23–30]. In this process,
Engineering, Tarbiat Modares University, P.O. Box: 14115-143, Tehran, Iran.
Fax: +98 21 66960664.
plasma discharge occurs which leads to partial fusion of an
E-mail addresses: maliofkh@gmail.com, khazraei@modares.ac.ir (M. oxide film and consequently formation of an extremely adhe-
Aliofkhazraei). sive oxide coating on the substrate [31]. The produced coatings
http://dx.doi.org/10.1016/j.jma.2017.02.004
2213-9567/© 2017 Production and hosting by Elsevier B.V. on behalf of Chongqing University. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Gh. Barati Darband, M. Aliofkhazraei, P. Hamghalam, N. Valizade, Plasma electrolytic oxidation of magnesium and its alloys: Mechanism, properties
and applications, Journal of Magnesium and Alloys (2017), doi: 10.1016/j.jma.2017.02.004
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2 G. Barati Darband et al. / Journal of Magnesium and Alloys ■■ (2017) ■■–■■
possess very good wear and corrosion resistance as well as responsible for good mechanical properties (wear resistance) and
proper electrical properties and high thermal stability [32–34]. corrosion resistance, the compact middle layer provides excellent
There have been many studies on PEO coatings on magnesium. corrosion resistance in coatings [37]. Surface of PEO coatings
Considering the fact that a comprehensive review article around generally include pancake-form structures with a discharge
PEO coatings on magnesium has not been published in recent channel in the center of each pancake. Molten substances effuse
years, the aim of the present text is to provide a full understand- through the discharge channels and quench while being exposed
ing on all aspects of this process. First, morphologies of all to the cold electrolyte. In results, distinct boundaries would
phases formed during the process were discussed. Afterwards, develop which separate the pancake [38]. Rather large voids at the
coating formation mechanisms were comprehensively studied center of each pancake indicate extreme discharge which may also
and then different properties of coatings including corrosion penetrate deep into the coatings. Pore size is a function of
resistance, tribological properties, biomedical properties and discharge density as well as process time. It is reported that the
effects of various parameters were considered. Finally, pore diameter in magnesium alloys is usually between 0.5 are
nanocomposite and hybrid coatings produced by PEO process 50 µm. Discharge channels are surrounded by molten substances
were investigated. and local micro cracks. Formation of micro cracks may be due to
quenching of molten substances while being exposed to the cold
2. Surface morphology and different phases formed on electrolyte. Extreme discharges possess high input energies which
magnesium substrate in PEO process causes fusion of considerable parts of the oxide film and substrate.
Microstructural characteristics of PEO coatings depend on Finally, molten substances flow out toward the surface and form
operational conditions, and coatings thickness may vary between large ceramic particles while they reach the cold electrolyte.
5 and 200 µm. Generally, the coating interface is in a zigzag form Molten oxides around the pores show the fact that momentary
which makes the coating seem integrated into the substrate. PEO temperature inside the micro-voids may reach several thousand
process consists of a plasma discharge procedure around an degrees [39]. Yerokhin et al. [40] stated that this temperature may
immersed metal in an environmentally friendly electrolyte. be around 2300 to 3000 K.
Discharge procedures significantly affect coatings structure and The nature of each phase that is formed in PEO process
consequently their physical and mechanical properties [35]. Three depends on the substrate and electrolyte type and species in the
processes occur simultaneously in the PEO treatment. These electrolyte. In PEO processes, the magnesium substrate is
include electrochemical and plasma chemical reactions as well as placed as anode in silicate based electrolytes; thus, magnesium
oxygen thermal diffusion. It is believed that PEO coatings on dissolution reaction occurs under a strong electric field produc-
magnesium substrates possess three-layer structures [36]. ing magnesium ions.
Fig. 1(a) and b show SEM micrographs of a coating surface and
cross section, respectively. A schematic design of the outer porous Mg → Mg 2 + + 2e − (1)
layer, the fairly compact layer in the middle and the thin and
compact layer (barrier layer) that sticks well to surfaces is Formation of oxide films on magnesium is due to outward
presented in Fig. 1(c). Although the compact middle layer is diffusion of magnesium ions and inward diffusion of SiO32−,
Fig. 1. Schematic of a) PEO coating surface b) cross section and c) different layer of PEO coating [36].
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G. Barati Darband et al. / Journal of Magnesium and Alloys ■■ (2017) ■■–■■ 3
Fig. 2. X-ray diffraction patterns of magnesium samples coated in silicate base electrolyte under different current densities [38].
OH − and F −under high potentials [38]. Film formation reac- In addition to MgO and MgF2, MgAl2O4 is also produced in
tions would occur once concentrations of these ions in alumina based electrolytes:
electrode/electrolyte interface reach a critical value. Mg2SiO4,
MgSiO3 and MgF2 are produced according to the following Mg 2 + + 2 AlO2− → MgAl2O4 (7)
equations: Finally, the following equation holds in phosphate based
2 Mg 2+
+ SiO2− −
+ 2OH → Mg 2 SiO4 + H 2O (2) electrolytes:
3
3Mg 2 + + 2 PO43− → Mg3 ( PO4 )2 (8)

Mg 2 + + SiO32 − → MgSiO3 (3)
X-ray diffraction patterns of magnesium samples coated in
Mg 2 + + 2 F − → MgF2 (4) silicate and phosphate based electrodes under different current
Also, MgO is produced through the following equations: densities are illustrated in Figs. 2 and 3, respectively. It may be
observed that Mg2SiO4 and MgO were the main phases formed
Mg 2 + + 2OH − → Mg (OH )2 (5) during coating in the silicate based electrolyte; while, MgO and
Mg3(PO4)2 were dominant in the phosphate based electrolyte
Mg (OH )2 → MgO + H 2O (6) [41]. Duan et al. [41] also investigated magnesium coating in
Fig. 3. X-ray diffraction patterns of magnesium samples coated in phosphate base electrolyte under different current densities [38].
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Fig. 4. Schematic of different approaches to study plasma electrolytic oxidation mechanism.
several electrolytes with different additives and observed many researchers [1,52–55]. A voltage–time plot in a PEO
various phases. process on magnesium substrate is shown in Fig. 5.
Metal dissolution and growth of the barrier layer happen in
3. Formation mechanisms of PEO coating on magnesium the beginning of PEO treatment on magnesium substrates or its
and its alloys alloys. It may be perceived in Fig. 5 that voltage rises linearly
Generally, study of formation mechanism of coatings may with increase in time in the first stage. In this stage, noticeable
help in understanding the procedure and finding the optimum
conditions for obtaining the best properties. Recently, PEO
coatings formation mechanism has attracted a great deal of
attention [42–46]. Formation mechanism of MAO coating is
somehow complicated due to many electrochemical, chemical
and thermal reactions [47–52]. Oxide film formation, primary
film dissolution and evolution of gas on anode surface consti-
tute the main reaction in a PEO process. Dominance of any of
these reactions depends on magnesium alloy composition, elec-
trolyte type, concentration of each component in the electrolyte
and applied current density. According to undertaken studies so
far, all comprehensive methods to study PEO coatings on mag-
nesium are schematically categorized in Fig. 4. In order to
understand the formation mechanism, each technique will be
separately studied here.
3.1. Voltage–time plots in constant current
Constant current method is mostly used for PEO processes;
thus, measuring voltage variations in electrochemical cells as a Fig. 5. Voltage–time responses for PEO process of magnesium alloys in solu-
function of time may reveal the main stages in PEO processes. tion containing Na2SiO3 · 6H2O 6 g/L, KF · 2H2O 4 g/L, KOH 2 g/L at 100 mA/
Voltage variations against process time have been studied by cm2 (curve a) and 50 mA/cm2 (curve b) for 15 min, respectively [56].
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Fig. 6. The relationship between PEO voltage–time response and four oxidation stages [56].
sparks cannot be seen on the metal surface and a thin, transpar- stage, the required voltage to keep current constant is less than
ent and passive layer is formed. In addition, oxygen molecules what was need for the last stage because electron current
evolved from water oxidation along with hydroxyl anions are density is not dependent on film resistance. In third stage, share
uniformly adsorbed on the metal surface. Anode surface is of electron current density in total current is significantly
enclosed with a thin dielectric film. The strong electric field increased due to dielectric fracture (electron avalanche). There-
offers the driving force required for movement of cations and fore, one may state that total current is not a function of film
anions that exist in the electrolyte across the barrier film. The resistance and consequently voltage–time curve slope plum-
movement would increase coating thickness up to 0.6 nm.V−1 mets rapidly up to zero [56].
[57]. This stage is actually representing a normal anodizing
process [58]. In the second stage, voltage of electrochemical 3.2. Study of coating deposition mechanism by optical
cells still increases linearly; however, the slope becomes less emission spectroscopy(OES)
steep. Here, small sparks may be observed all over the metal
surface. In the third stage, a uniform sparking state is developed OES has been recently employed to investigate discharge
and cell potential reaches an approximately constant value. behavior in plasma electrolyte oxidation processes [61–66]. It is
believed that substrate-related species (magnesium, aluminum
White sparks are replaced with orange ones which may be seen
and titanium) as well as electrolyte-related species (H, OH, Na
in certain locations. These sparks move slowly across all over
and K) contribute to plasma discharge reactions in PEO pro-
the metal surface. Size and density of sparks reduce gradually
[56]. The first inflection point in the voltage curve is associated cesses. Evaluation of the spectra created during the coating
with the breakdown voltage that occurs after the primary spark- treatment reflects the processes and mechanisms in plasma
ing phenomenon. breakdown voltage strongly depends on con- electrolyte oxidation. Optical measurements may provide infor-
centration and conductivity of electrolyte [59,60]. The second mation regarding time, size and spatial distribution. Optical
inflection point after which phenomena of the metal surface measurements on magnesium showed that discharge period
change dramatically is called the critical voltage. In this step, lasted 50 to 110 µs [67]. Electric measurements provide infor-
mation about discharge currents which are usually in range of 1
cell voltage reaches an approximately constant value and steady
to 100 mA [68]. When discharge diameter during plasma elec-
state sparking also takes place on metal surface. According to
trolyte oxidation is obtained via electric measurements, values
the voltage–time plot, the PEO process may be divided into
of current densities also may be determined [68]. Spectrum
three stages. But, four stages may be expressed when one is
analyses may be used to gain information about temperature,
considering the phenomena that occur in electrode/electrolyte
density and chemical composition of plasma [35,63]. Optical
interface. These stages include normal anodizing, spark anod-
emission spectrometry has been employed in plasma electrolyte
izing, micro-spark oxidation and arc oxidation. The association
oxidation to investigate the emitted light from plasma species in
of these stages with voltage–time plot in the PEO process is
aluminum [63,69], magnesium [67,68] and titanium [67,68]
presented in Fig. 6 [56].
alloys. This method has also been used to study mechanisms of
Combining the phenomena on metal surface and voltage–
plasma electrolyte oxidation [70,71]. Mécuson et al. [72]
time plot, variations in slope of the potential-time curve may be
studied composition of discharge micro-sparks and intensity of
explained: total current density during the whole PEO process
emitted lines on aluminum alloys in a silicate based solution
is:
using optical emission spectrometry. According to investiga-
is = ii + ie tions by Dunleavy et al. [68], plasma emitted spectrum con-
sisted of two separate plasma regions: a central core with high
Where is is total current density, ii is ionic current density
temperature (16000 to 35000 K) and high electron density
(which increases with increase in film resistance) and ie is
(5 × 1017 electron.cm−2) and a marginal area which probably
electron current density (relative to electron avalanche process
extends to near the electrolyte (with lower temperature and less
and remains constant with increase in film resistance). Ionic
electrons).
current density is the main current density in the first stage
(normal anodizing). The moving current through the oxide film
3.3. Study of different processes in PEO process on
is only expressed by the ionic current. Film growth rises inter-
magnesium by optical emission spectroscopy
face resistance; hence, voltage increase in order that current
remains constant. As sparking process starts, current density Hussein et al. [73] investigated mechanisms of plasma elec-
would become the sum of ionic and electron current densities trolyte oxidation on magnesium using OES method. They
(Electron current density is responsible for sparking). In this managed to record plasma temperature variations in PEO treat-
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the beginning due to primary discharges which have extremely

high densities. After 10 mins, temperature decreased up to
4500 K. It rose again up to 5000 K in 25 mins, yet, fell to 4500 K
after another 25 to 40 mins. It may be seen that plasma
temperature undergoes many up and downs during the PEO
process. Each up and down may be attributed to a type of discharge
that will be discussed in future sections [73].
PEO treatment on magnesium alloys is schematically illustrated
in Fig. 8. In PEO process, thickness of the thin magnesium oxide
film is increased by applying sufficient electric potential. This
natural film is not compact as its Pilling–Bedworth ratio is less than
unity [74]. As soon as the sample surface is covered with a non-
conductive oxide film, the voltage between substrate and
operational electrolyte increases immediately and reaches several
thousand volts. The voltage increase continues till plasma
microscopic discharges lead to coating breakdown and many ultra-
small plasma discharges with short lives are created.The discharges
Fig. 7. Plasma temperature as a function of treatment time (min) determined cause local plasma reactions with the high temperature and high
from the intensity ratio of H˛ (656.3 nm)/Hˇ (486.1 nm) [73]. pressure conditions which modify oxide growth. Also, the
breakdown leads to fabrication of a thicker coating which would
crack in the next cycle under a higher potential. PEO processes
ment via this technique. Temperature variations during the include fusion, melt flux, re-solidification, diffusion, sintering and
process are shown in Fig. 3. The average temperature is also compaction of the oxide film [73].
presented in Fig. 7: Three processes occur simultaneously in coating growth.
It is universally accepted that discharge occurs in PEO when These processes are electrochemical, chemical plasma and
the applied voltage exceeds a critical value. The critical voltage is thermal diffusion [27,75]. The main electrochemical processes
called breakdown voltage of the surface oxide film. This leads to occur in coating/electrolyte interface. Plasma chemistry of
creation of intensive light emissions at numerous micro-discharge surface discharges is problematical; where it includes charge
locations. Fig. 3 shows that temperature was 5500 K in transfer in substrate/electrolyte interface, on the one hand, and
Fig. 8. Schematic of the coating process during PEO treatment [73].
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Fig. 9. Schematic diagram of the discharge model showing the influence of B-type discharges on plasma temperature pro file, surface morphology and on the cross
section of the oxide coating [74].
intense ionization and effects of charge transfer between the It may be seen that the temperature recorded at 50 Hz was
substrate and electrolyte over the oxide film with plasma [73]. almost 3100 K higher than that recorded at 500 Hz. This is due
According to Hussain et al. [35], various types of discharges to duration of each cycle. A cycle lasts 4 ms at 50 Hz which is
may occur in plasma electrolyte oxidation process as shown in ten times more than what it lasts at 500 Hz (0.4 ms). It means
Fig. 9. that a higher continuous energy is exerted on electrode surface
It may be observed that three types of discharge may occur in each cycle. In result, intense discharges and large sparks may
in processes which are designated as type A, type B and type C. be observed at 50 Hz which, in turn, lead to increase in surface
Type B discharges represent plasma reactions in substrate/ roughness and pore size. The discussed results were in agree-
coating interface. The intense peaks in Fig. 3 are related to these ment with SEM findings.
discharges. Type B discharges harshly affect microstructure and Wang et al. [78] developed a model for micro-discharge
morphology of coatings. In fact, intense discharges may lead to channels based on OES studies. Surface discharges in PEO
formation of a porous coating [35]. Two other types originate process may be divided into three steps. This model is sche-
from gas discharge in micro pores of the oxide film (provided matically presented in Fig. 11. It may be seen in Fig. 11a that a
that dielectric breakdown of the barrier film started under the great deal of small gas bubbles are evolved on sample surface.
micro pores) [76]. Type A is associated with rather fine pores In addition, a thin oxide film with defects and dopant is fabri-
near the surface while type C pores are related to the discharges cated in the normal oxidation step. Several oxides may also be
in micro pores at relatively higher depths. Variations in thermal observed on sample surface. In passing step (Fig. 11b), a bubble
signals during PEO processes may be attributed to discharge layer is formed due to evolution of many gas bubbles. It is
types [35]. possible that electrolyte anions are drawn to the bubble layer
Yao et al. [77] investigated magnesium-lithium coatings by and many micro-zones with strong electric fields are formed on
means of OES method at two frequencies (50 and 500 Hz). the working sample (anode). Hence, gas species within the
Plots of discharge temperatures versus PEO treatment period bubble layer (H2O and O2) may undergo ionization. It is also
are illustrated in Fig. 10. possible that the bubble layer explodes under the effect of
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Fig. 10. Typical time variation of Te by Na I lines and Na 589.0 nm/Li 670.8 nm ratios [77].
Fig. 11. Schematic illustration of the model describing the appearance of plasma discharge during different stages of the PEO process (a) Conventional anodizing,
(b) Transition, and (c)–(d) Plasma discharge [78].
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Fig. 12. Stages of vapor gaseous envelope evolution: a — oxygen evolution; b — bubble boiling in the VGE; c — microdischarges in the VGE; d — microdischarge
treatment of the surface micro profile; 1 — working electrode; 2 — electrolyte; 3 — oxygen (a) and vapor (b) bubbles; 4 — microdischarges [80].
strong electric fields in micro-zones. These results are different studied by this method [84]. AE technique is used to record
from traditional findings where primary breakdown occurs with elastic waves (between 20 kHz and 1 MHz) passing through a
entrance of electrons to the film (electron avalanche) [79]. The substance with local micro-displacements. Main principles of
role of bubble layer was not considered in the traditional this technique may be found elsewhere [85]. In fact, elastic
process. It is stated that the bubble layer had an influential role waves are propagated within a sample when a part of the
in the oxidation and discharge processes during PEO; also, free released energy in PEO process converts to mechanical energy.
electrons may be initially produced in oxide/electrolyte inter- The elastic waves may be tracked by AE standard technique
face due to strong electric fields. In discharge step (Fig. 11c and [82].
d), discharge occurs in the weakest dielectric point which has Voltage changes and acoustic energy during plasma electro-
defects and dopant after explosion of the bubble layer. It, then, lyte oxidation process are plotted in Fig. 13. The curves may be
repeats in weak points. The gas in this step is mostly oxygen. divided into several steps. Within the first step, voltage and
Using high-speed digital cameras, one may capture plasma acoustic energy augmented linearly up to a constant value.
oxidation process. Fig. 12 shows a process progress in a) evo- Then, they remained constant for 3 mins (second stage). In the
lution of gas bubbles, b) formation of gas layer, c and d) dis- third stage, voltage and acoustic energy increased by a new
charge. Fig. 8, indeed, confirms real photographs of the level with some fluctuations. The PEO process stopped, then,
proposed model in Fig. 11 [80]. and voltage became zero. Whereas, acoustic did not reach zero,
even though, it decreased (fourth stage). A conceivable relation
amongst electrochemical and acoustic parameters may be
3.4. Study of PEO coatings on magnesium through acoustic
observed. Let us now discuss each stage of the curves.
emission technique
First stage: it was mentioned earlier that a great deal of
Acoustic emission is a useful and non-destructive method oxygen was evolved on metal surface in the first stage leading
that has been employed for three decades for electrochemical to formation of an oxide film. It is showed that the oxide film on
characterization of coatings [81]. Boinet et al. investigated aluminum is porous. The recorded acoustic signals in the first
mechanisms of PEO coatings formation via AE technique stage (normal anodizing) were in step form. Acoustic energy
[82,83]. Many microscopic transformations alike crack propa- and domain are approximately small in the first stage and
gation, phase transformations and fracture have been studied by increase time of many signals was about 27 µs. According to
means of AE technique. It also is used as a non-destructive calculations, frequency range in this stage may be between 90
analysis in industry. Growth of oxide film on aluminum was to 200 kHz; while the highest value was 171 kHz. These values
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Fig. 14. Diagram of the development of microdischarge with a mobile liquid

cathode: (a) formation of microdischarge; (b) development of microdischarge;
Fig. 13. Voltage and acoustic energy transients during PEO, Japp: 30 A cm2 (c) change in geometry, cooling of the cathode, and termination of
[82]. microdischarge; and (d) elimination of the steam gas bubble; (1) metal, (2)
oxide coating, (3) electrolyte, and (4) plasma formation [90].
are in accordance with Simescu et al. [86] Considering these

data, one may attribute the behavior in the first stage to evolu-
tion of oxygen bubbles in normal anodizing. first stage. It is believed that signals in the fourth stage are due
Second stage: in this stage, increase in electric field intensity to release of hydrogen bubbles from surface of the oxide film
within the barrier layer causes fracture of micro-discharge in [82].
electrode/solution interface. Here, the acoustic signals are in
3.5. A dynamic model for creation of fine discharge channels
resonance form. Domain and energy of signals are higher than
during plasma electrolyte oxidation
the first stage. Moving to the second stage, energy of dielectric
fracture is high when fracture potential is obtained. This leads It was mentioned earlier that the complex PEO method con-
to increase in acoustic energy within the second stage. Acoustic sists of electrochemical, chemical and plasma chemical reac-
energy, in second stage, may be attributed to plasma anodizing tions which are determined by micro-discharges in metal-
(in particular, micro-spark regime) [83]. oxide-electrolyte system. Interface processes are affected by
Third stage: passing from micro-spark to spark is usually many external factors and they even become more complicated
accompanied with increase in voltage by 70 to 75 V as well as due to synergistic effects of these factors. Micro-plasma pro-
in acoustic energy by 5 × 107 to 5 × 108 Aj. It is reported that cesses studies provide the required means to develop a model
passing stage is when the surface is totally covered by the for each stage of the process [87–89]. Accordingly, Nechaev
anodic film. Voltage variations increase in this stage, while, et al. [90] proposed a dynamic model for formation of micro-
sparks decrease. Acoustic signals (in resonance form) are like discharge channels in plasma electrolyte oxidation. Gas bubbles
the second stage with only having higher domain and energy. contain electrolyte ions which are accelerated under strong
Size and energy of sparks increase in this stage. Peak frequen- electric fields. The ions impact with the oxide film at the end of
cies are similar with the second stage; hence, phenomena such pores and increase temperature of the oxide film and gas
as micro-spark and sparking may be identified via acoustic bubbles. Free electrons are produced by impact ionization. The
energy value and pulse domains. The acoustic energy originates electrons also accelerate in electric fields and consequently
from the sparking energy in the third stage [82]. electron avalanche that causes electric breakdown begins
Fourth stage: although current becomes zero after stopping (Fig. 14a). Gas bubbles turn into plasma bubbles and discharge
of the anodizing process, fourth stage may be observed for channels are formed. One electrode is metal channel and the
acoustic energy. The recorded signals in this stage are similar other is electrolyte surface with negative charge. Thus, charge
with those recorded in the first stage. Peak frequencies are also remains constant due to emission of electron from the liquid
the same as the first stage. However, signal characteristics are cathode. Electron emission leads to electron avalanche and then
different i.e. energy and domain of signals are higher than the brings about plasma heating. Plasma expands when heated and
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interface. Outward diffusion of magnesium ions along with

inward diffusion of oxygen ions are responsible for growth
[73].
Curves of coating thickness variations, outward and inward
growth thicknesses, L0/Lt and Li/Lt are shown in Fig. 16. It may
be seen that thickness of PEO coating increases linearly with
increase in coating formation period. According to the mecha-
nism of PEO coating formation proposed by Sandrajan et al.
[91] linear increase in thickness may be related to Faraday’s
Electrolysis Law. L0/Lt was higher than Li/Lt in the beginning,
Fig. 15. Schematic diagram of dimension changes of magnesium alloy before
however, this trend is reversed with increase in PEO coating
and after PEO treatment [73]. period so as Li/Lt becomes higher. This means that outward
growth was initially dominant, whereas, inward growth
becomes dominant with increase in treatment time. This may be
electrolyte boundary moves from the end of pore toward its attributed to activation of diffusion by heat. In PEO process,
opening. Bubbles expand in pores width till they reach the heat-activated diffusion and ions transfer have special roles in
opening (Fig. 14b). As soon as a bubble reaches the opening, its coating growth [72]. In magnesium coating formation process,
expansion continues and surface area would increase due to magnesium cations diffuse out from the substrate and react with
change in its geometry. This leads to more reduction of spon- anions forming a ceramic coating. In other words, oxygen ions
taneous emission. End of emission leads to quenching and diffuse toward the magnesium substrate under strong electric
explosion of the bubble (Fig. 14c). Electrochemical reaction fields and react with magnesium ions in discharge channels
take place in metal/plasma interface, while, plasma chemical forming the oxide film. According to oxygen-regarding OES
reactions occur in plasma formation process. Metallic atoms or studies, dominance of inward growth at long durations is the
ions that evaporated from the anode surface may contribute to amount of excited oxygen after more than 45 mins.
chemical reactions regarding plasma formation. Reaction prod-
ucts precipitate in the end and walls of channels once bubbles 3.7. Study of PEO coating formation on magnesium
are quenched. Then, channels would be closed by products of according to electronic properties of the PEO film
electrochemical and plasma chemical reactions (Fig. 14 d). Electronic behavior of the electrode significantly influences
the properties of PEO coatings. Mechanism of oxide film for-
3.6. Oxide layer growth direction and its mechanism
mation may be realized by study of semi-conductive properties
PEO layer growth is reported to follow a linear order in of electrode in PEO process. Duna et al. [93] investigated semi-
literature while there are several studies that indicate the linear conductive properties of AZ91D alloy in order to provide a
function may deviate at long periods [75,91,92]. Hussain et al. better understanding around film formation process. Properties
studied growth direction of oxide films on magnesium sub- of semi-conductor/electrolyte may be explained by Mott–
strates [73]. Coating formation on magnesium in PEO process Schottky theory which shows the effect of applied potential on
is illustrated in Fig. 15. The dash line between L0 and Li repre- electrode capacity during plasma electrolyte process [94–96].
sents the primary magnesium alloy surface prior to coating The alkaline electrolyte that was used for PEO process had a pH
formation process. Generally, growth of PEO coating on mag- between 12 and 14 which included the AZ91D passivation
nesium is due to molted magnesium oxide, when it is flowing zone. Therefore, formation of a natural passive film on alloy
out through discharge channels. Magnesium oxide flows out surface is expected once the alloy is placed into the electrolyte.
through discharge channels and quenches in electrolyte/coating Capacity measurements (Fig. 17) showed that capacity of mag-
Fig. 16. Inwards and outwards coatings portion during PEO coatings (a), coatings portion ratios to the total thickness (b) vs. treatment time [73].
ARTICLE IN PRESS
Fig. 17. Mott–Schottky plots of magnesium alloy AZ91D substrate in PEO

electrolyte, the solid line is fitting result based on the linear equation [93].
Fig. 18. Variation of donor levels in the oxide films formed on magnesium
alloy AZ91D with cell potential and oxidation time during PEO process [93].
nesium substrate in PEO electrolyte reduced with application of
potential that led to creation of a straight line with positive
slope in Fig. 13. It reflects that magnesium substrate shows an With increase in potential (till fracture of the PEO film in
n-type semi-conductive behavior in PEO electrolyte. Nq param- silicate electrolyte), a strong electric field is formed due to high
eter in n type semi-conductors indicates the concentration of electric energy in the thin barrier oxide film. Some atoms are
donor in electrode/electrolyte interface. Donor often bears posi- affected in the oxide film lattice when the electric field energy
tive defects such as interstitial cations or void anions [97]. In is sufficiently high to excite doping (such as voids or
formation of passive films, magnesium atoms depart the metal interstitials), hence, electron-void couples are created. Finally,
lattice and enter the oxide lattice film. Then, oxygen voids are an extreme current would be formed and an electron/ion ava-
formed in electrode/passive film interface according to the fol- lanche happens in weak locations over the oxide film. The
lowing equation [98]: stored energy in doping is released in the form of kinetic energy
Mg → Mg M + VO2 + + 2e − (9) of ions or electrons, Joule heat and sparking [93].
After sparking, film growth process still maintains several
Where Mg is magnesium atom in metal lattice, MgM is features in common with normal anodic oxidation process.
magnesium atom in oxide film and VO2+ represents oxygen However, there are also obvious differences. A similar feature is
voids. Oxygen voids cause n type semi-conductive behavior of that the film growth basically depends on defects or ions dis-
magnesium electrode when dipped in PEO electrolyte. Since placement under strong electric fields. A different feature of
the natural film is extremely thin, the major charge transfer type PEO process compared with normal anodic oxidation is pres-
is direct electron transfer between oxidative-reductive electron ence of sparks and effects of sintering and solidification. Sub-
couples in electrolyte and metallic substrate via tunnel strate and electrolyte components turn into vapor or plasma
phenomenon. under strong electric fields [99]. Consequently, rate of PEO film
Oxide film growth is similar with normal anodic oxidation in formation increases as plasma has more conductivity and reac-
the first stage of PEO process (prior to sparking). With an tivity rather than ions. Also, spark sintering leads to completion
increasing potential over time, oxidation reaction occurs on of PEO processes as well as formation of more oxide products.
electrode surface and a thin magnesium film is formed on Simultaneously, molten oxide solidifies quickly as electrolyte
magnesium surface. The continuous oxide film increases elec- temperature is much inferior than that of the molten oxide.
tron and ion passage resistance in electrode/electrolyte inter- Hence, the synergistic impact of strong electric field and solidi-
face. In PEO process, growth of PEO film is mainly caused by fication of PEO electrolyte causes an accelerated growth in
displacement of voids or interstitials under strong electric fields oxide film. One may come to the conclusion that once fracture
[99]. Capacity measurements revealed n type semi-conductive potential is reaches, PEO coatings would experience faster
behavior at all times and applied potentials. However, donor growth rates [93]. Therefore, oxide film growth is basically
concentration underwent changes in different stages of PEO pursued by an electric field-assistant mechanism.
process. As it may be seen in Fig. 18, concentration of magne-
sium electrode donor decreased; in addition, electron and ion 4. Properties of PEO coatings deposited on magnesium
passage resistance increased severely due to formation of a thin
4.1. Corrosion resistance
oxide film on magnesium electrode. Presence of a thin dielec-
tric oxide film is necessary for formation of a strong electric Poor corrosion performance of magnesium alloys is a main
field and plasma discharge sparking in PEO process. limiting factor in broader application of these alloys in indus-
ARTICLE IN PRESS
Fig. 19. Effective parameters in corrosion resistance of PEO coatings.
trial and biomedical sectors [100]. Plasma electrolyte oxidation sulfate electrolyte, increase in chloride concentration led to
has been recognized as an effective method to overcome this increasing corrosion rates and decreasing electrochemical
problem. Efficiency of PEO ceramic coatings on corrosion impedance. The increased ratio of corrosion current density
resistance has been investigated in previous studies. In some along with the decreased ratio of charge transfer resistance
cases, corrosion current densities of uncoated samples were indicate that extent of corrosion damage in PEO coated AZ31
reported to be 100 times [101] or more [102–105] lower than alloys is much more severe when chloride concentration is
uncoated ones. However, these coatings were considerably higher than 5% [107].
porous and it has been concluded that this is a main factor It was observed that coatings produced on AM50 magne-
preventing more corrosion resistant coatings to be obtained. sium alloy using phosphate electrolytes and manly consisted of
Effects of different parameters including electrolyte compo- MgO were quickly dissolved in acidic NaCl solutions (pH = 3)
sition, electrical factors such as current type and intensity as and lost their protective features. This event delayed in neutral
well as procedure time, alloy composition and pre-treatments NaCl electrolytes and corrosion damage became local instead.
applied on the alloy are extensively discussed in the present On the other hand, MgO underwent an insignificant loss in
review paper. The effective parameters in corrosion resistance alkaline NaCl solutions (pH = 11) [108]. An analysis of the
of PEO coatings are schematically described in Fig. 19. experimental data led the researchers to propose that in case of
It was shown that corrosion of PEO-coated magnesium MA8 alloy which was coated in a silicate-fluoride electrolyte
alloys in chloride media increased with an increasing chloride using bipolar current, the corrosion process within damaged
concentration. Electrochemical tests on PEO coatings on area mainly happened in magnesium/coating interface
AZ91D magnesium alloy fabricated by means of AC current in [109,110] . 5.0wt.% NaCl salt spray test on PEO-coated AZ31
an alkaline silicate electrolyte revealed that pitting occurred at magnesium alloy (carried out in different times) revealed that,
high NaCl concentrations (1%, 3.5% and 5%) while coatings in the beginning, the corrosive solution penetrated in the struc-
suffered uniform corrosion at low concentrations (0.1% and tural defects (including pores and cracks) and brought about
0.5%). PEO coatings on AZ91D alloy provide a better protec- corrosion of substrate alloy. Charge transfer was disrupted due
tion against corrosion in dilute NaCl solutions [106]. In case of to accumulation of corrosion products after 48 h. The stress
AZ31 alloy on which PEO coating was fabricated in a sodium caused by accumulation of corrosion products, with further
ARTICLE IN PRESS
Fig. 20. Stress–strain diagram of AM50 samples (with and without PEO coating) tested in air and ASTM solution [113].
continuation of tests up to 120 h, led to creation of new solution. It was reported that fatigue limit of samples fabricated
microcracks in the coating which, in turn, provoked corrosion in an electrolyte containing pyrosulfate, silicate and fluoride
[111]. reduced in air and 3.5%NaCl solution by 38 and 58 percent,
Prior to providing a detailed discussion about the above- respectively. This was attributed to roughness of coating/
mentioned cases, the studies carried out by Srinivansan et al. substrate interface, stress concentration and cracking of coating
[112–116] will be explained. Those studied dealt with the effect under stress which consequently led to creation of Numerous
of PEO coatings on stress corrosion cracking in some Mg initiation sites for fatigue cracks. The situation was worse in
alloys. Srinivansan et al. reported that AM50, AZ31, AZ61 and 3.5% NaCl solution due to corrosive effect of the media on
AZ31HP alloys (which was previously subjected to autogenous sample especially near Al-Mn particles [118]. Hence, it is sug-
laser beam weldment and PEO treated in silicate-based electro- gested that future researches address improvement of coatings
lytes) did show a higher resistance against general corrosion. performances and optimization of PEO-treatment parameters
However, PEO coating had an insignificant impact on samples for application in under-stress operating conditions.
performance in slow strain rate test in ASTM D1384 solution
and failed in prevention of SCC occurrence. It was also 4.1.1. Effect of electrolyte ions on corrosion resistance
observed that PEO coatings on welded zones of wrought AZ61 Alkaline electrolytes are commonly used for PEO treatment
alloy could not prevent stress corrosion cracking [117]. of magnesium alloys; so that a stable coating would be achiev-
PEO coatings that were fabricated on AZ31 alloy in able and quick dissolution of anode may be avoided, consider-
phosphate- and silicate-based electrolytes also did not notice- ing high chemical activity of magnesium in acidic media [119].
ably change SCC behavior of alloy [116]. It may be observed in Alkaline metals hydroxides (such as NaOH [120,121] and KOH
Fig. 20 that the coated sample, yet better than the uncoated one, [122,123]) are generally used to adjust pH in electrolyte baths
showed lower ultimate tensile stress values compared with the employed for PEO processes. In addition to adjust pH, these
coated sample tested in air. In all four studies, PEO coating led compounds also improve conductivity of solution which is to be
to reduction of sample elongation at breakdown point in air. It used for PEO treatment [119].
implies that cracking of PEO coating (which is brittle due to its Acidic electrolytes, containing fluorozirconate and similar
ceramic nature) during sample deformation provides suitable inorganic salts were also reported to be used for PEO processes,
areas for crack initiation [113]. but even in these cases researchers tend to carry out first treat-
Cracking of the corrosion product layer in untreated alloy ment steps in alkaline electrolytes in order to achieve a stable
and that of hard ceramic coating in PEO sample as well as coating and avoid quick anodic dissolution of magnesium due
hydrogen ingress caused by electrochemical processes were to high instability of the magnesium substrate in acidic electro-
recognized responsible for SCC-triggered failure [116]. Similar lytes [108,124,125].
effect regarding deterioration in performance of PEO-coated Addition of various compounds to the electrolyte may bring
AZ61 samples under tension were observed in fatigue test. about variations in coatings properties through several mecha-
Samples were subjected to stress cycles in air and 3.5% NaCl nisms such as changing electrolyte properties (thus altering
ARTICLE IN PRESS
Fig. 21. Surface morphology of oxide layer of AZ91 Mg alloy formed by PEO process at 10 A/dm2 in electrolyte with/without potassium fluoride; (a),(b): samples
coated from Bath A (0.08 M/L KOH +0.04 M/L Na2SiO3) for 120 and 600 s, respectively, (c),(d): samples coated from Bath B (0.08 M/L KOH +0.04 M/L
Na2SiO3 + 0.08 M/L KF) for 120 and 600 s, respectively [128].
working and final voltages) or contribution of additives in struc- 11 g.dm−3 sodium silicate (Na2SiO3) and 2.5 g.dm−3 potassium
ture of PEO coatings. Effects of different anions and cations hydroxide (KOH) led to significant changes in voltage–time
[126,127] in solutions on corrosion properties of the coating response in AZ61 alloy during PEO process using bipolar pulse
have been proved in many studies. current. For instance, the voltage required for initial sparking
Fig. 21 shows the effect of KF addition to an electrolyte decreases, while, at longer periods, as the coating process con-
containing KOH and Na2SiO3 on surface appearance of the tinues, sparking voltage is higher in KF-free baths. The coatings
PEO coating formed on AZ91 substrates under different oxida- produced in electrolytes with potassium fluoride contained 2–4
tion times. It was observed that corrosion resistance of the at% F [131]. Corrosion resistance was observed to be depen-
coating produced in KF-bearing electrolyte was Superior to the dent on MgF2 content. Accordingly, high corrosion resistance
one produced in KF-free electrolyte. In spite of larger pores on and low susceptibility to pitting corrosion was found in films
the coating surface, the oxide layer possessed a compact produced in electrolytes with high KF concentrations (which
barrier-type passive film with fluoride ions in presence of KF promotes formation of MgF2) [132]. Liu et al. reported that
+in the electrolyte. It was concluded that presence of MgF2 and presence of KF in PEO treatment bath for AM50 alloy may be
MgO could provide a beneficial impact on corrosion resistance of great importance in occurrence of in-situ sealing of pores in
[128]. PEO coating. This was reported to be due to lower solidifying
Introduction of potassium fluoride to the electrolyte solution point of MgF2 compared with other coating constituents [133].
leads to reduction of pores size and surface roughness as well as It was reported that electrolytes with potassium ions in the
increase in compactness of micro-arc oxidation coating. Mean- form of hydroxide, phosphate or combined, produce films with
while, it alters composition of coatings phases due to contribu- more compactness than those bearing sodium compounds. On
tion of KF in the reactions during the coating formation process the other hand, smaller pores were seen in the outer part of
and its presence in the PEO coating [4]. PEO processing in coatings produced in Na-bearing electrolytes [134].
Na2SiO3-KOH electrolytes bearing 0.05, 0.15 and 0.2 mol.lit−1 Fig. 22 shows the effect of different KOH concentrations on
KF led to noticeable changing of corrosion potential (300– AZ91D alloy in an electrolyte containing 0.5M KF + 0.25M
500 mV) toward nobler areas. Corrosion rates of coated Na3PO4.12H2O. The coating produced in 3M KOH electrolyte,
samples were considerably less than uncoated ones, especially under low current density and long anodizing time, had a better
when KF concentration was at an average level (0.01– corrosion performance than that produced in 1.5M KOH elec-
0.05 mol.lit−1) [129]. trolyte. This was reported to be due to reduction in coating
It was seen that coating thickness increased with addition of porosity [135]. Ko et al. [136] also reported that different KOH
KF to an aluminate-based electrolyte (bearing NaAlO2). In concentrations led to significant variations in morphology of
addition, corrosion resistance was improved by formation of an coating layers. Two cells were used for the process that each
internal compact film with MgAl2O4 crystallines and F ions contained 0.04 M Na2SiO3 and 0.09M KF. KOH concentration
[130]. Addition of 8 g.lit−1 KF to a silicate-phosphate electro- in cell (A) was 0.09 while it set at 0.27 in cell (B). Pores with
lyte 10 g.dm−3 sodium pyro-phosphate (Na4P2O7.10H2O), larger size than the one on cell (A) sample were observed in the
ARTICLE IN PRESS
Fig. 22. SEM observations of anodized AZ91D Mg Alloys in (a) 1.5M KOH electrolyte and (b) 3M KOH electrolyte (30 mA.cm−2 – 10 min) [135].
oxide film produced in cell (B). The average diameter of pores higher thickness and porosity than that produced in a silicate
in cell (B) coating was almost 5 µm while it was about 2 µm in electrolyte under the similar current densities. This was
cell (A) coating. However, the electrolyte with higher KOH explained to be in relation to loss of dielectric stability and
provided a better corrosion resistance for magnesium alloy application of a lower current. Corrosion resistance of the
which may be explained by different conditions and electrical coating may be associated to its uniform and compact structure
properties in electrolytes due to different KOH concentrations. which acts as a barrier against transition of corrosive ions from
According to observations, MgO content increased in coating the aggressive electrolyte into the coating [38]. Mori et al. [139]
with an increasing KOH concentration. It should be considered studied the optimized ratio of the two anions in an electrolyte
that corrosion behavior is strongly affected by MgO content. containing both silicate and phosphate. They realized that
Aluminates, silicates and phosphates are other common micropores and micro-canals became smaller at lower phos-
additives for electrolytes in PEO treatment of magnesium phate concentrations, making the coatings formed in low phos-
alloys. Added singular or combined, these additives may bring phate concentrations more resistant to corrosion. However,
about considerable changes for coating properties. It was shown pitting corrosion was observed in these coatings. They also
that anions directly contribute to coating formation process. reported that the amorphous phosphate existed in coatings with
Aside from MgO which is the common constituent in all types
of coatings, special phases including MgSiO4, Mg3(PO4)2 and
MgAl2O4 are formed with Si-, P- and Al-bearing electrolytes
respectively [137].
A general view of PEO coatings fabricated in phosphate
(10 g.lit−1 Na3PO4) and silicate electrolytes (10 g.lit−1) on AM50
alloy is illustrated in Fig. 23 and Fig. 24. Unipolar pulsed
current was used and 1 g.lit−1 KOH was added to the electro-
lytes. It was seen that PEO coatings obtained from the silicate
electrolyte were comparatively thinner and had smoother sur-
faces with smaller pores compared with those produced in
phosphate based electrolytes.
A close look at the cross sections revealed that +substrate/
coating interface region, in Si-PEO coating (Fig. 23a), was very
thin and had few defections providing suitable adhesion to the
substrate. On the other hand, P-PEO coating had a more coarse
interface region with many micropores (Fig. 24a). Mg3(PO4)2
and Mg2SiO4 are formed in coatings produced in phosphate and
silicate based electrolytes, respectively. Meanwhile, MgO is
present in all coatings.
Corrosion performance of Si-PEO coating was better in both
short- and long-term tests. Denser inner layer, less porosity and
better interface along with the chemical stability of Mg2SiO4
are named as probable causes for better performance of Si-PEO
coatings in long-term corrosion tests [138].
In another study on pure magnesium using AC current, the Fig. 23. Surface and cross-section morphology of PEO coatings formed in
coating formed in a phosphate electrolyte was observed to be of silicate based electrolyte [138].
ARTICLE IN PRESS
and KF by bipolar current mode. High polarization resistance

values (1.04 × 106 V for the P-film and 2.62 × 105 V for
Si-film) were recorded which indicated efficiency of PEO
process in improvement of corrosion resistance of coatings.
Similar to previous cases where KF was present in electrolytes,
a fluoride-rich film was also created here on coating/substrate
interface using both electrolytes [142]. In contrast with former
findings, Ma et al., using HPO42− hydrogen phosphate solution
for comparing P- and Si-bearing coatings, reported that P-PEO
coatings had a corrosion resistance ten times higher than
Si-PEO coatings [143].
Aluminates are another substance being commonly used in
the PEO process. As it was mentioned earlier, presence of
aluminates in the solution promotes formation of MgAl2O4
[104,122], which is highly stable [104]. It was observed, in a
KOH-containing electrolyte, that the coating became richer in
MgAl2O4 with increase in NaAlO2 concentration. A greater
proportion of MgAl2O4 against a lesser proportion of MgO is
reported to be helpful in improvement of corrosion resistance
[123].
It was seen, in PEO treatment on AZ91D alloys in electro-
lytes containing silicate or silicate/aluminate, that the coating
formed in presence of both of these additives showed a better
Fig. 24. Surface and cross-section morphology of PEO coatings formed in
performance in terms of corrosion resistance (through EIS
phosphate based electrolyte [138]. tests) compared with the coatings produced in electrolytes with
only one of them. Besides, a self-sealing mechanism was iden-
tified in PEO coatings immersed in a chloride containing solu-
tion [144].
high silicate/phosphate ratio which had an important role in Rama Krishna et al. [145] obtained the optimum concentra-
corrosion resistance of PEO coatings by involvement in self- tions of aluminate and silicate in an electrolyte containing both
repairing mechanism. The optimum P:Si ratio in electrolyte was additives (4 g.lit−1 NaAlO2 and 6 g.lit−1 Na2SiO3). Direct current
reported to be 20:80. Zhang et al. also achieved an optimum density of 0.2 A.cm−2, potential of 180 to 200 V and the afore-
concentration for sodium silicate in a P-containing electrolyte mentioned concentrations led to the least amount of pores and
through use of phytic acid (C6H18O24P6). The optimum concen- a 100 times reduction in corrosion current in comparison with
tration of sodium silicate for the best corrosion resistance in an uncoated samples.
electrolyte with 12 g.lit−1 phytic acid and 10 g.lit−1 sodium Presence of SiO32− in the electrolyte, in PEO treatment on
hydroxide was reported to be 10 g.lit−1. The coating became AM50 alloy, led to production of a more stable passive layer
thicker with increase in sodium silicate concentration while the than once PO43− existed in the electrolyte. Although the latter
structure and micropores grew rougher and larger, respectively resulted formation of a more stable passive layer than the
[140]. coating produced in an AlO2−-containing electrolyte, silicate-
Gua et al. studied AZ31B PEO treatment in an electrolyte bearing electrolyte produced a coating with best corrosion per-
containing 6 g.lit−1 Na2SiO3, 2 g.lit−1 KF, 2 g.lit−1 KOH and formance [137]. Using AC current elsewhere, the same
10 ml.lit−1 glycerol at current density of 30 mA.cm−2. They concentration of 10 g.lit−1 was reported to be optimum concen-
stated that MgO formation mechanism was similar to regular tration for these three electrolyte constituents (Na2SiO3,
anodizing, whereas, Mg2SiO4 formation could be attributed to a NaAlO2 and Na3PO4) when they all exist in the PEO bath. The
phase transformation between SiO2 and MgO due to high- deposited coating showed suitable corrosion resistance with a
temperature conditions and rapid cooling effect of the electro- certain passivation area in anodic zone [146].
lyte in PEO process [141]. (NaPO3)6 is another P-bearing compound that may be added
There are different ideas in literature around efficiency of P- to PEO electrolytes. Corrosion resistance was observed to
and Si-containing electrolytes in improvement of corrosion diminish with increase in concentration of (NaPO3)6 in an elec-
resistance of PEO coatings. Mostly, coatings produced in trolyte bearing Na2SiO3 and NaOH. This was mainly due to the
Si-containing electrolytes are reported to have a better perfor- fact that the excellent microstructure is obtained at low
mance in regard with corrosion resistance than those deposited (NaPO3)6 concentrations [147]. It was seen, elsewhere, that
in P-containing electrolytes [38,138,139,142] For instance, two thickness of PEO coating increased with increase in concentra-
PEO coatings were applied on AZ91D alloy in a P-containing tion of (NaPO3)6 while surface roughness and micropores size
electrolyte with (NaPO3)6, Na3AlF6, KOH and triethanolamine also increased. The optimum concentration level of (NaPO3)6
and a Si-containing electrolyte with Na2SiO3, Na2B4O7, KOH was reported to be 5 g.lit−1 [148].
ARTICLE IN PRESS
Like (NaPO3)6, increase in K4P2O7 over a critical concentra- Figures d and e show that surface conditions were worsened in
tion brings about undesirable consequences regarding corrosion coatings with further increase in K2TiF6 concentration up to
behavior of the fabricated coatings. Size of surface pores 10 g.lit−1. TiO2 and Mg2TiO4 were detected in the coating formed
increased at high K4P2O7 concentrations. The optimum level for in the electrolyte containing K2TiF6. The optimum K2TiF6
potassium pyrophosphate was reported to be 0.03 mol.lit−1 concentration for achieving the best corrosion resistance was
which produced a coating with the best corrosion properties. reported to be 8 g.lit−1 [58]. Black PEO coatings formed in a
Also, K4P2O7 had a positive effect on corrosion behavior of K2TiF6-containing electrolyte showed photocatalytic properties
internal barrier layer [149]. due to presence of TiO2 [157]. Zr-bearing additives have also
Application of 2 g.lit−1 sodium tetra borate (Na2B4O7.10H2O) attracted attentions due to high chemical stability of ZrO2.
was seen to significantly improve corrosion performance of PEO Corrosion damages in coatings that contained ZrO2 were seen
coatings by producing a less porous coating layer. Corrosion to be minimized in 3.5wt.% NaCl solutions at long-term
resistance of this coating was 2 × 106 times superior to that of the experiments [124]. ZrO2-containing coatings were successfully
substrate. It was also 35 times better than the coating fabricated prepared using an electrolyte with sodium dihydrogen phosphate
in the base electrolyte containing 10 g.lit−1 Na2SiO3.9H2O+ (1 g.lit−1, NaH2PO4) and potassium fluorozirconate (3 g.lit−1
4 g.lit−1 KOH [150]. Introduction of sodium borate to an K2ZrF6) [158,159]. Among Zr-containing additives K2ZrF6
electrolyte containing C6H18O24P6 caused reduction of solution produced better corrosion properties than ZrOCl2 and Zr(NO3)4
conductivity. added up to 10-30 g.lit−1, sodium borate reduced due to formation of a denser internal film and a more uniform
final voltage value, while the final voltage increased at addition surface [160]. Table 1 summarizes the effect of some inorganic
of 40 g.lit−1 sodium borate. The coatings became thicker and additives on corrosion performance of PEO coatings on
their structure roughened which is caused by larger sparks on magnesium.
surface of the samples at this high concentration. Mg3B2O6 was
identified in coatings fabricated in electrolytes with 10-30 g.lit−1 4.1.2. Effect of organic additives on corrosion resistance
sodium borate. However, corrosion properties of coatings which Organic additives are also used to modify PEO
were produced in no-sodium borat electrolytes were reported to electrolytes; however, fewer articles have been published on
be superior [151]. Addition of Na2B4O7.10H2O to PEO this area than inorganic additives. Micropores and
electrolyte for treatment of ZM21 alloy led to creation of a thick microcracks in surface were reduced in size and number by
and low-porosity coating not adjacent to the substrate. In other introduction of glycerol (C3H8O3) to the base electrolyte
words, the barrier film of this coating became thicker and less- containing Na2SiO3-NaOH-Na2EDTA. By being substituting
porous for the sake of this additive. The corrosion resistance of water molecules when being adsorbed on anode surface as
coating, hence, was improved by 200 times [152]. It was seen, in well as on anions produced by dissolution of sodium silicate,
electrolytes with silicate and phosphate, that addition of this additive creates smaller but more frequent sparking events
Na2B4O7 assisted the self-repairing mechanism in oxide film sparks in PEO process. addition of glycerol increased the
caused by strong binding forces between silicate and phosphate volume portion of MgO. The optimum concentration of
ions and Mg2+ ions (which dissolved from the substrate). In glycerol for the best corrosion properties was reported to be
addition, Na2B4O7 effectively reduced crack initiation in 4 ml.lit−1. Corrosion current density of coatings produced in
repaired films [153]. this electrolyte reduced by 100 times in potentiodynamic
Song et al. carried out PEO process in an electrolyte con- polarization tests compared with coatings produced with the
taining 3 g.lit−1 NaOH, 6 g.lit−1 (NaPO3)6, 2 g.lit−1 Na5P3O10 and base electrolyte [171]. It was stated that introduction of this
10 g.lit−1 K2TiF6. They expressed that self-sealing properties additive to treatment bath led to fabrication of a more dense
could be detected. Fluorides (whose self-sealing effect was coating with more uniform pores. It also proved helpful in
previously addressed in KF-containing electrolytes [133]) and refinement of sparking and its thermal impacts [172].
magnesium oxide are among the main sealing components. Phytic acid (C6H18O24P6) and sodium silicate (Na2SiO3) were
Titanium oxide and phosphates were also identified in the used in separate electrolytes to provide P and Si, respectively,
coating. Concentration of fluorides was higher within the inter- for PEO treatment of AZ91HP alloy. The coating produced in
nal layer. Self-sealing of pores mainly originates from various the phytic acid electrolyte was seen to be slightly thinner than
sintering temperature of components in the film [154]. The that formed Si electrolyte and according to the electrochemical
residual titanium oxide with high chemical stability may effec- tests, it showed a better corrosion resistance. This indicated that
tively restrain inward movement of the corrosive medium. more desirable corrosion properties may be achieved when
Changed color of the PEO film after corrosion may be attrib- large molecules of phytic acid are used in order to produce
uted to formation of white Mg(OH)2 (as corrosion product) P-containing coatings. It was observed that pores of the coating
[155]. produced in Si electrolyte were worse in terms of uniformity.
As it may be observed in Fig. 25(a), the PEO coating formed on The Si-electrolyte film was amorphous while the coating
AZ91D alloy in a K2TiF6-free electrolyte (containing 10 ml.lit−1 of formed in the phytic acid electrolyte mainly consisted on MgO
triethanolamine, sodium hydroxide, hexametaphosphate and phase [173]. The optimum concentration of phytic acid to
sodium) had rather uniform surface with many pores (with obtain the best corrosion properties was reported to be 8 g.lit−1,
approximate diameter of 50 µm). Size of pores plummeted with elsewhere. Increasing phytic acid concentration led to reduction
increase in K2TiF6 concentration from 0 to 8 g.lit−1 (Figures b to d). of electrolyte conductivity and increase in breakdown voltage.
ARTICLE IN PRESS
Fig. 25. Coatings deposited at different K2TiF6 concentrations. (a) 0 g.lit−1, (b) 2.0 g/L, (c) 6.0 g.lit−1, (d) 8.0 g.lit−1, (e) 10.0 g.lit−1, (f) 12.0 g.lit−1 [156].
EDX analysis showed that phosphorous content increased in the Further research is required to acquire broad information
film with addition of phytic acid [174]. regarding effects of organic additives on improvement of cor-
Introduction of 8-HQ as an organic additive to a silicate rosion properties and modification of self-treatment mecha-
solution may improve conductivity and promote coating forma- nisms; however, environmental issues have to be considered
tion. Addition of this substance to PEO bath was observed to when selecting the organic chemicals.
cause formation of insoluble Mg(HQ)2 and decrease in pores
size. Potantiodynamic polarization tests revealed that the best 4.1.3. Effect of electrical variables on corrosion resistance
corrosion performance was obtained by PEO treatment in an Considering the electrochemical nature of plasma electrolyte
electrolyte with 10 g.lit−1 NaOH, 18 g.lit−1 Na2SiO3 and 2 g.lit−1 oxidation processes, voltage/current characteristics of the
8-HQ [175]. The insoluble magnesium-tannate compound may applied electricity may noticeably affect the coatings features.
be obtained by addition of tannic acid. Tannic acid addition may In this regard, several parameters such as state and polarity of
also lead to reduction of stress in gas–liquid and gas–solid current and voltage, frequency, current density and duty cycle
interfaces. The film structure was more homogenous and have been addressed in literature.
thicker rather than the one produced in the electrolyte without Unipolar and bipolar current types are used for PEO treat-
tannic acid [151]. The effect of some organic additives on ment processes. Bipolar current has been more studied in
corrosion performance of PEO coatings on magnesium is achieving desirable corrosion properties. Unipolar and bipolar
briefed up in Table 2. current types were used in studying PEO treatment on AJ62
ARTICLE IN PRESS
Table 1
Effect of some inorganic additives on corrosion performance of PEO coatings on magnesium.
Substrate Base electrolyte Additive Coating Thickness Porosity Effect on corrosion Ref
alloy (BE*) composition (concentration) composition (avg pore behavior
diameter)
AZ91 KOH + KF + Na2SiO3 KMnO4 MgO and Mn2O3 11.19 to 4.84 NM About 10 times lower corrosion [161]
current density in presence of
KMnO4
Pure 0.05M Na3PO4.12H2O + KMnO4 MgO, Mg3(PO4)2 and 15~20 to 30~40 NM Shift in Rp from 4.31 Ω.cm2 in BE to [162]
0.2M Na2SiO3 (0 to 0.015 M) Mg2SiO4 18.39 Ω.cm2 in 0.001M KMnO4 and
.9H2O+1M NaOH to 5.75 Ω.cm2 in 0.001M KMnO4
AZ91D 15 g/L NaAlO2 + 1.2 g/L CeCl3 NM Similarly 5 µm 27% to 1.7% Corrosion current density 9 times [163]
KOH (0.08 g/L) higher in coating formed in BE
AZ31 15 g/L Na2SiO3 Cerium nitrate MgO and MgSiO3. 13.2 to 11.9 ~5 µm Rp is ~6.5 times lower than the [126]
+5.0 g/L NaOH 0.1 g/L coating formed in BE
Lanthanum nitrate MgO and MgSiO3. 13.2 to 15.1 ~5 µm Rp is ~55 times lower than the
0.1 g/L coating formed in BE
AZ91D 3 M KOH+0.5 M K2SnO3 · 3H2O MgSn(OH)6 and between 7 and NM Improved pitting resistance [164]
KF+0.25 M Na3PO4.12 (0 to 0.5M) amorphous MgO 10 µm in BE to Pitting potential shifts from −1.30
H2O 0.1 M 5 µm (V/SCE) in BE to −1.04 (V/SCE) in
0.1 M K2SnO3
AZ91 5 g/L KOH + 5 g/L KF+ Na2SnO3(0 to 3 g/L) MgO, SnO, Mg2SiO4, ~2.3 µm to ~6 µm NM The sample coated in BE has a lower [165]
3 g/L Na2SiO3 and MgF2. resistance to localized attack than the
sample coated in K2SnO3-containing
electrolyte
AZ91HP 10 g/L NaOH and 12 g/L Na2WO4 ~30% mass fraction of NM (1.0 µm in BE, NM The immersion test showed that [166]
phytic acid 0 to 8 g/L W in coating formed in quantitatively with Na2WO4 decreases the corrosion
BE+8 g/L Na2WO additive added but resistance of the coated samples as
larger than BE) more corrosion pits were observed in
samples after immersion with
increasing Na2WO4 in coating bath
LA141 2.0 g/L NaOH Na2WO4 MgO, Mg2SiO4 and WO3 ~12 µm in BE to (0.7 to 4 µm in BE Rp value is 1.78 times bigger in [167]
15.0 g/L Na2SiO3 0 to 0.6 g/L 22 µm in BE + 1 to 2.5 µm in BE + electrolyte containing 0.6 g/L
5 mL/L triethanolamine 0.6 g/L Na2WO4 0.6 g/L Na2WO4) Na2WO4
AZ91D 2 g/L KOH Na2SiO3·5H2O MgO and Mg2(SiO4)and ~30 µm in BE + NM ~26 times higher polarization [168]
(3.18 to 31.8 g/L) alpha-SiO2 in 31.8 g/L resistance than the substrate alloy in
BE+31.8 g/L Na2SiO3·5H2O BE+31.8 g/L Na2SiO3·5H2O
Na2SiO3·5H2O
AZ91D 10 g/L 8 g/L NaF MgF2, some Al2O3 and ~55 µm NM Rp is ~5.32*104 times higher than [104]
Na3PO4 · 12H2O+1 g/L MgAl2O4 phases substrate alloy
KOH 8 g/L NaAlO2 Al2O3 and spinel ~25 µm NM Rp is ~1.25*104 times higher than [104]
MgAl2O4 phases with a substrate alloy
little amount of AlPO4
and MgO phases
AM60 50 g/L NaOH+ 10 g/L Na2SiO3 MgO, MgAl2O4 and NM NM Anodic film with 10 g/L Na2SiO3 [105]
Na2B4O7+ 20 g/L 5 to 25 g/L MgSiO3 additives has the best anti-salt spray
H3BO3+10 g/L potential and shows over 272 h
C6H5Na3O7+ 2 g/L of anti-salt spray time based on ASTM
unspecified organic B117 standard
additive
AZ91D 0.05 mol/L KOH+ KF MgSiO3 (93–96%). Increases with NM Results in significant (300–500 mV) [129]
0.15 mol/L Na2SiO3 0–0.2 mol/L About 3–5% of MgO increase in KF shift of the corrosion potential to the
and amorphous phase, concentration nobler direction. Corrosion rates of
however about 20% samples oxidized in Electrolyte B are
fluorine is seen close to also considerably lower than those of
oxide layer untreated samples, especially for the
moderate concentrations of KF
(0.01–0.05 mol/L).
AZ31 4.0 g/L KOH+ 20.0 g/L KF varied from 0 to MgSiO3 and Mg2SiO4 NM 0.3–0.7 µm in BE A decrease in pitting-corrosion [132]
Na2SiO3+ 10 mL/L 8.0 g/L. and MgF2 1–2.7 µm in KF tendency with an increase in KF
glycol from 0 to 8.0 g/L concentration and more than 40 times
higher Rcorr in the electrolyte
containing 8 g/L
AZ91 0.04M Na2SiO3 + 0.09 KOH (0.09M and MgO and MgOH2 ~1.4 µm in both 0.5 µm in Rp is 9.35 × 102 in BE+0.09M KOH [136]
KF 0.27M) electrolytes BE+0.09M KOH while
and 0.2 µm in Rp is 7.86 × 103 in BE+0.27M KOH
BE+0.27M KOH
(continued on next page)
ARTICLE IN PRESS
Table 1 (continued)
Substrate Base electrolyte Additive Coating Thickness Porosity Effect on corrosion Ref
alloy (BE*) composition (concentration) composition (avg pore behavior
diameter)
AM50 10 g/L KOH 10 g/L Na2SiO4 MgO and Mg2SiO4 8 µm Pores density icorr is 3.2 × 10−6 mA/cm2 [137]
(pores/mm2) is 4410
10 g/L Na3PO4 MgO and Mg3(PO4)2 4 µm Pores density icorr is 9.5 × 10−4 mA/cm2 [137]
(pores/mm2) is
31,340
10 g/L NaAlO2 MgO and MgAl2O4 1 µm Pores density icorr is 8.7 × 10−3 mA/cm2 [137]
(pores/mm2) is
74,450
AM50 1.0 g/L KOH 10.0 g/L Na3PO4 Mg3(PO4)2 and MgO 25 ± 2 m In two ranges, 30 min after immersion, [138]
3–7 µm and icorr is 6.9 × 10−5 mA/cm2
8–20 µm
10.0 g/L Na2SiO3 MgO and Mg2SiO4 15 ± 2 m In three ranges, 30 min after immersion, [138]
1–2 µm, 3–6 µm and icorr is 3.8 × 10−6 mA/cm2
7–10 µm
AZ91HP 10 g/L NaOH + 12 g/L 0 to 34 g/L Na2SiO3 Mainly MgO 6.5 m in Largest pores are icorr is minimized in BE+10 g/L [169]
phytic acid BE+10 g/L 3 µm in BE+10 g/L Na2SiO3, less than half of Icorr in BE
Na2SiO3 Na2SiO3
AZ91 0.12M KOH + 0.04M K4P2O7 (0 to 0.15M) No XRD reported ~3.8 m in NM quantitatively, Rp is more than 103 times higher in [149]
BE+0.03M smallest in BE+0.03M K4P2O7 than that in BE
K4P2O7 BE+0.03M K4P2O7
AZ31 10 g/L Na2SiO3.9H2O + 2 g/L NaAlO2 MgO, Mg2SiO4, and 42 µm (20 µm in % area of Rp is 2.1 times higher than BE [150]
4 g/L KOH MgAl2O4 BE) porosity = 2.8
Average size = 10.85
pore/mm2
2 g/L MgO and Mg2SiO4 24 µm (20 µm in % area of Rp is 35.5 times higher than BE [150]
Na2B4O7.10H2O BE) porosity = 1.1
Average size = 5.64
pore/mm2
2 g/L K2TiF6 MgO, Mg2SiO4, and 50 µm (20 µm in % area of Rp is 6.8 times higher than BE [150]
MgF2 BE) porosity = 2.3
Average size = 7.4
pore/mm2
2 g/L Na3PO4.12H2O MgO, Mg2SiO4, and 22 µm (20 µm in % area of Rp is 3.5 times higher than BE [150]
Mg3(PO4)2 BE) porosity = 3.6
Average size = 9.6
pore/mm2
2 g/L CH4N2O MgO and Mg2SiO4 16 µm (20 µm in % area of Rp is 6.8 times higher than BE [150]
BE) porosity = 2.6
Average size = 7.97
pore/mm2
AZ91 15 g/L Na2SiO3+ 3 g/L Na2MoO4 (0 to MgO, Mg(OH)2, about 1 µm in NM icorr is 3.5 × 10 − 5 [A/cm2] in BE [170]
NaOH+ 10 ml/l 3 g/L) Mg2SiO4 and SiO2. BE+0.3 g/L While it drops to 1 × 10 − 6 A/cm2 in
diethylamine (trace amounts of MoO3 Na2MoO4 BE+ 0.3 g/L Na2MoO4
and MgMoO4) in
BE+0.3 g/L Na2MoO4
* Base electrolyte.
alloy in aluminate electrolytes. They were both reported to be section to current during PEO process is effective in achieving
successful in improving corrosion resistance of coated samples. a more dense and homogenous coating. Due to higher thickness
However, bipolar current type was stated to be of more effi- and density, bipolar-made films provide a stronger protection
ciency than unipolar type [178]. This may be due to fact that the against corrosion [181].
coating produced in the unipolar state suffers from pores and Contrarily, Gao et al. reported of superiority of unipolar
defects created by entrapped gas within the coating [179]. In PEO coatings on pure commercial magnesium in resistance
comparison with unipolar pulse current, using bipolar pulse against in vitro corrosion. In their work, bipolar coatings
current improves plasma thermal conditions. It was seen that showed less porosity with a dense internal film; however, pres-
with accurate control of negative and positive pulses ratio, one ence of macro-scale defects in these coatings along with higher
may avoid very strong plasma discharge and consequently stability of unipolar films were reported responsible for better
sudden extremely high temperatures. As a result, the quality of performance of unipolar coatings. PEO coating could not be
films would be improved [178]. Optimum values for pulse formed with increase in cathodic current density up to
initiation delay and pulse duration were 6 and 4 ms for positive 20 mA.cm−2 due to a transient passivity state [182].
polarization while they were 2 and 6 ms for negative polariza- Cathodic current density affects morphology and corrosion
tion, respectively [180]. properties. EIS results showed that polarization resistance of a
Films produced by bipolar pulses are usually thicker than sample with anodic/cathodic ratio of 2:3 was almost 44% more
those formed via unipolar pulses. Application of cathodic than that with the same ratio of 2:1. In other words, corrosion
22
Table 2
Effect of some organic additives on corrosion performance of PEO coatings on magnesium.
Substrate Base electrolyte (BE*) Additive (concentration) Coating composition Thickness Porosity (avg. pore diameter) Effect on corrosion behavior Ref
alloy composition
G. Barati Darband et al. / Journal of Magnesium and Alloys ■■ (2017) ■■–■■

AZ31B 45 g/L NaOH, polyaspartic acid Mainly MgO and 6.4 to 7.5, 14.6 and (1 to 5 µm in 28.8 g/L PASP) 1.831 × 10−5 A/cm2 in BE [176]
100 g/L Na2SiO3 (PASP) MgSiO4 23.5 µm 16.2 µm 1.071 × 10−6, 2.229 × 107, 2.204 × 10−7 and
9.6, 19.2, 28.8 and 1.388 × 10−7 A/cm2 in polyaspartic acid
38.4 g/L (PASP)
ARTICLE IN PRESS
9.6, 19.2, 28.8 and 38.4 g/L respectively
Mg–5Li–3.5Al–1.2 6 g/L Na2SiO3 + 3 g/L EDTA MgO and Mg2SiO4 ~13 in BE to ~9.5 in (~10 µm in BE, NM icorr is 1.37*10−6 A/cm2 in BE and 3.76*10−8 [55]
Zn–1.2 Ce of Na3PO4+ 1.5 g/L 0.5 g/L (MgO is the dominate EDTA electrolyte quantitatively with additive A/cm2 in EDTA electrolyte
NaF + 1.5 g/L NaOH crystal phase) added but smaller than BE)
AZ31B 40.0 g/L NaOH, 10.0 g/L of each MgO, MgSiO3 and NM quantitatively, NM quantitatively, gets more icorr of the coating formed in [177]
50.0 g/L Na2SiO3, ethylene glycol (EG) Mg2SiO4 gets more smooth uniform with the addition of BE = 3.673 × 10 − 6
30.0 g/L Na2B4O7, and oligomers with the addition of EG, PEG400 and PEG1000 icorr of the coating formed in EG
10.0 g/L C6H5O7Na3 (polyethylene glycols: EG, PEG400 and electrolyte = 1.965 × 10 − 6
PEG400, PEG1000 PEG1000 icorr of the coating formed in PEG400
and PEG4000) electrolyte = 1.542 × 10 − 7
separately icorr of the coating formed in PEG1000
electrolyte = 1.232 × 10 − 7
icorr of the coating formed in PEG4000
electrolyte = 3.831 × 10 − 7
measured as (A.cm−2)
AZ31 10 g/L Na2SiO3.9H2O 2 g/L CH4N2O MgO and Mg2SiO4 16 µm (20 µm in BE) % area of porosity = 2.6 Rp is 6.8 times higher than BE [150]
+ 4 g/L KOH average size = 7.97
pore/mm2
AZ91 10 g/L NaOH+ 8-hydroxyquinoline MgO, Mg2SiO4, 6.0 µm in BE+ 2 g/L number of micropores per icorr decrease from 40 µA/cm2 in BE to 2.2 [175]
18 g/L Na2SiO3 (0 to 8 g/L) Mg(HQ)2 HQ (5.0 µm in BE) area on coating surface µA/cm2 in BE+2 g/L HQ)
decreases from 0.17 in BE to
0.12 µm2
AZ91 10 g/L NaOH+ 4 g/L tannic acid Includes insoluble 6.6 µm in BE+4 g/L pore number in BE is 6 per 4.4 time lower icorr in BE+ 4 g/L tannic acid [151]
18 g/L (C76H52O46) magnesium–tannate tannic (4.4 µm in BE) µm2, but it becomes 4 per than in BE alone
Na2SiO3 · 9H2O complex µm2 in BE+4 g/L tannic acid
* Base electrolyte.
ARTICLE IN PRESS
Fig. 26. SEM images showing surface view of PEO-coatings produced at different frequencies: (a) 60, (b) 500, (c) 1000, (d) 2000 Hz [186].
resistance increased with an increasing cathodic current density [186]. It was stated, elsewhere, that residual stresses decreased
which may be attributed to low porosity and more compactness with increase in frequency [188]. At high frequencies, lower
of coatings produced at high current densities [53]. power and shorter time exist for electrical discharge in each
Duty cycle i.e. ratio of duty time to overall time in a cycle is cycle, thus, fewer discharges may occur at a given location and
another parameter affecting coating properties. Anodic reaction sparks are weaker. Consequently, the coatings seem smooth
and water electrolysis are intensified with increase in duty cycle with a little disfigurement . However, less difference was
at a given voltage and frequency. This, in turn, leads to increase reported for values of corrosion current densities for coatings
in thickness and porosity. It was reported that coatings were not formed at relatively higher frequencies [185].
able to provide an effective corrosion resistance when duty Lv et al. stated that the coating produced at 100 Hz had a
cycle is less than 40% or more than 60% [183]. However, rougher surface appearance with larger pores and poorer cor-
reduction of the final voltage down to less than 480 V makes rosion performance than the one produced at 800 Hz. However,
duty cycle insignificant [184]. longer discharge events caused higher temperatures which, in
Applied frequency is also an important electrical factor in turn, pour more amount of molten material into electrical dis-
morphology and corrosion resistance of PEO coating on mag- charge channels. In result, the coating produced at 100 Hz had
nesium alloys. Reportedly, chemical composition, morphology greater growth rate [187].
and corrosion resistance may be considerably improved by Elsewhere in a study by Srinivasan et al. [190] and in con-
taking accurate adjustments on frequency [185]. trast with aforementioned data, it was seen that a coating
Fig. 26 Illustrates surface view of coatings produced at fre- formed at 10 Hz was denser than the one produced at 1000 Hz.
quencies between 60 to 2000 Hz. It is clear that size of surface It also showed a better corrosion resistance. It is worth men-
pores decreased with increase in AC current frequency. Higher tioning that the thicker coating with higher growth rate was
intensity of micro-sparks in a cycle during treatment is respon- again achieved at low frequencies. They suggested that higher
sible for enlargement of pores at low frequencies [186]. corrosion resistance of the coating produced at low frequencies
It was seen in many research that coatings deposited at high may be due to better sintering conditions during negative pulses
frequencies had better corrosion properties [185–189]. Accord- with higher energy and formation of phases which require high
ing to EIS results, corrosion resistance of the PEO film fabri- plasma temperatures which exist when producing the coating at
cated at 1000 Hz was approximately 32 times higher than the low frequencies.
one formed at 100 Hz frequency, as the coating tends to create Considering oxidation characteristics, anodic coatings may
a less porous and more compact structure of the coating at the be categorized into three types: passive film, micro-spark
higher frequency [189]. Increase in frequency leads to increase ceramic and spark ceramic coating. These types are depicted in
in number of discharge channels and reduces their size. Hence, Fig. 27. Among these coatings, only the second type may
porosity decreases and the film becomes dense [185,186,189]. provide desired corrosion resistance. Hence, the voltage is
It was also seen that MgO content increased at high frequencies required to be maintained so that it remains within micro-
ARTICLE IN PRESS
Under constant voltage conditions: 375 V, frequency:

400 Hz and duty cycle: 40%.
Under constant power conditions: 3kW, frequency: 200 Hz
and duty cycle: 25%.
Chen et al. [199] provided optimum conditions for electrical
parameters.
Current density of 20A.dm−2, frequency of 500 Hz, duty
cycle of 40% and oxidation time of 15 min.
Chang et al. [183] determined the effects of process factors
on corrosion resistance of coatings to be in this order:
Applied voltage > duty cycle > frequency
In addition, optimum values of parameters in the process

were:
Applied voltage: 140 V, frequency: 2000 Hz
Fig. 27. Variations in coating thickness with applied voltage [191]. and duty cycle: 0.4.
4.1.4. Effect of oxidation time on corrosion resistance

sparking range and consequently the best protective properties Oxidation duration and current density have similar effects
may be acquired [191,192]. on corrosion resistance of PEO coatings [197]. However, effect
An increasing pulse voltage leads to thicker oxide coatings. of oxidation time is reported to be quantitatively less than that
Ma et al. [193] reported that the pulse voltage should vary of the current density [200].
between 300 and 438 V in order to achieve desired corrosion Considering occurrence of fewer defects at low current den-
properties. By employing single-variable tests, Jiang et al. sities, it was observed that applied coatings had the best corro-
[194] concluded that negative voltage of 20 V can form a sion resistance at long time periods and low current densities
smooth and thicker PEO coating with optimized characteristics [135]. Where other parameters are kept constant, initially, cor-
and best corrosion resistance. rosion resistant of the coatings improves by prolongation of
Applied current density is another parameter in PEO process oxidation time; however, it decreases after oxidation time
that affects coating properties. Growth rates of 1, 2 and exceeds an optimal value [197,201]. In case of excessively long
3 mm.min−1 were recorded for applied current densities of 15, durations, it is possible that the coating dissolves and becomes
75 and 150 mA.cm−2. Coatings produced by low current densi- completely destroyed which significantly diminishes corrosion
ties are generally thin, dense and bear few defects. According to resistance [202]. However, it was reported elsewhere by Lv
electrochemical tests, these coatings also showed better corro- et al. that optimum durations for PEO Processing with pulsed
sion resistance [195]. Thickness increases almost linearly with DC current on AZ91D alloy were 2.5 and 20 mins (two differ-
increase in current density [195,196]. It was observed, else- ent oxidation time values). The obtained coatings were homog-
where, that corrosion resistance was improved by increase in enous with dew defects and showed the best corrosion
oxidation time or current density up to an optimum value. performance [121].
Further increase, however, had adverse impacts on corrosion
resistance [197]. Increase in current density generally enhances 4.1.5. Effects of substrate alloy and pre-treatments on
growth rate, however, it leads to deterioration in coating uni- corrosion resistance
formity [5]. Liang et al. carried out coating process using two In PEO treatment on different magnesium alloys, each PEO
different methods for current application where current was film has a different phase composition and surface morphology
reduced in the end of process in two forms of either decaying because of the effects of alloying elements. This, sequentially
freely current density or stepped decreasing current density. affects corrosion mechanisms [203].
They observed that optimization of current waveforms may Introduction of Al and Zn to magnesium alloys leads to
improve coating microstructure (in comparison with constant increase in average growth rate of PEO coatings. The increase
current mode) due to change of sparking conditions. The is of a gradual nature regarding Mg-Al alloys; whereas, it esca-
optimum sparking form was decaying freely current density lates with raising Al content in case of Mg-Al-Zn alloys. It
where the most intact and homogenous microstructure was seems that Zn (by playing a catalyst role) improves oxidation
achieved. Corrosion resistance of this coating was approxi- rate of Al and Mg throughout coating formation process. It was
mately 56% higher than that produced using constant current observed that the internal barrier layer was dense and crack-free
density [26]. in substrate/coating interface of triple alloys. However, some
Optimum values of process parameters were reported by Cui defects were identified in binary alloys as well as in pure mag-
et al. [198]. nesium [204]. According to EIS data, bipolar PEO coatings
Under constant current conditions: 5A, frequency: 600 Hz were arranged into the following order (in terms of corrosion
and duty cycle: 40%. resistance) after immersion in 3.5% NaCl solution:
ARTICLE IN PRESS
Fig. 28. Cross sections of PEO coatings on different magnesium alloys [103].
Mg uncoated < Coated pure Mg < Coated AJ62 in resistance against galvanic corrosion and formation of a PEO
< Coated AM60B < Coated AZ91D coating with dense microstructure [208].
In addition to the substrate chemical composition, surface
This may be attributed to the discharge behaviors, coating conditions including roughness and grain size are important in
structure, thickness and porosity [203]. corrosion properties of coatings. Effect of surface roughness on
Cross sections of PEO coatings on different magnesium alloys corrosion performance of PEO coatings on AZ31B alloy was
are illustrated in Fig. 28. Pure magnesium and WE43 alloy had the investigated by Yoo et al. [209]. DC polarization and impedance
lowest (3.8 µm.min−1) and the highest (7.4 µm.min−1) coating spectroscopy revealed that corrosion resistance decreased with
growth rates. It was also observed here that in Al-containing increase in surface roughness. Same observations were reported
alloys, coating growth rate increases with increasing aluminum in longterm salt spray tests. Gheytani et al. [210,211] studied
content [103]. WE43-T6 has a better corrosion resistance than surface grain refinement by means of surface mechanical attri-
AZ91D in 3.5% NaCl solution, while, the latter became superior tion treatment (SMAT) as a pre-treatment for PEO on AZ31B
in corrosion resistance after PEO process. At long immersion substrate. Using curve area in potential-time plots as a criterion
durations, PEO coating on WE43-T6 sample could not provide the of consumed energy during process, they showed SMAT-treated
desired corrosion performance and a uniform corrosion film was samples needed less energy for coating formation compared
produced on the coating. On the other hand, AZ91D had a much with coarse-grained ones. Also, growth rate was accelerated in
better corrosion performance with no sign of corrosion in SMAT-treated samples, particularly when PEO was carried out
substrate/coating interface [205]. in phosphate electrolytes. However, refinement did not signifi-
Generally, coatings formed on AZ series are more smooth cantly improve corrosion properties. Chen et al. [212] studied
and dense than those created on AM series. The former also refinement effect on corrosion properties of calcium phosphate-
shows better corrosion resistance [206]. contained PEO coatings on AZ31B alloy by means of ultrasonic
It was seen that addition of even minor amounts of alloying cold forging technology (UCFT). Comparing with coarse-
elements can change the formation process and corrosion per- grained samples, the least weight loss and corrosion current
formance of AM50 alloys. Corrosion resistance and degrada- density were obtained in the fine-grained substrate (with grain
tion behaviour of coatings are strongly dependent on the size of 49 nm). Refinement was reported to improve corrosion
substrate substance and its inherent corrosion properties. Intro- properties up to a great extent.
duction of cerium to AM50 substrate leads to reduction of Grain refinement of AZ91D alloy by ECAP method prior to
localized pitting corrosion and formation of passive films which PEO treatment process reduced corrosion rate in 3.5wt.% NaCl
provoke uniform corrosion. Hence, it finally improves corro- solution. Ultrafine-grained magnesium in matrix with fine β
sion behavior of the alloy and prevents early failure of the phase lead to homogenous sparking during PEO process;
applied coating [207]. It was reported, elsewhere, that addition hence, the produced coatings would be dense and uniform.
of minor amounts of neodymium to AZ91 alloy causes increase Besides, high-energy defects that remain after ECAP alloy were
ARTICLE IN PRESS
helpful in coating formation so that thicker coatings were coatings on magnesium alloys is limited. Improvement of tribo-
formed on fine-grained alloys [194]. Laser surface melting logical properties in magnesium alloys can be very important
(LSM) on AZ91D substrate prior to PEO process in a phosphate due to various applications of magnesium in transportation
electrolyte caused a significant improvement in corrosion prop- industries and the need to reduce weight in order to lower fuel
erties. LSM treatment changes crystalline transformation of the consumption and pollution. In a study that was aimed to
substrate metal and transforms β morphology. These changes improve wear properties of AJ62 alloy used in engine cylinders,
lead to contribution of more aluminum to MgAl2O4 spinels. it was found that tribological behavior of PEO-treated magne-
Coatings produced on pre-treated alloys had a more dense cross sium alloy was even better than hypereutectic Al-Si alloy which
section with fewer surface cracks The aforementioned modifi- is commonly used for the same application [215]. Considering
cations in surface properties reduced corrosion current density the increasing application of PEO-treated magnesium alloys for
by ten times compared with coatings on samples without LSM biomedical purposes, wear behavior [216] and erosion corro-
pre-treatment [213]. Corrosion parameters were observed to be sion [217] of these coatings in biological media were investi-
approximately similar at different locations of an FSW weld gated. Now let us address the important factors in PEO process
joint on an AZ31B sample after it was PEO-coated. It was that affect tribological properties of coatings.
concluded, accordingly, that PEO treatment may be of consid-
erable efficiency in improving corrosion resistance when the 4.2.1. Effect of electrolyte ions on tribological properties
underlying magnesium substrate has been subjected to a As also mentioned in previous sections, electrolyte compo-
welding treatment [214]. sition may be of great importance in morphology, chemical
composition and microstructure of produced coatings which, in
4.2. Tribological properties
turn, lead to different tribological performances by coatings
PEO coatings deposited on magnesium substrates are gen- formed in different types of electrolytes.
erally hard and have potentially high wear properties. Yet, the Fig. 29 illustrated morphology of wear tracks (after pin-on-disk
number of publications about tribological properties of PEO test) on AM60B magnesium alloy samples that had been PEO-
Fig. 29. Wear track morphologies of the specimens after pin-on-disk tests for the uncoated substrate (a), and the samples coated in electrolytes with different
concentrations of NaAlO2: 12 g.lit−1 (b); 18 g.lit−1 (c); 24 g.lit−1 (d) [218].
ARTICLE IN PRESS
treated in electrolytes containing different NaAlO2 addition, both samples failed under 5N loadings but the Si-PEO
concentrations. It is quite obvious that wear tracks on the uncoated sample tolerated the test for 20 m.
sample were very wider and deeper. Amongst the coated samples, Both coatings showed a better performance than the
the one treated in 12 g.lit−1 electrolyte had the lowest wear uncoated sample under the 2N loading which was due to high
resistance. In fact, wear resistance was found to improve with hardness of applied coatings. This trend, however, reversed
increase in aluminate concentration. Same observation also under the 5N loading so that the uncoated sample had the best
existed for the thickness of coatings and increase in aluminate performance. This was explained by three-body abrasive
concentration caused formation of thicker coatings with increased wearing caused by hard ceramic particles in wear tracks.
surface roughness. Coatings mainly consisted of MgO and Samples demonstrated a combination of abrasive and adhesive
MgAl2O4 spinel while content of the latter increased at higher wearing mechanisms. The abrasive ball also showed formation
NaAlO2 concentrations. High microhardness of coatings caused of a discontinuous transient film [219].
significant improvements in wear resistance of magnesium Srinivasan et al. obtained two coatings with MgO and ZrO2
samples. Accordingly, volume loss caused by wearing was as main constituents using phosphate- and fluorozirconate- con-
reduced by one order of magnitude. High microhardness and low taining electrolytes, respectively. Constant voltage of 420 V
wearing rate persuaded the authors to suggest aluminate for was applied. Similarly, the coating produced in the phosphate
improving performance of magnesium alloys and consequently electrolyte (with thickness of 30 µm) was resistant against the
the feasibility of their application in transportation and aviation 2 N load in sliding wear test; yet, it failed under 5N load as its
industries [218]. It was also reported, in PEO-treatment on AJ60 load-bearing ability was low. Due to three-body abrasive
alloy using aluminate-bearing electrolytes, that thickness and wearing in the wear track that is caused by crushed ceramic
surface roughness increased with increasing concentration of particles, the phosphate coating had a wear rate higher than the
aluminate. The deposited PEO film consisted of an outer porous substrate alloy. The coating created in the acidic electrolyte
layer and an inner barrier with nanocrystalline structure. The containing K2ZrF6 was seen to possess a sponge-like structure
nanocrystalline structure was stated to be responsible for with a worse behavior compared with the bare underlying sub-
improvement of load-bearing ability [215]. strate under 2 and 5N loadings. Hence, it was not recommended
Pure commercial-grade magnesium was coated by means of for direct application in case of tribological properties improve-
PEO process in sodium silicate- and sodium phosphate- ment [125].
containing electrolytes. Coatings produced in the silicate- Introduction of sodium tungstate to electrolyte was found
containing electrolyte bore Mg2SiO4 and MgO, while, coatings useful for improving tribological properties. Increasing
deposited in the phosphate-containing electrolyte had Na2WO4 concentration up to 6 g.lit−1 in electrolytes that con-
Mg3(PO4)2 and MgO. It was also observed that the coatings tained silicate and KOH during PEO-treatment of AM60B alloy
produced in the silicate electrolyte were harder than those led to increase in porosity. Besides, W was slightly present in
created in the phosphate electrolyte. This was due to harder the coating while Mg2SiO4 content also increased. It was
nature of Mg2SiO4 compared with MgO and Mg3(PO4)2. Adhe- observed that microhardness and wear rate increased from
sion level of all coatings was excellent. At equal thicknesses, 510Hv and 3.55 × 105 mm3.N−1m−1, in the base electrolyte, to
the coatings produced in the silicate electrolyte had a higher 710Hv and 2.54 × 105 mm3.N−1m−1, in the base electrolyte with
adhesion than those created in the phosphate electrolyte. Wear 6 g.lit−1 Na2WO4. Hardness improvement and reduction of wear
resistance of both coatings was superior to that of the uncoated rate could be explained by increase in content of hard Mg2SiO4
sample, besides, wear resistance of coatings produced in the in the coating corresponding with addition of sodium tungstate
silicate electrolyte was measured higher than those formed in [220].
the phosphate electrolyte, due to presence of the hard Mg2SiO4 AFM micrographs of PEO coatings on AZ31 magnesium
phase [196]. alloy showed that addition of 3 mg.lit−1 borax (Na2B4O7) to the
Similar observations were also reported in PEO-treatment of base electrolyte containing 10 g.lit−1 sodium silicate and
AM60B alloy under constant current densities in silicate- and 4 g.lit−1 potassium hydroxide caused reduction of surface
phosphate-bearing electrolytes. The thick coating produced in roughness by about 50 percent. This was stated to be due to
the silicate electrolyte was harder than the one fabricated in the change of sparking characteristics during the process. EDS and
phosphate electrolyte. In dry sliding conditions, wear rate of the XPS analyses revealed that boron contributed to the deposition
silicate coating was half of that measured for the phosphate process. XRD analysis proved that amorphous boron existed in
coating. However, the silicate coating showed a higher friction the coating. Microhardness and density of PEO coating
coefficient in friction test [1]. improves with addition of boron. According to results of recip-
MRI230D magnesium alloy samples that had been cast in rocal wear test, wear rate of the underlying magnesium alloy
permanent dies were PEO-treated using silicate- and (uncoated) was 86.83 × 10−4 mm3.N−1m−1. However, it was
phosphate-bearing electrolytes. The silicate coating had a sig- 20.96 mm3.N−1m−1 and 6.69 mm3.N−1m−1 in borax-free and
nificantly hardness value of 1660 ± 367Hv, while, hardness of borax-bearing coatings, respectively. Therefore, it may be
the phosphate coating was 560 ± 153Hv. These high values may deduced that addition of borax can significantly affect wear rate
be explained according to the ceramic nature of coatings. In dry reduction in the coatings [221].
sliding test, the Si-PEO sample could tolerate a 2N loading Addition of ethylene glycerol and three different poly-
while the P-PEO sample suffered damages in several areas. In ethylene glycols to a silicate electrolyte in PEO-treatment of
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Fig. 30. Average hardness of pure magnesium and PEO coatings produced by different current densities and electrolytes (silicate- and phosphate-bearing
electrolytes) [196].
AZ31B alloy led to the researchers to conclude that coating unipolar currents is important. Reportedly, coatings had better
morphology has a great dependence on the applied composition tribological properties when deposition ended at the bipolar
and its EG segments in the electrolyte. Implementation of current mode [223].
ductile PEG segments into the coating during PEO process and Average hardness of pure commercial magnesium is almost
their performance as lubricants may be accounted responsible 40Hv (as seen on Fig. 30). Under current densities of 0.06,
for high anti-friction ability of coatings. However, the accuracy 0.085 and 0.14A.cm−2 at 30mins of deposition, hardness values
of this expression needs further studies [177]. for coatings produced in a silicate electrolyte were 260, 370 and
As another organic additive, effect of glycerol (C3H8O3) on 575Hv, respectively. While, they were obtained as 175, 230 and
root-mean-square (RMS) roughness of PEO coatings on 300 Hv for coatings produced in a phosphate solution.
AZ91D alloy was investigated. RMS roughness improved ini- Wear rates of the same silicate and phosphate coatings
tially with increase in C3H8O3 and then dropped with further applied under different current densities at 30mins are illus-
addition of it. The lowest surface RMS roughness (174 nm) was trated in Fig. 31. It may be observed that, regardless of electro-
obtained in an electrolyte with 4 ml.lit−1 glycerol. Noticeable lyte type (phosphate or silicate), wear rate decreased with
changes in morphology are mainly due to adsorption of glyc- increase in current density from 0.6 to 0.14A.cm−2. Increase in
erol (instead of water molecules) on anode surface along with current density improves hardness and density of coatings as it
silicate anions from sodium silicate dissolution that causes increases Forsterite (Mg2SiO4) content. This is stated to be the
smaller but more sparks in PEO process [171]. cause of wear resistance improvement [196].
Average values of thickness and roughness of AM50
4.2.2. Effect of electrical variables on tribological properties magnesium samples that had been PEO-treated in a silicate
It was reported in most studies that coatings obtained using electrolyte under direct current and various final voltages are
bipolar current mode had more desirable wear properties than shown in Fig. 32. An increasing final voltage led to higher
those created by unipolar currents. In AZ91D alloy PEO- thickness and roughness values due to formation of larger sparks
treatment, the coating produced using bipolar currents was at higher voltages and apparently solidification of a greater
denser, harder, and showed a lower friction coefficient (also amount of coating compounds. The lost volume during the wear
with a higher oxidation rate) than the one produced using uni- tests on coatings obtained at different voltages are shown in
polar currents. Both samples performed better than the under- Fig. 33. Before 440 V, the applied coating was seen to worsen wear
lying substrate in wear test, though, bipolar current sample resistance of coatings. This was justified by the proposed process
showed the lowest wear rate of all [222]. of detachment of hard ceramic particles, broken off from the
A direct relationship was identified between surface coating, this debris is then trapped in wear tracks and cause
roughness (Rz) and friction coefficient in PEO treatment of three-body wear phenomenon. Moreover, damages on the
AM60B magnesium alloy. Surface roughness is lower in case abrasive steel ball were harsher than testing with the uncoated
of bipolar current application. Together with its higher sample. This was due to abrasive effect of the hard ceramic PEO
density, low surface roughness improves tribological coating. On the other hand, wear behavior of the sample treated at
performance of coatings produced using bipolar currents in 440 V was quite different. Depth of the wear track was 4 µm while
pin-on-disk and inclined impact-sliding tests. In case of using it was 23–29 µm in previous samples. The low depth indicates that
hybrid current modes, application order of bipolar and a considerable part of the coating still existed unharmed on alloy
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Fig. 31. Wear rates of pure magnesium and PEO coatings produced by different current densities and electrolytes (silicate- and phosphate-bearing electrolytes)
[196].
surface in the end of the test, resisting against the wear process
[224].
In another PEO technique called “rapid forming” by the
researchers, applied voltage is increased up to the initial spark-
ing limit. Thenceforth, it is increased step by step at certain
values under given stages. The required time for formation of a
coating with a given thickness reduced dramatically with apply-
ing this technique [225]. Lu et al. [225] studied the effect of
voltage increase values in every step on tribological properties
of coatings by using a silicate electrolyte for PEO-treatment of
AZ91D magnesium alloy. Voltage increased after sparking
through four steps by 5 V to 30 V in each sample. It was seen
that surface roughness increased with increase in excess
voltage. Friction coefficient increased with increase in voltage
Fig. 32. Thickness and roughness of PEO coatings as a function of final
voltage [224].
addition levels. The best wear behavior was seen when voltage
increase level was 10 V. Wear mechanism in these coatings
consisted of abrasive and micro-machining wear.
Frequency of the applied current is another electrical param-
eter that may affect coating properties. At high frequencies, a
coating with lower roughness was achieved due to shorter elec-
trical discharges with lower power and focus. Consequently, it
may be perceived that friction coefficient decreases at high
frequencies. Dense structure of coatings produced at 1500 Hz
was responsible for their superior wear resistance compared to
those deposited at lower frequencies (400 and 800 Hz) [185].
4.2.3. Effect of deposition time on tribological properties
Roughness and thickness of PEO coatings were seen to
increase with increase in deposition time [215]. Thickness was
observed to have a significant influence on improvement of
wear resistance of PEO coatings applied on AZ91 alloy. Sub-
strate deformation at higher initial stress levels, particularly
when coatings are thin, leads to cracking and detachment of
coatings. Under such circumstances, increase in coating thick-
ness may improve load-bearing ability and wear resistance.
Fig. 33. Effect of PEO coating at different final voltages on wear rate of However, in spite of improving the wear resistance of the
samples (at 5 N load) [224]. coating, increase in thickness may cause abrasive wear in the
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Mg-Al-Zn alloys is greatly dependent on aluminum content in

the substrate. It also seems that Zn does not have any significant
role in the matter. Effect of aluminum on hardness of coatings
is explained by the fact that Al encourages formation of hard
MgAl2O4 phase [204].
4.3. Biomedical properties of PEO coatings on magnesium

and its alloys
4.3.1. Classification of biomaterials
Generally, materials in biomedical applications may be divided
into two categories: biodegradable and unbiodegradable.
Unbiodegradable materials last in the body till the end of
treatment period and have to be removed, then, by a second
surgery. Due to corrosion or wear, these materials may release
Fig. 34. Microhardness values of PEO coatings deposited on seven magnesium
toxic ions in the body that cause undesirable infection and physical
alloys under similar conditions are shown [204].
activities that would lead to some issues. On the other hand,
biodegradable materials would be utterly dissolved, absorbed or
steel ball. Wear rate of the steel ball depends on the applied load defecated after a certain amount of time; hence, there would be no
and wear mechanism. Oxidation of the abrasive steel ball was need for a second surgery and consequently treating costs are
expressed to be important in lowering friction coefficient (and reduced [227–229]. As polymeric biodegradable materials have
consequently wear rate) at high applied loads [226]. weak mechanical properties, researchers have paid a great deal of
attentions, so far, to metallic biodegradable materials [230–235].
4.2.4. Effects of substrate alloys and pre-treatments on
tribological properties
4.3.2. Advantages and disadvantages of magnesium as a
Although tribological properties of different magnesium
biodegradable material
alloys with PEO coatings have not been addressed yet in a
Magnesium as a biodegradable material bears several advan-
comprehensive study, the effect of substrate alloy on
tages and disadvantages. Biocompatibility of magnesium and
microhardness of coatings was investigated by Krishna et al.
its alloys is much better than stainless steels, titanium and
Microhardness values obtained from PEO coatings depos-
cobalt alloys. Magnesium ions are the fourth most prevailing in
ited on seven magnesium alloys under similar conditions are
human body and are necessary for biological performance of
shown in Fig. 34. Hardness of PEO coatings on pure magne-
almost all of the living cells. Approximately, 30 g of magne-
sium, Mg-3%Al and AZ31 were from 320Hv to 380Hv.
sium exists in a 70 kg human body. A daily supply of 420 mg of
However, coatings formed on Mg-9%Al and AZ91 were much
Mg is required in order to maintain body activities at a normal
harder (hardness values ranged from 750 Hv to 775 Hv).
level [236–239]. Besides, magnesium ions take part in many
Dependence of coating hardness on aluminum content in the
biological processes within the human body such as DNA
underlying substrate is described in Fig. 35. It is clear that
repair, protein transition, enzyme activities, etc [240,241]. In
hardness of PEO coatings applied on binary Mg-Al and ternary
addition to biocompatible, having desirable mechanical proper-
ties is another reason for application of magnesium alloys for
biomedical purposes. Density and elastic modulus of Mg-based
alloys and bones are very close; thus, stress in the bone/implant
interface is decreased which, in turn, improves stability and
growth of bones [241]. Magnesium corrosion can be controlled
in some of physiological media which is why it is primarily
used in coronary stents and bone treatment scaffolds [241]. In
spite of many advantages for magnesium in medical applica-
tions, this metal is not being used widely due to several restric-
tions. The main disadvantage of magnesium is that it is
corroded very quickly in human body so that a great deal of
hydrogen is produced. Also, pH locally increases above the
endurable levels [242,243]. Presence of hydrogen molecules
may lead to segregation of tissue layers that retards recovery of
a living tissue [243]. Hydroxyl ions caused by corrosion pro-
cesses may locally alkalinize some areas beside a tissue
[238,244]. As human health is very sensitive to pH variations,
Fig. 35. Relationship between PEO coatings hardness and aluminum content in then magnesium corrosion may bring about a lot of problems
the Mg alloys [204]. for human body. Low wear resistance of magnesium is known
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as another constraint for its applications in medical implants 4.3.5. Fabrication of biocompatible phases in PEO coatings
[243]. on magnesium
It was mentioned previously that the presence of calcium and
4.3.3. Improvements of magnesium alloys for application as phosphorous in PEO coatings on magnesium is the main factor
a biodegradable material in manufacture of biodegradable coatings. Some of the works in
Chemical composition improvement and surface treatment this regards are reviewed in this section.
methods are generally employed to enhance Mg-based alloys Pan et al. [257] fabricated calcium phosphate on ZK60 mag-
for biomedical applications. Many impurities in magnesium nesium alloy by means of plasma electrolyte oxidation. They
including iron, nickel, cobalt and copper diminish corrosion used an electrolyte that contained calcium stat monohydrate
resistance by forming cathodic micro-sites [245–247]. It may and disodium hydrogen sulfate. XRD analysis revealed success-
be deduced, therefore, that purification is a solution for improv- ful formation of β-Ca3(PO4)2 in the coating. It was also reported
ing corrosion resistance in magnesium-based alloys. Addition that β-Ca3(PO4)2 is a very biocompatible phase that dissolves in
of alloying elements is another way to enhance mechanical human body [258]. Increase in electrolyte concentration led to
properties and corrosion resistance. Generally, addition of alu- increase in absorption of elements in the solution. In the same
minum, manganese, zinc, zirconium and calcium is helpful in research, an immersion test was carried out in a simulated body
enhancing corrosion resistance and mechanical properties fluid to assess biocompatibility and biodegradability of coat-
[248–250]. Excessive use of aluminum is not recommended ings. After 30 days of immersion in SBF solution, calcium
due to the many problems that it causes for the human body phosphate coating effectively decreased degradation rate. The
[251]. Surface treatment is also available for improving corro- calcium phosphate coating was covered with a layer of
sion resistance of magnesium alloys. There are many tech- hydroxyapatite after 30 days.
niques for magnesium surface treatment such as conversion Vu et al. [259] fabricated PEO coatings on AZ91D magne-
coatings and electroplating which are being used in order to sium alloy under constant current of 20 mA.cm−2 in an electro-
achieve better corrosion resistance and optimize surface lyte with 3 mol.lit−1 KOH, 0.5 mol.lit−1 KF and 1 mol.lit−1
mechanical properties [7,252]. Selection and design of a K2HPO4. They studied the effect of CaO addition to electrolyte
coating for biomedical purposes depends on the intended appli- on biocompatibility of films. Presence of calcium and phospho-
cation. A poor choice of coating for materials may cause clini- rous was confirmed via XRD analysis. With 1 g.lit−1 CaO in the
cal issues. Any substance that is aimed to be used as biological electrolyte, morphology and corrosion resistance of coatings
material has to possess the following features [253]: were improved in SBF solution. It also accelerated formation of
a hydroxyapatite layer on magnesium after the immersion test
• Biocompatible
in SBF solution. However, excessive CaO in the electrolyte
• Adhesiveness
(3 g.lit−1) led to formation of coatings with too many cracks
• Wear resistance
that, in turn, deteriorated corrosion resistance.
• Degradability
Pan et al. [260] coated calcium phosphate films on
Recently, PEO coatings have been also investigated for bio- Mg-Zn-Zr magnesium alloy by PEO technique in electrolytes
medical purposes. Application of PEO coatings to improve containing calcium stat monohydrate and various phosphates
biocompatible properties of magnesium alloys is discussed in including hydrogen disodium dodecahydrate phosphate,
the following sections. sodium phosphate and sodiumhexametaphosphate. It was
reported that calcium and phosphate ions were successfully
4.3.4. Usage of plasma electrolyte oxidation on magnesium deposited in coatings. The calcium phosphate film effectively
for biomedical applications enhanced corrosion resistance. Besides, a hydroxyapatite layer
Corrosion resistance enhancement is the main reason to covered the calcium phosphate film after the immersion test in
employ PEO processes for manufacture of magnesium biode- SBF solution. The coating produced in the electrolyte with
gradable implants. It is basically required that biodegradable sodiumhexametaphosphate was thicker, more adhesive and
implants maintain well enough corrosion resistance and more biocompatible. It also had a lower degradability rate and
mechanical properties for at least 12 weeks in human body a better ability to form hydroxyapatite.
[254]. Reduction of degradation rate builds the main strategy in Yao et al. [261] fabricated ceramic films containing
employment of PEO technique for magnesium alloys. There calcium and phosphorous on AZ91D magnesium alloy by
have been many researches around fabrication of coatings with means of PEO process in NaOH and Ni2SO3 systems.
a chemical composition which is biologically consistent with Sodiumhexametaphosphate and calcium hypophosphide were
human body. Hydroxyapatite (Ca10(PO4)6(OH)2, HA) and employed as calcium and phosphorous providers, respectively. In
tricalcium phosphate (Ca3(PO4)2, TCP) are very well consistent NaOH system, great deals of micro-pores were observed to be
with human body [255,256]. Hence, calcium and phosphorus uniformly distributed over the surface. In addition, both calcium
(which form the major constituents in HA and TCP) should be and phosphorous were present in the coating. Number and
introduced to the PEO films so that they become Biocompatibe. distribution uniformity of micro-pores became less in the Ni2SO3
Addition of Ca and P ions to the coating solution is the best way system. Notably, calcium and phosphorous could be found.
to incorporate calcium and phosphorous to PEO coatings on Calcium : phosphorous ratio was controlled by changing coating
magnesium. parameters.Accordingly, adjusting calcium ion concentration was
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Fig. 36. Effects of various parameters on biomedical properties.
seen to be more efficient to control calcium: phosphorous ratio in 4.3.7. Coating parameters and conditions
both systems.
4.3.7.1. Voltage and current density. Coating voltage and
Pan et al. [23] fabricated a ceramic coating on ZK60 mag-
current density are among the important factors that affect
nesium alloy by PEO process under constant voltage at different
properties and morphology of PEO coatings. We now review
Ca and P concentrations. Biocompatibility and biodegradability
several works addressing the effect of these parameters on
of coatings were analyzed by immersion test in a simulated
biocompatibility of PEO coatings on magnesium alloys.
body fluid. SEM micrographs showed that pores of different
Gu et al. [263] carried out PEO process on Mg-Ca magne-
sizes were distributed all over the surface. Besides, thickness of
sium alloy (which is known as a biodegradable material) at 300,
films increased with increase in calcium-to-phosphorous ratio.
360 and 400 V. They studied voltage impact on surface mor-
XRD tests also confirmed formation of bioactive phases includ-
phology, phases, hydrogen emission and pH variations through
ing hydroxyapatite and calcium phosphate on coatings
immersion and biodegradability tests. It was reported that
immersed in the SBF solution. This, in turn, stands a reason for
thickness and pits size increased at high voltages. The coated
high bioactivity of PEO coatings on magnesium. Degradation
film at 360 V showed the best corrosion resistance in long-term
rate, then, decreases with increase in calcium: phosphorous
immersion test. Variations in hydrogen emission and pH versus
ratio.
time at different voltages are plotted in Fig. 37. It may be seen
Srinivasan et al. [262] coated Ca-bearing PEO coatings on
that hydrogen emission on surface reduced drastically with
AM50 magnesium alloy by use of alkaline electrolytes. They
formation of a PEO coating. The lowest hydrogen emission was
studied through three alkaline electrolytes with calcium
recorded in the sample coated at 360 V. With a PEO coating, pH
hydroxide and sodium phosphate at different ratios. All three
fluctuation also decreased.
coatings bore considerable contents of calcium and phospho-
Lin et al. [264] performed PEO process on ZK60 magne-
rous. It was reported that the highest P content in a coating was
sium alloy in a silicate-based electrolyte at 230, 300, 370 and
acquired from the electrolyte with the highest phosphate
450 V in order to reduce degradation rate as well as to improve
concentration.
biological properties. Degradation rate was significantly
reduced after the coating process. Corrosion resistance
4.3.6. Effects of various parameters on performance of improved with increase in coating voltage. It was also shown
biocompatible PEO coatings on magnesium that structure and thickness might be controlled via adjustment
There are many parameters that affect performance of of coating voltage. Plot of pH variations against immersion
biocompatible PEO coatings on magnesium which are sche- time revealed that coating treatment reduced pH fluctuations
matically described in Fig. 36. with the least of all was observed at 400 V. A degradation model
In the next section, each parameter and its effect on biomedi- was suggested in that work to elucidate degradation process of
cal PEO coatings would be discussed. the film during immersion test. Accordingly, morphology and
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Fig. 37. a) Hydrogen emission variations versus immersion time at different voltages and b) pH variations versus immersion time in coatings fabricated at different
voltages [263].
phase composition are the main two factors controlling long- Chang et al. [265] coated calcium phosphate coatings on
term protectiveness of coating. In order to achieve a uniform AZ31 magnesium alloy at 350, 420 and 450 V in an electrolyte
degradation behavior, the PEO coating has to be dense and containing 15 g.lit−1 NaAlO2, 2 g.lit−1 KOH, 4 g.lit−1 Na2HPO4
include phases with equal dissolution rate. This mechanism is and 4 g.lit−1 EDTA-Ca by means of plasma electrolyte oxidation
schematically drawn in Fig. 38. and low-temperature hydrothermal process. Biological corro-
Fig. 38: a schematic drawing of degradation process in PEO sion resistance of coatings before and after hydrothermal
coating; a) outer porous layer and part of inner dense layer process was evaluated by anodic polarization and EIS in Hank’s
exposed to the electrolyte, b) development of new defects and solution. It was observed that the produced PEO coatings con-
their enlargement may speed up degradation. While, deposition tained calcium and phosphorous. Besides, the highest
of insoluble produces may retard degradation process, c) for- calcium-to phosphorous ratio was obtained at 450 V, hence, that
mation and enlargement of defects is decreased and more sedi- coating was selected for hydrothermal process. It was reported
ments are produced, d) some parts of coating detach from the that hydrothermal process not only caused formation of DCPD
substrate and corrosion products beneath the coating are and β-Ca3(PO4)2 crystallites, it also improved magnesium alloys
exposed to the fluid [106]. resistance against biological corrosion. Fig. 39 shows XRD
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Fig. 38. A schematic drawing of degradation process in PEO coating; a) outer porous layer and part of inner dense layer exposed to the electrolyte, b) formation of
new defects and their enlargement may accelerate degradation. While, deposition of insoluble produces may retard degradation process, c) formation and
enlargement of defects is decreased and more sediments are produced, d) some parts of coating detach from the substrate and corrosion products beneath the coating
are exposed to the fluid [264].
patterns of samples before and after hydrothermal process in an Coatings were deposited in an electrolyte with KOH and
autoclave for 2 h at 150 °C. DCPD and β-Ca3(PO4)2 were iden- Na3PO4. Then, KOH was replaced by Ca(OH)2 or Ca(NO3)2 to
tified after hydrothermal process. provide a Ca/P ratio similar to that of hydroxyapatite. Corrosion
Zhang et al. [140] performed PEO process on AZ31 magne- resistance was analyzed by means of electrochemical imped-
sium alloys at 250, 300 and 350 V in a phosphate-based elec- ance or potentiodynamic polarization in SBF. It was shown that
trolyte to improve corrosion resistance. Effect of applied corrosion procedure in SBF was controlled by diffusion. Coat-
voltage on corrosion resistance of films was investigated by ings formed in calcium electrolytes under 40 and 50 mA.cm−2
potentiodynamic polarization and electrochemical impedance demonstrated a considerable corrosion resistance in SBF
in a simulated body fluid after 7 days of immersion. Corrosion solution.
resistance decreased with increase in processing voltage and the
4.3.7.2. Time. Deposition time is another important factor that
best corrosion resistance was obtained at 25 V.
affects morphology, corrosion resistance and thickness of PEO
Gao et al. [266] formed PEO coatings on pure commercial
films on magnesium substrates. The effect of deposition time on
magnesium under current densities of 30, 40 and 50 mA.cm−2.
biocompatibility of PEO film which has been investigated by
some researchers [267–269] is explained in this part.
Gu et al. [267] studied the effect of duration time on corro-
sion resistance of PEO films on AZ31 magnesium alloy in a
SBF solution. The process was accomplished in 1, 3, 5 and
8 mins. Potentiodynamic polarization and electrochemical
impedance spectroscopy tests were used to assess corrosion
resistance. According to XRD analysis, main constituents of
coatings were Mg, MgO, MgAl2O4 and Mg3(PO4)2. The lowest
corrosion current density and the highest impedance were seen
for the film formed at 5 mins. It can be stated that, hence, this
film had the best corrosion resistance. Hydroxyapatite covered
films surfaces after immersion in the SBF solution. In fact,
hydroxyapatite formation implies the great role of SBF in pre-
diction of PEO coatings bioactivity within the human body.
Ca2+ and HPO2−4 were responsible for formation of hydroxy-
apatite. Due to high biocompatibility and bioactivity, hydroxy-
apatite is known as an excellent substance for medical implants
[270]. A physical model was developed by Gu et al. for corro-
sion process of PEO films on AZ31 magnesium alloys after
Fig. 39. XRD patterns of samples before and after hydrothermal process [265]. immersion in an SBF solution (Fig. 40). In initial steps of
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Fig. 40. Physical model of corrosion process of PEO films formed on magnesium substrate in SBF solution [267].
corrosion, the equivalent circuit consisted of two pairs of resis- Seyfoori et al. [273,274] compared biodegradability
tor and CPE regarding the porous and barrier layers. This indi- of PEO coatings deposited on AZ31 magnesium alloys using
cated that the magnesium substrate could not be exposed to the silicate and phosphate-based electrolytes in SBF solution. Cor-
SBF solution (due to short immersion time). At longer immer- rosion behavior of coatings was analyzed by means of
sion times, the SBF solution penetrated into the porous layer potentiodynamic polarization and open-circuit potential curves.
and then into the barrier layer and substrates. Consequently, a It was found that films produced in the silicate-based solution
pair of charge transfer resistor and capacitor was added to the were thicker and had a better corrosion resistance than those
equivalent circuit (Fig. 4b and c). Corrosion products formed formed in the phosphate electrolyte [273]. Besides, more
slowly during these two steps. PEO coating and corrosion prod- apatite was formed on the coating that was deposited in the
ucts obstruct SBF penetration into the substrate so that they silicate-based electrolyte [274]. Different content of apatite
improve corrosion resistance. After complete destruction of the formed on these coatings was associated to the corrosion
PEO film, the substrate becomes thoroughly exposed to the behavior and biodegradability [275]. In order that bone-like
SBF solution. A passive layer, then, covers the magnesium apatite phase is formed, pH value has to be sufficiently high.
substrate. Summarized results are presented in Table 3. Fig. 41 illustrates pH increase variations in silicate- and
phosphate-based electrolytes. It can by deduced that the main
reason for formation of more apatite on the silicate coating was
4.3.7.3. Electrolyte composition and additives. Electrolyte less emission of hydroxyl ions in the phosphate-based electro-
chemical composition has a significant role in properties of lyte [274].
plasma electrolyte oxidation coatings on magnesium substrates. Tang et al. [276,277] produced CaTiO3-containing PEO
This section is contributed to effect of concentration on bio- films on AZ31 magnesium alloys. Corrosion resistance of films
medical properties of PEO films on magnesium alloys. in SBF solution was evaluated by means of electrochemical
Wang et al. [272] deposited metasilicate-based coatings on method. Corrosion resistance and apatite formation ability were
AZ91D magnesium alloys in a sodium silicate electrolyte. improved by the PEO films that were deposited in presence of
Ca(H2PO4)2 concentration in the electrolyte was maintained at CaTiO3. Surfaces of coated and uncoated samples after seven
5, 10 and 15 g.lit−1. Corrosion resistance was studied by means days of immersion in SBF solution are displayed in Fig. 42. It
of electrochemical and immersion tests in SBF solution. Cor- may be concluded, accordingly, that plasma electrolyte oxida-
rosion resistance improved greatly due to formation of tion increased apatite formation ability on AZ31 magnesium
biocompatible phases such as CaSiO3, CaMgSiO4 and alloy.
Mg2SiO4. Besides, increase in Ca(H2PO4)2 concentration led Recently, strontium addition was tested to improve biologi-
improvement of corrosion resistance in AZ91D alloy. cal activities in magnesium alloys [278–280]. Lin et al. [281]
ARTICLE IN PRESS
Table 3
Effect of operation conditions on biodegradability of PEO coating.
Substrate Electrolyte Operation conditions Phases Results Thickness Ref
Mg-Ca 10 g/L sodium silicate Frequency: 700 Hz duty MgO, Mg2SiO4, Mg2Ca and 360 and 400 volt treated PEO 4.5 µm [271]
with 3.5 g/L sodium cycle: 30% applied voltage: Mg(OH)2,Ca2P2O7 after coating is the best coating for
hydroxide 300,360,400 immersion in Hank’s corrosion behavior and
solution biocompability point of view
ZK60 10 g/L Na2SiO3.9H2O, Frequency: 1000 Hz duty MgO, Mg2SiO4 Fabricated coating is biocompatible 10–25 µm [264]
10 g/L KOH and 8 g/L cycle: 40% applied voltage: due to MgO, Mg2SiO4 phases
KF.2H2O 230,300,370, 450 time:
5 min
Mg 15 g/l NaAlO2, 2 g/l Frequency: 100 Hz duty MgO, MgAl2O4 and Hydrothermal treatment led to 5–14 µm [265]
KOH, 4 g/l Na2HPO4, cycle: 35% applied voltage: CaHPO4.2H2, β-Ca3(PO4)2 increase biocompability of coating
4 g/l EDTA–Ca 350,420,450 current density: after hydrothermal treatment
100Ma/cm2
AZ31 10 g/l Na3PO4 in Frequency: 100 Hz duty — The coating which fabricated at — [140]
distilled water cycle: 30% applied voltage: 250 V have best coating properties
250,300,350 time = 5 min in biocompatibility and corrosion
resistance point of view
Pure Mg Na3PO4 · 12H2O, Ca current density: 30,40,50 MgO, Mg3(PO4)2 Fabricated coatings are suitable for 10 µm [266]
(NO3)2 · H2O, KOH Ma/cm2 biological applications
AZ31 30 g/L sodium phosphate Frequency: 3000 Hz applied Mg3(PO4)2, MgO, MgAl2O4, The coating which is formed at 5–20 µm [267]
current density:150Ma/cm2 HA 5 min has highest corrosion
time = 1,3,5,8 min resistance and HA formed after
immersion in SBF solution
formed MAO films on ZK60 magnesium alloys in a phosphate- Seyfoori et al. [283] synthesized nano-composite and PEO
based electrolyte to reduce initial biodegradability rate. They coatings on AZ31 magnesium alloy using a solution containing
also investigated the effect of strontium on bioactivity of films. hydroxyapatite nanoparticles in order to expand corrosion
Degradability findings showed that the Sr-bearing MAO film resistance and biomedical behavior of magnesium. Corrosion
had a better initial corrosion resistance inside human body. This behavior of coatings was evaluated using potentiodynamic
was explained through the good barrier layer (with more thick- polarization and electrochemical impedance spectroscopy tests
ness) as well as the longer protection ability due to apatite in SBF solution. Nano-composite coatings were seen to have a
formation. It was observed that MAO film degradation was higher resistance due to blocking of the corrosive medium
accompanied with formation of a degraded film and Ca-P pre- penetration into the coating by nanoparticles. Also, more apatite
cipitation. In addition, pH fluctuations in Sr-bearing electrolyte
were less than other coatings that indicates the lower corrosion
rate of this coating.
Ceramic composite coatings containing zirconium were
deposited on magnesium alloys using a silicate-phosphate elec-
trolyte that was reinforced with zirconium salt and sodium
hydroxide by Chu et al. [282]. They studied the effect of sodium
hydroxide concentration in the electrolyte on biodegradability
behavior in SBF and SIF solutions.
Fig. 42. Coatings surface morphology, a) uncoated magnesium and b) coated

Fig. 41. pH variations versus time in different coatings [274]. magnesium after seven days of immersion in SBF solution [276].
ARTICLE IN PRESS
growth increases at higher phosphate concentrations [287]. It

deemed possible to create amorphous PEO coatings with sealed
discharge channels in alkaline phosphate electrolytes that
contain Montmorillonite clay particles. Lu et al. [288] investi-
gated the effect of different phosphate and hydroxide concen-
trations in an electrolyte with clay particles on biodegradability
behavior of coatings. It was found that chemical composition
was the most important factor affecting biodegradability.
Then it was coating microstructure that was important in
biodegradability.
Corrosion resistance of metallic implants is influenced by
organic molecules such as serums and proteins, the effect of
which on corrosion rate of magnesium alloys is addressed in
Refs. 289 and 290. Wan et al. [291] produced PEO coatings on
magnesium alloys for biomedical applications. They also
studied the effect of albumin presence in the corrosive solution
on corrosion mechanism. It was observed that albumin acted as
a inhibitor by being adsorbed on surface and hindering further
dissolution. Hindering corrosion progress was attributed to
protein adsorption and precipitation of insoluble salts.
Silver (metal or salt) is used as an anti-microbial agent in
wounds [292,293]. Necula et al. [294] used silver nanoparticles
in a PEO bath to coat magnesium alloys for biomedical
purposes.
Silicon is the main element in animal nutriments and has an
important role in provocation of bone formation [295]. It has
been reported in many researches that glasses and silicate-
bearing ceramics are biocompatible and can establish chemical
bonds with bone tissues [296,297]. Yang et al. [298] formed
Mg2SiO4-bearing PEO coatings on Mg-Zn-Zr alloys in order to
enhance biocompatibility. They observed a noticeable improve-
Fig. 43. Apatite formation ability, a) MAO pure coating and b) nano-composite ment in biocompatibility behavior of coatings. Summarized of
coating after three days of immersion in SBF solution [283].
results are presented in Table 4.
4.3.7.4. Post-treatment. Oxide films produced on magnesium

was formed on the nano-composite coating than the pure PEO and its alloys are porous, thus, the corrosive medium may
one. Apatite formation ability after 3 days of immersion in SBF penetrate through the pores and achieve the substrate leading to
solution for both coatings is illustrated in Fig. 43. It may be early corrosion of implants. Generally, there are many post-
observed that more apatite was formed over the nano-composite treatment methods available for improving the efficiency of
sample. This is primarily due to bioactive nature of apatite in an coated implants. Now we consider effects of different post-
oxide film structure [284] and also high surface roughness of treatments on biomedical behavior of PEO coatings.
nano-composite coating [285].
Wang et al. [286] deposited PEO coatings on AZ91 magne- 4.3.7.4.1. Sealing treatment. In principle, sealing treatment
sium alloys for biomedical applications in a silicate-based solu- is employed after PEO coating treatment to improve efficiency
tion. They also studied the effect of titania addition on of coatings in biomedical applications and also other properties
microstructure, chemical composition and biodegradation of oxide films by filling the pores in coatings. Chu et al. [299]
behavior of coatings in SBF solution. Electrochemical tests fabricated PEO coatings on magnesium wires to be used for
results showed that presence of 5 to 10 volume percent titania in biomedical purposes. They analyzed the effects of three sealing
the solution led to reduction of corrosion resistance due to treatments after coating treatment (including boiling water, zir-
increase in amorphous components. Results obtained from conia sol-gel deposition and organic gelatin hydroxyapatite
long-term immersion test in SBF solution were also in line with deposition) on biodegradability properties. TEM micrographs
the electrochemical tests results. of coated and then sealed samples are shown in Fig. 44. Accord-
It was realized that increase in KOH concentration in PEO ing to Fig. 44a, unsealed samples had micropores uniformly
electrolytes leads to higher volume percentages of MgO in the distributed all over the surface. Sealing in boiling water,
coating that improves corrosion resistance [136]. Meanwhile, however, led to blocking of discharge channels and fewer pores
addition of Na3PO4 causes uniform distribution of sparks so that (Fig. 44b). This was attributed to reactions between films com-
the final coating would be more uniform. Kinetics of coating ponents and boiling water that led to fabrication of oxide and
ARTICLE IN PRESS
[276] hydroxide and blocking of pores. Fig. 44c shows that many
[281]
[282]
[283]
[286]
[291]
[294]
Ref
pores still existed on the surface after deposition of zirconia

sol-gel coating. In addition, pores sizes increased comparing
10 and 20 µm with the reference sample due to contraction during drying of
18–22 µm
Thickness
7–18 µm
zirconia sol-gel coating. It may be seen in Fig. 44d that coating
5 µm
7 µm
surface was cover with an organic layer after gelatin hydroxy-
–
corrosion and biological behavior of MAO coating apatite deposition process. Corrosion resistance improved after
any sealing treatment, however, the best corrosion performance
used for the synthesis of MgO–Ag nanocomposite

Introduction of Sr into electrolyte lead to improve
Hap additive cause the better corrosion resistance
Improve in biological properties of MAO coating
the PEO process suggests that the process can be

Successful deposition of Ag nanoparticles during
Incorporation of NaOH into electrolyte improve
Albumin act as inhibitor and improve corrosion

MAO coating improve corrosion resistance and
in SBF solution was observed with the sample deposited by a

of coating and greater apatite forming ability
gelatin hydroxyapatite film.
the biological properties of MAO coating
Sol-gel treatments after PEO process to enhance coatings

properties have been broadly discussed in literature [300–303].
Shi et al. [300] employed TiO2 sealing process through sol-gel
resistance of resultant coating immersion deposition technique and hydrothermal treatment to
with addition of titania sol
improve corrosion resistance of PEO coatings, produced in a

silicate/fluoride electrolyte, on magnesium implants in SBF
solution. It was stated that MAO-TiO2 coatings on magnesium
apatite formation
enhanced corrosion resistance of magnesium in SBF solution.

This would lead to fabrication of biodegradable implants.
coatings.
Results
Zhang et al. [301] fabricated PEO coatings in a phosphate-

based electrolyte to improve corrosion resistance of Mg-Zn-Ca
alloy in SBF solution. Since TiO2 films create biocompatible
immersion in SBF solution
Mg2SiO4, Anatase, Rutile,
coatings on implants [304–306], a TiO2 film was deposited on

Mg2SiO4, MgSiO3, MgO
Mg2SiO4,Hap,β-TCP
the porous PEO coating by means of sol-gel immersion process

MgHPO4.3H2O after
TiO2, MgO, CaTiO3
MgO, MgSiO3, and
and annealing in order to improve corrosion resistance and

MgSiO3, MgF2,
reduce exposure to the SBF solution. It was revealed that

Mg, MgO, Ag
MgO, MgF2
surface pores on PEO process were suitable sites for growth of

TiO2 film. Consequently, pores were blocked and biomedical
Phases
MgO
performance of alloy was enhanced. According to the obtained

results, TiO2 deposition on PEO coatings caused corrosion
Applied current density = 0.02 A/cm2
Applied current density = 3, 5 A/dm2
current density to decrease down to one-third of the original

Frequency: 1000 Hz duty cycle:10%
value.
Immersion in concentrated alkaline solutions is a simple and
economic way to seal pores over the surface. However, a con-
Applied voltage = 370 V
applied voltage: 400 V
tinuous film may not be formed on the surface due to the fact
Operation conditions
that deposition of electrolyte species in pores is controlled by

Time = 1–10 min
temperature and duration of process [31]. As an alternative for

Time = 10 min
Time = 15 min
Time = 15 min
Time = 5 min
Time = 5 min
alkaline solutions, sol-gel post-treatment can be used to reduce

pores density. There have been many studies concerning
improvement of corrosion resistance in magnesium alloys with
MAO-sol-gel treatment [307,308]. Malayoglu et al. [31] syn-
nanoparticles
thesized PEO coatings on AM50B and AM60B magnesium

Titania sol
Effect of additives on biodegradability of PEO coating.
Strontium
alloys. In order to achieve better corrosion resistance, samples

Albumin
Additive
CaTiO3
NaOH
were post-treated by immersion into alkaline phosphate and

HAp
Ag
silicate solutions as well as sol-gel to seal coating pores.

According to electrochemical tests results, sealing treatments
Na2SiO3 (7 g/L), NaF(5 g/L)
led to closure of coatings pores and reduction of surface rough-

Na2SiO3 · 9H2O (10 g/L)
sodium phosphate (5 g/L)
sodium silicate (10 g/L)
ness. The best corrosion properties were obtained via sol-gel

C3H7O6PCa (6 g/L)
process.
Na2SiO3(15.0 g/L)
KF · 2H2O (8 g/L)
NaOH(10.0 g/L)
8 g/l KF · 2H2O
K2ZrF6 (3 g/L)
K2TiF6 (4 g/L)
3 g/l (NaPO3)6
NaOH (6 g/L)
KOH((2 g/L)
KOH (1 g/L)
KF(8.0 g/L)
4.3.7.4.2. Deposition of a second layer of

Electrolyte
Keronite
hydroxyapatite. Hydroxyapatite is a very good biocompatible

substance as it improves bone growth and forms strong bonds
with a living bone tissue [309–311]. Formation of two-step
coatings and deposition of hydroxyapatite on PEO films
Substrate
pure Mg
AZ31B
Table 4
improves biological properties of implants and increases its

AZ31
ZK60
AZ31
AZ91
Mg
efficiency [312–315]. Subsequent hydroxyapatite deposition is
ARTICLE IN PRESS
Fig. 44. Surface morphology of magnesium wires deposited by PEO process after different sealing treatments, a) unsealed sample, b) sealed in boiling water, c)
sealed by zirconia sol-gel deposition and d) sealed by gelatin hydroxyapatite film [299].
often carried out through electrical, electrophoretic and solu- Sreekanth et al. [314] synthesized PEO coatings on magne-
tion treatment processes. In this regard, MAO/ECD composite sium alloys. Afterwards, they applied a hydroxyapatite film by
coatings were produced for biomedical applications on magne- means of electrophoretic method to improve biodegradability
sium alloy by Zhao et al. [312], Chen et al. [313] and Gao et al. of coatings. Potentiodynamic polarization tests were performed
[315]. They initially formed MAO films on magnesium alloy in in SBF solution to evaluate biodegradability of films. It was
an electrolyte with calcium and phosphorous; then, hydroxy- realized that formation of a second layer made of hydroxyapa-
apatite was deposited on MAO films through electrical process. tite on PEO films would lead to improvement of corrosion
Corrosion resistance of coatings was estimated in SBF solution resistance in SBF solution.
by means of electrochemical testing. It was reported that for- Tang et al. [316] fabricated hydroxyl apatite on already
mation of composite coatings with hydroxyapatite effectively PEO-coated AZ31 magnesium alloys by means of solution
reduced corrosion rate and improved bioactivity. Polarization treatment in order to improve biodegradability of alloys.
curves of the magnesium substrate, MAO-coated magnesium Potentiodynamic polarization and electrochemical impedance
and MAO/ECD-coated magnesium in SBF solution are illus- spectroscopy tests were conducted in SBF solution. Apatite
trated in Fig. 45. It may be seen that corrosion resistance of
coatings improved significantly with formation of the compos-
ite coating.
It was reported that application MAO/ECD composite coat-
ings on magnesium would find useful clinical purposes in the
future [312,313]. Radiographs of bone tissues and samples
taken at 1, 4 and 8 weeks after surgery are shown in Fig. 46. No
gas bubble may be seen. The substrate and coated sample main-
tained their initial shape after the first week (Fig. 46a, d).
Degradation through a distance between sample and bone
occurred after four weeks (Fig. 46b, c). The distance was
created due to rapid degradation with no instant replacement by
the new bone tissue. However, no considerable degradation was
observed around the coated sample after eight weeks (Fig. 24e).
Besides, the composite coating degraded slightly (Fig. 46f). The
substrate and coated sample were not seen in the radiographs
after 32 and 48 weeks. This indicates utter degradation of all Fig. 45. Polarization curves of the magnesium substrate, MAO-coated magne-
species [313]. sium and MAO/ECD-coated magnesium in SBF solution [312].
ARTICLE IN PRESS
Fig. 46. Radiographs of the substrate (a–c) and coated samples (d–f) at 1, 4 and 8 weeks after surgery [313].
formation ability was also investigated in this work. It was

shown that solution treatment sealed the existing pores and
cracks on MAO surface by forming a barrier film. Fig. 47 shows
cross sections of MAO and MAO-ST coatings. It may be
observed that solution treatment sealed the pores and cracks on
MAO surface so that corrosion resistance was improved.
PEO coatings were applied on AZ91D magnesium alloys by
Song et al. [317]. By means of electrical deposition, they
applied another film of hydroxyapatite on PEO coatings. Bio-
degradability was investigated through electrochemical and
immersion tests. According to the results, HA film significantly
decreased biodegradability of AZ91D magnesium alloys in
SBF solution.
4.3.7.4.3. Other treatments. In recent decades, various sub-
stances nano-hydroxyapatite, carbonate, TiO2, Chitosan, etc.
were employed to enhance corrosion resistance of magnesium
alloys through coating [318]. Bai et al. [319] deposited PEO
films on Mg-Zn-Ca alloy to enhance biocorrosion behavior.
Then, they immersed the films in Chitosan solution. Corrosion
resistance was analyzed by anodic polarization measuring in
SBF solution. It was observed that corrosion resistance of com-
posite coatings was considerably improved due to sealing of the
surface pores.
Hydrofluoric acid (HF) treatment has been studied by many
researchers as an acid washing treatment for magnesium alloys
[320,321]. In HF process, a layer of insoluble magnesium fluo- Fig. 47. Cross sections of a) MAO and b) MAO-ST [316].
ARTICLE IN PRESS
Fig. 48. Surface morphology of a) MAO, b) calcium phosphate on MAO, c) high magnification and d) elemental analysis of the given area [325].
ride is produced which prohibits corrosion progress [321]. It A PEO film was initially applied on the substrate, then,
was reported elsewhere that magnesium hydroxide coverts to dicalcium phosphate dihydrate was deposited on the PEO film.
magnesium fluoride films during the HF process [322]. Lin Corrosion behavior and apatite formation ability in SBF solu-
et al. [323] formed PEO coatings on biodegradable ZK60 mag- tion were analyzed through hydrogen emission and scanning
nesium alloys. Then, they performed HF treatment on samples electron microscopy. MAO-DCPD coating was seen to signifi-
to improve properties of coatings. The porous PEO coating cantly improve both corrosion resistance and apatite formation
faded after HF treatment and magnesium fluoride constituted ability.
the essential part of the coating. However, microcracks were Mechanism of calcium phosphate formation on PEO films
seen abundantly over the surface after HF treatment which has not been much studied. Theoretical analyses revealed that
diminished corrosion resistance. Microcracks could be different environments may affect calcium phosphate nucle-
removed via sealing treatments. ation and growth [327–329]. Lin et al. [330] applied calcium
Due to proper bioactivity and having the ability to form phosphate on PEO films in order to improve biocompatibility
bone-like compounds (such as hydroxyapatite), calcium phos- by means of chemical methods. Regarding mechanism of
phate was used to improve biodegradability of PEO coatings by calcium phosphate formation, they proposed that MgO dis-
deposition of a second film. In addition, calcium phosphate may solves when a clean surface is placed in an acidic electrolyte.
enhance natural bonds among bones and implants surfaces This leads to formation of Mg(OH)2 which is partially soluble
[324]. Liu et al. [325] fabricated bioactive calcium phosphate in Ca(NO3)2 solution. Consequently, an alkaline area is formed
films on PEO-coated magnesium substrates through chemical near to the substrate. Mg(OH)2 on the substrate may be consid-
treatment in order to improve biodegradability of alloys. Fig. 48 ered as a suitable site for nucleation of calcium phosphate
shows TEM micrographs of coated samples. A normal porous [331,332]. Initially, Mg(OH)2 forms hydroxyl bond groups
structure may be seen in Fig. 48a. Fig. 48b illustrates morphol- which may lead to nucleation of hydroxyapatite [333,334].
ogy of samples after calcium phosphate PEO coating deposition High concentration of HPO2−4 and low concentration of Ca2+ in
where consists of spherical and planar microstructures. Spheri- acidic solution may influence DCPD deposition on the substrate
cal crystallites seemed to be porous at high magnifications. [330].
Ca/P ratio was 1.43 which was less than stoichiometric HA Calcium phosphate was deposited on PEO films already
ratio. Immersion results showed that new apatite phases formed synthesized on magnesium substrates by Lin et al. [335]. It was
on surface. Apatite formation was improved by dissolution of aimed to study the effects on corrosion resistance in SBF solu-
DCPD into the SBF solution. tion. The produced coating contained DCPD and hydroxyapa-
Shi et al. [326] synthesized MAO-DCPD coatings on AZ80 tite. In addition, corrosion resistance of the substrate was
magnesium alloy in order to improve biocompatibility behavior. improved due to formation of new bone-like hydroxyapatite. In
ARTICLE IN PRESS
other words, a thick and dense apatite film may protect the effect and mechanical mixing of the melted magnesium oxide
substrate against corrosion well. zones [347,363]. In another study where films were formed on
Hydrothermal treatment is a simple and economic technique 99.9% Mg samples, adding zirconium oxide monoclinic
for coating of metallic substances. Its application for magne- nanoparticles to a silicate electrolyte was investigated. It was
sium alloys to improve corrosion resistance has been paid a observed that these particles abundantly participated in the
great deal of attention over the last few years [336–339]. Chang outer layer and even trace amounts of particles were seen within
et al. [265] formed calcium phosphate on AZ31 magnesium the inner layer. In addition, MgO and Mg2SiO4 were identified
alloy through MAO fabrication process. They also applied low- in the coating while silicon content in the inner layer was less
temperature hydrothermal treatment to enhance performance of than the outer one. Formation of Mg2ZrO5 was also confirmed
alloys in biomedical purposes. Biocorrosion behavior of coat- at micro-sparks positions due to local increases of temperature
ings before and after hydrothermal treatment in Hankel’s solu- [364].
tion was investigated through anodic polarization and Lee et al. [348] studied addition of zirconia and titania
electrochemical impedance spectroscopy tests. According to nanoparticles with size of 150–200 nm to phosphate electro-
the findings, hydrothermal treatment not only transformed lytes. Increase in voltage was observed at separate baths which
amorphous calcium and phosphorous into DCPD and was correlated with increase in electrical resistance of films due
β-Ca(PO4)2 but also improved resistance against biocorrosion to addition of zirconia and titania. Similar to any other PEO
(especially pitting corrosion) in magnesium alloys. Summa- films produced in phosphate electrolytes, cross section analysis
rized of results are presented in Table 5. revealed formation of a coating with inner and outer layers
[138]. Zirconia particles could be observed very clearly in SEM
5. Nanocomposite PEO coatings studies. However, titania particles were not found which is due
to lower melting point of titania than zirconia. Consequently, it
Harder, more wear resistant and more corrosion resistant
is safe to assume that plasma temperature on sample surface
films than magnesium alloys may be synthesized in coating by
was between melting point of titanium and zirconium oxides
plasma electrolytic oxidation. However, PEO films are porous
(2116 K–2643 K).
and thus cannot account for long-term protection. Sealing and
avoiding formation of porous coatings, is of great importance. 5.2. Titania nanoparticles
Electrolyte chemical composition is a determining factor in
Adding TiO2 particles to the PEO electrolyte is important
properties of films [342,343]. Electrolytes with certain chemi-
due to applicability for solar energy [365,366], air refinery
cal composition are often used for PEO process. Wear resis-
[367,368], photo catalysis [369,370] and corrosion protection
tance, corrosion resistance and hardness may be changed by
[371–373]. Introducing 4.8 g.lit−1 titanium oxide particles to an
adding new particles in order to be incorporated in the films and
aluminate electrolyte was reported to reduce corrosion potential
form various types of phases. Chemical composition of the
(by 180 mV) and corrosion current and also increase drop time.
electrolyte and the consequential coating formation conditions,
Thickness also increased from 19 to 24 µm with increase in
along with other factors such as the stirring rate of the electro-
TiO2 concentration from 0 to 4.8 g.lit−1. Color of coatings went
lyte and properties of the added particles such as their concen-
from light grey to dark grey. However, excessive addition of this
tration, melting temperature, chemical stability, bonds types
substance may lead to demolition of coatings [374]. White et al.
and particles size, one may predict contribution level of par-
[375] formed PEO coatings on AZ31D alloy at 5 mins using a
ticles. [344] . Summary of results studied in this section are
phosphate electrolyte with 6 g.lit−1 TiO2 nanoparticles. XRD
presented in Tables 6 and 7, which depict the processing param-
patterns confirmed presence of Mg2TiO4 that was produced by
eters and coating properties with addition of nanoparticles to
reaction between MgO and TiO2. There was also no peak indi-
the electrolyte, respectively.
cating any form of TiO2 (rutile or anatase) which may be due to
extremely low amounts of their crystalline phases at short
5.1. Zirconia nanoparticles
periods of process. Corrosion resistance of TiO2-bearing PEO
Arrabal et al. [361] added monoclinic zirconia particles films obtained from phosphate electrolytes was evaluated. Elec-
(150–300 nm) to alkaline silicate and phosphate-based electro- trochemical parameters are presented in Table 1. The effect of
lytes. The effect of these particles on properties of films pro- TiO2 nanoparticles on hardness of coatings has also been con-
duced on magnesium by means of PEO for 2400 s using direct firmed elsewhere. Forty percent improvement in hardness com-
current was analyzed. It was revealed that zirconia particles pared to samples without nanoparticles was reported in a
were present within the underlying layer of coatings after phosphate-silicate-tetraborate electrolyte. The same research,
passing the outer transient layer. Tetragonal zirconia particles however, did not mention any considerable changes in corro-
were also observed in the outer layer which may be formed due sion resistance after addition of 4 g.dm−2 TiO2 [376]. It was
to temperatures higher than 1513 K. Besides, annealing treat- reported, elsewhere, that color of coatings went from grey to
ment on zirconia-bearing coated samples improved corrosion blue after addition of 4 and 6 g.lit−1 titanium oxide
resistance due to sintering of zirconia particles [362]. Accumu- nanoparticles to a phosphate electrolyte (Fig. 1). XRD investi-
lation of zirconia nanoparticles at coating pores which led to gations revealed that apart from MgO and Mg3(PO4)2, rutile and
improvement of corrosion resistance was reported elsewhere. Mg2TiO2 were also identified after addition of titanium oxide
Accumulation of particles was attributed to the electrophoretic nanoparticles. SEM studies showed that thickness increased
Table 5
Effect of different post treatment on biodegradability of PEO coating.

Substrate Electrolyte Post treatment Operation condition Phases Results Thickness Ref
Pure Mg NaOH (2 g/l), Na4SiO4 (8 g/l), sol–gel TiO2 sealing Frequency: 50 Hz MgF2, MgO, TiO2 TiO2 sol-gel sealing significantly improved 10 µm [340]
NaF (2 g/l) corrosion resistance of sample in hanks solution
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Mg-Zn-Ca 0.1 mol/l Na3PO4 · 12H2O, sol–gel TiO2 sealing Applied voltage: 120,140 V Mg3(PO4)2 TiO2 sol-gel sealing significantly improved – [301]
0.05 mol/lNaOH Time = 20–30 min corrosion resistance and biodegradable behavior of
sample
AM50B KOH, NaAlO2 and K3PO4 Alkaline phosphate, Current density: 20–30 A/dm2 MgO, MgAl2O4 Post treatment sealing improved corrosion behavior 10,25 µm [31]
AM60B alkaline silicate, Time: 7, 14 min of coating due to sealing the micro pores
sol-gel sealing
AZ31B Calcium gluconate (4 g/L), Electrochemical Frequency: 600 Hz duty cycle:20% MgO, CaHPO4. Electrochemical deposition of HA coating was 16–20 µm [312]
sodium hexametaphosphate deposition of HA applied voltage: 200–320 V 2H2O, HA improved biological behavior of PEO coating
(3 g/L), sodium hydroxide coating
(6 g/L)
Mg-Zn-Ca Na3PO4 (0.5 molL1), NaOH Electrochemical Current density:0.4 mA/cm2, Time Mg3(PO4)2, MgO, and Post treatment was improved biological behavior of 10 µm [313]
(0.05 molL1) deposition of HA 30 min HA,OCP after post PEO coating
coating treatment
Mg-Zn-Ca 0.1 mol/l Na3PO4 · 12H2O, Electrochemical Applied voltage:165–175 V Mg3(PO4)2, HA Electrochemical deposition of HA coating was – [341]
0.028 mol/l deposition of HA Time: 30 min improved biological behavior of PEO coating
CH14N2Na2O8 · H2O, coating
0.01 mol/l Na2SiO3 · 9H2O,
0.28 mol/l KF · 2H2O
AZ31 NaOH (6 g/L), Na3PO4 · 12H2O Solution treatment Frequency: 1000 Hz duty cycle:10% Mg. HA solution treatment by sealing the micro pores and 20 µm [316]
(12 g/L) applied voltage: 400 cracks of coating improve the corrosion resistance
Time = 10 min and apatite formation
ZK60 10 g/L Na2SiO3 · 9H2O, 1 g/L Hydrofluoric acid Frequency: 1000 Hz duty cycle:40% MgO, MgF2, HF treatment is promising as a post treatment 10 µm [323]
KOH, 8 g/L KF · 2H2O post treatment applied voltage: 300 Mg2SiO4, method for the MAO coating on biodegradable
Time = 5 min Mg9F2(SiO4)4 magnesium alloys
43
44
Table 6
The effect of nanoparticle addition on PEO processing parameters.
Substrate Electrolyte Additives Condition Frequency Current VSpark initiation Time Duty Thickness(µm) Phases Ref
(Hz) density (volt) (min) cycle PEO PEO + adds
(A/dm2)
Mg 99.9% 0.025M ZrO2 2 g/l DC — 3 ~170 (1) 40 — ~15 (1) MgO-Mg2SiO4-ZrO2 (1) [345]
Na2SiO3.5H2O//0.05M ~225 (2) ~37 (2) MgO-Mg3(PO4)2-ZrO2-Mg2Zr5O12
KOH(1) (2)
0.025M Na3PO4.12H2O/1.5M
NH4OH(2)
0.025M ZrO2 10 g/l AC 50 20 (RMS) ~250 40 — ~40 MgO-Mg2SiO4-ZrO2-Mg2Zr5o12 [346]
Na2SiO3.5H2O//0.05M KOH

AZ91 0.089M KOH//0.052M KF// ZrO2 9 g/l AC — 5 ~170 8 — — — MgO-Mg3(PO4)2-ZrO2 [347]
0.009M K4P2O7
0.09M KOH//0.05M ZrO2 9 g/l AC — 5 ~250 8 — ~10 MgO-ZrO2 [348]
KF//0.01M K4P2O7 TiO2 9 g/l MgO-TiO2-MgTi2O4
ARTICLE IN PRESS
20 g/l NaAlO2//5 g/l NaOH TiO2 1.6 g/l AC 700 4 ~340 60 — 19 22 MgO-MgAl2O4 [349]
TiO2 3.2 g/l 24
TiO2 4.8 g/l 25
AZ91D 15 g/l Na2SiO3//9 g/l SiC 4 g/l DC 520 15+ ~300 15 38%+ 23 26 MgO-MgAl2O4-Mg2SiO4 [350]
NaAlO2//2 g/l Na2B4O7//3 g/l 18− 30%−
NaOH//5 ml/l C3H8O3//7 g/l
C6H5Na3O7
6 g/l (NaPO3)6//3 g/l TiO2 2 g/l DC 200 3 ~280 15 15% ~29 ~31 MgO-Mg3(PO4)2-TiO2- [351]
NaOH//10 ml/l TiO2 4 g/l ~300 ~35 Mg2TiO4-MgAl2O4
triethanolamine TiO2 6 g/l ~300 ~30
1 g/l KOH//10 g/l NaAlO2 Al2O3 5 g/l — 500 ~53 ~400 12 50% 23 33.5 MgO-MgAl2O4-Al2O3 [352]
Al2O3 10 g/l 36.9
Al2O3 15 g/l 40.4
20 g/l NaAlO2//3 g/l NaOH SiC 2 g/l DC 500 5 — 45 — 12 MgO-MgAl2O4 [353]
700 20
900 21
AZ31 1 g/l NaH2PO4.2H2O//10 g/l TiO2 6 g/l AC 1000 — — 5 — 2–4 MgO-Mg2TiO4 [354]
NaOH
10 g/l Na2SiO3//3 g/l KF CeO2 10 g/l DC 100 5 ~250 10 6% ~10 CeO2-Mg2SiO4 [355]
CeO2 20 g/l
CeO2 30 g/l
0.03M KOH//0.05M Ta2O5 1 mg/l DC 500 0.7 ~150 20 50% 12.5 13.8 MgO-Mg3(PO4)2-Ta2O5 [356]
KF//0.2M Na3PO4 Ta2O5 5 mg/l ~150 14.6
Ta2O5 10 mg/l ~413 15.7
AZ31B 4 g/l Na3PO4//1.5 g/l KOH WC 5 g/l — — 5.5 ~460 5 — 9.67 6.34 — [357]
10 11.49 10.15
15 12.58 12.06
20 18.30 14.76
AM50 1 g/l KOH//10 g/l Na3PO4 Si3N4(0.1–0.8 µm) 5 g/l DC constant — — — 10 11% 40 25 MgO-Si3N4 [358]
Si3N4(1–5 µm) 5 g/l voltage 10
1 g/l KOH//20 g/l Na3PO4 SiO2(nano) 5 g/l DC constant — ~2.7 — 10 11% 45 25 MgO-SiO2 [359]
SiO2(micro) 5 g/l voltage 33
MA8 15 g/l Na2SiO3//5 g/l NaF ZrO2 40 g/l — 300 — — 13 50% — — MgO-ZrO2 [360]
SiO2 40 g/l MgO-Mg2SiO4
Table 7
PEO coating parameters applied with addition of nanoparticles to the electrolyte.
Substrate Electrolyte Adds Wear rate Hardness Corr. test Corrosion properties Ref
(×10−4 mm3/Nm) condition PEO PEO + adds
icorr(µA/cm2) Ecorr (v) Rp (Ω∙cm2) icorr(µA/cm2) Ecorr (v) Rp (Ω∙cm2)
AZ91 0.089M ZrO2 9 g/l — — 3.5 wt.% 0.727 −1.40 3.09 × 10 5
0.0703 −1.31 1.79 × 106 [347]
KOH//0.052M KF// NaCl (Ag/AgCl) (Ag/AgCl)
0.009M K4P2O7
20 g/l NaAlO2//5 g/l TiO2 1.6 g/l — — 3.5 wt.% ~10 −1.51 — ~10 ~−1.41 — [349]
NaOH TiO2 3.2 g/l NaCl ~10 ~−1.38
TiO2 4.8 g/l ~10 ~−1.41

AZ91D 15 g/l Na2SiO3//9 g/l SiC 0 g/l 0.0267 mg/min 445.3 3.5 wt.% 0.0099 −1.460 4607591 0.0077 −1.374 5470203 [350]
NaAlO2//2 g/l SiC 4 g/l 0.0133 NaCl (Hg/Hg2Cl2) (Hg/Hg2Cl2)
Na2B4O7//3 g/l
NaOH//5 ml/l
ARTICLE IN PRESS
C3H8O3//7 g/l
C6H5Na3O7
6 g/l (NaPO3)6//3 g/l TiO2 2 g/l — — 3.5 wt.% 0.69 −1.514 — N/A N/A — [351]
NaOH//10 ml/l TiO2 4 g/l NaCl (SCE) 0.019 −1.488
triethanolamine TiO2 6 g/l 0.038 −1.433
(SCE)
1 g/l KOH//10 g/l Al2O3 5 g/l — ~275 3.5 wt.% 4.48 −0.7239 9827 3.79 −0.5845 11321 [352]
NaAlO2 Al2O3 10 g/l ~350 NaCl (SCE) 0.56 −0.5086 58763
Al2O3 15 g/l ~375 0.63 −0.4460 66548
(SCE)
1 g/l TiO2 10 g/l — — 3.5 wt.% — — — 2.64 −1.418 1.65 × 105 [354]
NaH2PO4.2H2O//10 g/l NaCl (SCE)
NaOH
10 g/l Na2SiO3//3 g/l CeO2 10 g/l — — 3.5 wt.% 8.6 −1.54 — 1 −1.53 — [355]
KF CeO2 20 g/l NaCl (SCE) 0.2 −1.52
CeO2 30 g/l 0.04 −1.45
(SCE)
0.03M KOH//0.05M Ta2O5 1 mg/l ~0.2 µm3/cycle ~300 SBF 0.6158 −1.3970 — 0.1430 −1.2544 — [356]
KF//0.2M Na3PO4 Ta2O5 5 mg/l ~0.18 mN ~350 (SCE) 0.0721 −1.1211
Ta2O5 10 mg/l ~0.9 ~370 0.0712 −1.0512
(SCE)
AZ31B 4 g/l Na3PO4//1.5 g/l WC 5 g/l 9.711 ×10−4 232* — — — — — — — [357]
KOH 9.14 mg/m N 244
6.86 231
6.67 442
AM50 1 g/l KOH//10 g/l Si3N4(0.1–0.8 µm) 5 g/l — — 0.5 wt.% 0.09 −1.509 — 0.19 −1.559 — [358]
Na3PO4 Si3N4(1–5 µm) 5 g/l NaCl (Ag/AgCl) 0.13 −1.575
(Ag/AgCl)
AM50 1 g/l KOH//20 g/l SiO2(nano) 5 g/l 4 ×10−4 396 0.5 wt.% 0.12 −1.588 — 0.24 −1.550 — [359]
Na3PO4// SiO2(micro) 5 g/l 7.3 mm3/Nm 338 NaCl (Ag/AgCl) 0.19 −1.566
(Ag/AgCl)
MA8 15 g/l Na2SiO3//5 g/l ZrO2 40 g/l 0.29 × 10−5 mm3/Nm 4.7 Gpa 3 wt.% NaCl 0.11 −1.52 240000 0.053 −1.42 490000 [360]
NaF SiO2 40 g/l 0.35 × 10−5 3.8GPa 0.082 −1.50 320000
* In 5,10,15 and 20 minutes.
45
ARTICLE IN PRESS
Fig. 49. SEM micrographs of PEO coatings a) without nanoparticles, b) with 1 g.lit−1 nanoparticles, c) with 5 g.lit−1 nanoparticles and d) with 10 g.lit−1 nanoparticles
(high focus) on AZ31 alloys [382].
and pores size reduced after adding titanium oxide the solution for 1, 5 and 10 g.lit−1. It may be seen in Fig. 49 that
nanoparticles up to 4 percent. This, in turn, led to enhancement particles fully participated in layer formation process and pref-
of corrosion resistance. However, corrosion resistance was erably filled the existing pores and cracks. This improved cor-
deteriorated with further increase in TiO2 concentration due to rosion resistance which was proved by potentiodynamic
thermal conditions intensification and crack initiation. Placing polarization and impedance tests. Phase analyses showed that
coated samples that contained nanoparticles into methylene MgO was dominantly present within the inner layer while
blue solution, it was observed that MB concentration decreased Mg3(PO4)2 and Ta2O5 were identified on the outer layer. In
due to the photo catalytic effect of titanium oxide [351]. addition, thickness and uniformity of films were improved with
Table 1: Electrochemical parameters regarding the AZ31 increase in concentration of particles due to decrease in elec-
substrate and PEO film that was synthesized at 5 mins [375]. trolyte conductivity. Although wear resistance was improved by
5.3. Ceria nanoparticles adding 5 g.lit−1 Ta2O5 to the electrolyte, it dropped after further
increase in Ta2O5 concentration up to 10 g.lit−1 [382]. (Fig. 50)
Among all nanoparticles, cerium-rich compounds have 5.5. Alumina nanoparticles
attracted great attention due to many promising results achieved
from adding rare earth elements in order to alter surface prop- Wang et al. [352] studied the effect of Al2O3 addition to
erties [377–380] Ceria nanoparticles have also been added to electrolytes on corrosion resistance and hardness of coatings. 5,
the PEO coating bath on titanium and showed high potential in 10 and 15 g.lit−1 nanoparticles were added to separate electro-
improvement of properties of the resulted coatings [381]. Lim lytes. Voltage–time plots of PEO process revealed that alumi-
et al. [355] produced PEO films on AZ31 alloys in a Na2SiO3- num oxide nanoparticles mainly contributed to the process in
based electrolyte containing CeO2 nanoparticles. Cerium oxide the second step (micro arc oxidation) when de-charging is
nanoparticles utterly contributed to the coating and filled pores intensified. Besides, Al2O3 particles underwent chemical reac-
and cracks all over the surface. The expected improvement in tions and turned into MgAl2O4 which has desirable mechanical
corrosion resistance was confirmed via potentiodynamic polar- and corrosion properties. Nanoparticles addition also improved
ization and impedance tests. In addition, resistance against thickness, hardness and corrosion resistance. But, corrosion
pitting corrosion was analyzed by immersion test using 3.5wt% resistance did not change after increasing nanoparticles content
NaCl solution. Associated SEM micrographs showed that pores from 10 g.lit−1 to 15 g.lit−1. This was caused by a series of
became quite small in CeO-bearing films compared with other complicated processed during the MAO which limits participa-
films. tion of particles. Adding 10 g.lit−1 Al2O3 nanoparticles to the
electrolyte, therefore, may be expected to provide films with the
5.4. Ta2O5 nanoparticles
best chemical composition in terms of corrosion resistance and
Effect of Ta2O5 nanoparticles addition on properties of AZ31 hardness. Adding aluminum oxide particles to an aluminate
magnesium alloy has been studied. Nanoparticles were added to electrolyte in PEO coatings of AM60B alloy was investigated
ARTICLE IN PRESS
Fig. 50. Backscattered scanning electron micrographs of cross section of PEO coatings, a) PPEO(S), b) PPEO(M) and c) PPEO(L) [358].
elsewhere. According to the results, no sign of Al2O3 was that final and striking voltages increased by addition of 4 g.lit−1
observed. Also, a new mechanism for chemical reactions of nanoparticles. Besides, porosity decreased and density
Al2O3 particles was proposed. These reactions that are stimu- increased in samples with nanoparticles which, in turn, led to
lated by micro-sparks include three processes. However, these improvement of corrosion and wear resistance and reduction of
findings may only apply to the specific experimental conditions friction coefficient. It was stated that thickness and hardness
in this research. It is not possible to overlook the probability of increased by adding 4 g.lit−1 SiC. Current frequency was also
mechanical trapping occurrence exclusively or chemical reac- changed in order to study its effect on properties of films on
tion and mechanical trapping combined in other experimental AZ91D alloys that were produced in an alkaline electrolyte with
situations [383]. 2 g.lit−1 SiC nanoparticles. Thickness and growth rate increased
with increasing the applied current frequency from 500 Hz to
MgO(s) → MgO(l) (10)
700 Hz and 900 Hz. Else, A finer microstructure was detected
at 900 Hz. The lowest friction coefficient was measured at
Al2O3(s) → Al2O3(l) (11)
900 Hz where a 10 N load was applied [353]. Effectiveness of
MgO(l) + Al2O3(l) → MgAl2O4 (12) SiC nanoparticles on growth rate increase in silicate-
hexametaphosphate electrolytes was confirmed in a work by Yu
5.6. Tungsten carbide nanoparticles et al. [386]. SEM and XRD studies showed that SiC
nanoparticles participated in coating. It was also mentioned that
Nasirivatan et al. [384] added 5 g.lit−1 tungsten carbide adding SiC nanoparticles not only improved corrosion resis-
nanoparticles to a phosphate electrolyte in PEO coating of tance by a considerable extent, but it also enhanced wear resis-
AZ31B magnesium alloy. They reported that nanoparticles tance due to removal of weak sites during wear process (which
were adsorbed on the pores. Sparking voltage in WC-bearing are observed in no-nanoparticle samples due to inhomogeneity
samples was 10–15 V less than those without any of PEO films).
nanoparticles. Pores size also decreased with addition of
5.8. Si3N4 nanoparticles
nanoparticles. Finally, wear rate reduced by adding
nanoparticles and increase in Coating time. Silicon nitride (Si3N4) addition was also studied due to its
unique properties including high hardness, high wear resis-
5.7. Silicon carbide nanoparticles
tance, neutral chemical affinity and high-temperature applica-
Silicon carbide nanoparticles are also used in order to tions [358,387]. Adding Si3N4 (in different particle sizes) to
improve properties of PEO coatings. Wang et al. [385] added phosphate based electrolytes in PEO process on AM50 alloys
SiC nanoparticles with approximate size of 40 nm to the elec- was investigated using a unipolar pulsed power source at pulse
trolyte used for PEO coating of AZ91D alloy. It was observed ratio of ton : toff = 2 ms : 18 ms. 5g Si3N4 particles with size of
ARTICLE IN PRESS
Fig. 52. Cross section morphology of triple-layer coating produced by PEO,

SANP and electroless Ni plating [389].
Fig. 51. XRD patterns of PEO coatings in a phosphate electrolyte a) without with nanoparticles; while, basic samples showed the least hard-
SiO2 particles, b) by adding SiO2 nanoparticles and c) by adding SiO2
microparticles [359].
ness and wear resistance. Also after SiO2 particles addition,
only a minor reduction in corrosion resistance was seen; there-
fore, these coatings would be suitable for biomedical applica-
tions. They also divided participation of particles in PEO
0.02–0.1 µm (PPEO(S)), 0.8 µm (PPEO(M)) and 1–5 µm
process into two stages. The first stage includes adsorption of
(PPEO(L)) were added to 1lit electrolyte. Voltage was main-
nanoparticles by electrophoretic forces before reaching the
tained throughout the process at 450 V and process duration
breakdown voltage. This makes nanoparticles to adhere to cor-
was 10mins. XRD and EDS analyses revealed that Si3N4 par-
rosion products around intermetallics. In the second stage, after
ticles did not react during the process which might be due to
reaching the breakdown voltage, nanoparticles participation
insufficient electrical discharge energy for melting the particles.
occurs through open pores like discharge channels in sponge
However, it was clear that micropores and microcracks were
structure of coatings. Microparticles adhered to the molten
entirely filled with these particles. Thickness of PEO films was
materials and were surrounded during film growth [388].
adversely affected by increase in Si3N4 particles size. Corrosion
(Figs. 52–57)
resistance did not improve by adding these particles [358].
Gnedenkov et al. [394] studied coatings produced in silicate-
fluoride electrolytes (15 to 5 g.lit−1) by adding ZrO2 or SiO2.
5.9. Silica nanoparticles
XRD analysis ZrO2 peaks while no SiO2 trace could be found.
Lu et al. [359] added micro- and nano-scaled SiO2 particles This was associated to the fact that SiO2 nanoparticles are
to phosphate-based electrolytes for PEO coating of AM50 amorphous in the coatings.
alloys. It was stated that particle size was important in the Polytetrafluoroethylene (PTFE) is used in many industries
manner of particles contribution to the process. Higher final due to low friction, low chemical affinity, hydrophobicity and
voltage value in voltage–time plot of samples containing high corrosion and wear resistance [395]. PTFE particles were
nanoparticles in comparison with samples with microparticles added to an alkaline phosphate electrolyte in PEO coating of
and without any particles at all implies the lower electrical AM60B by Guo et al. [396]. It was reported that corrosion and
resistance of samples produced in the simple electrolyte. In wear resistance was incredibly increased by adding these par-
addition, microparticles did not affect roughness but surface of ticles. They also reduced friction coefficient. Water contact
sample with nanoparticles was smoother. Thickness values angle (CA) in samples with PTFE was 92–101 degrees which
of samples without particles, with nanoparticles and was considerably more than samples without PTFE particles.
microparticles were 45 ± 5, 25 ± 4 and 33 ± 3 µm, respectively. This can be stated as a major factor in reduction of corrosion.
In XRD analysis, SiO2 peaks were identified in samples with
6. Hybrid coatings with plasma electrolytic oxidation on
coarse particles. On the other hand, no SiO2 peak could be
magnesium alloys
found for samples with nanoparticles due to melting of fine
particles during the process. XRD results are shown in Fig. 51. Corrosion performance and tribological properties of mag-
The highest hardness and wear resistance was seen in samples nesium alloys such as friction coefficient and wear resistance
ARTICLE IN PRESS
treatment for 7h at 120 °C. It was also observed that corrosion

resistance in Hanks solution increased by 30 times after appli-
cation of a sol-gel film [300]. A sol-gel solution composed of
3-metacryloxypropyl trimethoxysilane (MEMO 10.4g), dis-
tilled water (4.9g), ethyl alcohol (15.8g Fulka 96%) and
butylhydroperoxide (1.9g Aldrich 99.7%) was used elsewhere.
Sol-gel films were sprayed onto the PEO-coated sample. Each
layer was cured for 24h at 70 °C except the last one which was
cured for 48 h. It was reported that application of additional
sol-gel films led to enhancement of corrosion potential and
wear resistance and also reduction of corrosion current density
[403]. Ge et al. [390] used tetraethoxysilane (0.1 mol) and dis-
tilled water as precursors, ethyl alcohol (20 ml) as solvent and
hydrochloric acid (1 ml) as catalyst to synthesize SiO2 sol on
PEO-coated samples. It was found that SiO2 film physically
sealed PEO film pores and improved corrosion resistance acting
Fig. 53. OCP variations against time in a 3.5wt% solution for PE (PEO+EN) as a barrier. In another research, PEO samples were immersed
and PSE (PEO+SANP+EN) [389]. into a 20% HF solution for 24h as a pretreatment to create silica
sol. Corrosion potential was reported to improve compared to
samples without any pretreatments [404]. Corrosion resistance
may be improved by application of ceramic coatings through improvement by applying SiO2 sols was also studied in other
PEO process. However, these coatings contain micro pores and work [405].
micro cracks [397] which are formed due to intense sparking
and gas evolution on sample surface [398,399]. Corrosive sub- 6.2. Electroless
stances can penetrate into the substrate through these defects Electroless deposition may be used to improve properties of
and corrode the underlying metal. There are many additional PEO coatings on magnesium alloys. EP is a cheap and easy
procedures to improve protection ability of PEO coatings [400]. technique to produce a uniform and wear resistant coating
[406]. Zeng et al. [407] electroless deposited PEO-coated
6.1. Sol-gel
AZ91D alloy using a bath containing NiCO3.2Ni(OH)2.4H2O,
Sol-gel which is known to be a clean, environmentally NaH2PO2.H2O, C6H8O7.H2O, CH3COONa, NH4HF2 and
friendly, inexpensive and readily prepared process has been NH3.H2O. It was seen that the amorphous EP Ni-P layer
used to improve corrosion resistance of anodized magnesium increased OCP from −1.57 V (in the uncoated sample) to
alloys [401]. In a research, SiO2-ZrO2 sol was used to create a −0.4 V (in the double-layer coated sample). Pitting corrosion
film on a PEO-coated AZ91D alloy. The sol-gel film was seen to resistance was significantly improved by forming the double-
cover the majority of the micro pores and micro cracks. In layer coating. Sealing effect of electroless Ni-P coating was
addition, the film physically sealed the surface so that corrosion confirmed in another study [408].
current reduced by two orders of magnitude. Corrosion poten- Electroless nickel plating is known to be an efficient method
tial also increased by 920 mV [302]. Impedance behavior of to improve corrosion resistance of PEO coatings on magnesium
coatings in simulated saline water was investigated elsewhere. alloys. However, galvanic corrosion between Magnesium alloy
Protection ability of PEO coatings reduced with increase in and Nickel, due to the existing pores in PEO coatings, remains
immersion duration; whereas, protection ability of double-layer an important issue in application of double-layer coatings.
coatings initially increased and then decreased [402]. The posi- Hence, formation of multi-layer coatings on PEO films is con-
tive effect of TiO2 sol-gel films on corrosion resistance of PEO- sidered. Self-assembled nano-phase particle technology
coated pure magnesium was confirmed [303]. Improvement in (SANP) is a new hybrid organic-mineral system which may
corrosion resistance was reported to be due to sealing of pores produce mineral silica nanoparticles in an aqueous sol-gel
by TiO2 which remained amorphous after a mild hydrothermal process [409–415]. The ability of these nanoparticles to diffuse
Fig. 54. Surface morphology of a) PEO film and b and c) double-layer coating [390].
ARTICLE IN PRESS
Potentiodynamic polarization curves showed that the corrosion

potential of PEO coated sample changed from −1.41 V to
−1.13 V after electrodeposition. Corrosion current density also
dropped from 4.276 µA.cm−2 to 2.521µA.cm−2. The electrode-
posited coating contained Ca3(PO4)2 and CaHPO4.2H2O [421].
6.4. Electrophoretic deposition
Poor corrosion resistance of PEO films which is an impor-
tant disadvantage may be corrected approximately by means of
electrophoretic technique [422]. Due to presence of an outer
porous layer in PEO coatings, electrophoretic deposition (EPD)
film may form a strong bond between the ceramic coating and
EPD film [142,423]. Jiang et al. [424] created a three-
micrometer electrophoretic film on a PEO-coated AZ91D alloy
using HED-5000 cathodic electrophoretic paints with electrical
conductivity of 1544 µs.cm−2 at pH of 5.9 and voltage between
Fig. 55. Dry friction behavior of various samples against a ball made of Si3N4 100 and 200 V for 1 to 4 mins. Uniformity of PEO film and
[391]. organic layer through physically interlocking was clear. Diffu-
sion of organic layer into pores of the PEO coating may be
observed in Fig. 54a. Potentiodynamic polarization showed that
into pores of PEO films has been confirmed [416,417]. Guo corrosion current density in the double-layer coating reduced
et al. [389] studied SANP application as an intermediary layer by three and two orders of magnitude compared to the uncoated
in electroless nickel plating on PEO-coated AZ31B alloys. AZ91D alloy and PEO coating, respectively. The existing pores
SEM micrographs and potentiodynamic polarization and EIS in the PEO coating were specified in Fig. 7c as A, B and C.
curves showed improvement of resistance against general cor- Coating adhesion reached level zero and 11.3N.mm−3 at rough-
rosion in triple-layer (PSE sample) and double-layer (PE ness of 0.2245 µm. Damping loss factor (DLF) of EPD coatings
sample) coatings in comparison with PEO coated and uncoated produced on PEO film was studied, elsewhere, in a positively
magnesium alloys. Protection against both long-term immer- charged particle bath where cathodic-type electrophoresis
sion corrosion and galvanic corrosion in the PSE sample were paints along with bi-components epoxy resins were used. DLF
better than the PE sample. of PEO/EPD coating was higher than that of uncoated magne-
According to Zeng et al. [418] and Fan et al. [419], combin- sium sample due to presence of epoxy resins with proper
ing anodic oxidation and EN plating may provide a better cor- damping ability [425]. Razavi et al. [426] formed EPD films on
rosion resistance compared with either of the techniques alone. PEO film using nano-structured diopside powders. In order to
It is necessary to mention that PEO films are not conductive and make the powders, the following routine was used. 0.125 mol
no catalytic activity occurs during EN plating process. There- MgCl2.6H2O and 0.125 mol Ca(NO3)2.4H2O were solved in
fore, the PEO film has to be activated by catalytic particles prior 150 ml ethanol. After stirring and heating, 0.25 mol Si(OC2H5)4
to this process. Song et al. [420] employed immersion in silver was added to the solution. The solution was dried after 24h of
ion ink for activation. SEM micrographs showed deposition of stirring and the remaining was powdered using a ball mill. PEO
silver nanoparticles on the PEO film in accordance to the fol- samples were placed into a solution containing 10g powder and
lowing equation: 100 ml methanol at 100 V. SEM micrographs of PEO and PEO-
55°C
diopside coated samples (after being exposed to SBF solution
2 AgNO3 (l ) → 2 Ag ( s ) ↓ +2 NO2 ( g ) ↑ +O2 ( g ) ↑ for 72h and 672h) revealed that the more intense corrosion
occurred in the PEO samples. This was also confirmed by
This step may be used to reduce process costs. Afterwards, potentiodynamic polarization curves. Wang et al. [427] studied
samples were immersed in Ni-B bath for 10 mins and then in adhesion and corrosion resistance of electrophoretic coatings
Ni-P bath for 90 mins. Electrochemical studies showed that the produced on PEO films. PEO-coated samples were placed in an
30-micrometer, dense, tight and continuous Ni-B/Ni-P coating electrophoretic bath containing 1.8wt% aluminum silicate,
on PEO film may favorably reduce the probability of galvanic 3.2wt% titanium dioxide, 17–25wt% epoxy resin and
corrosion between nickel and magnesium substrate. Besides, it 70–78wt% deionized water at 225 V for 2 mins. A perfect adhe-
improved adhesion between the EN coating and PEO film. sion between the two layers was created due to attachment of
E-coats with the pores on PEO coating surface. EIS and polar-
6.3. Electrodeposition
ization curves showed the better corrosion resistance of double-
Another method that is frequently used to improve PEO layer coating compared to the PEO film.
coatings properties is electrodeposition. In a research, an
6.5. Other techniques
AZ91D alloy sample which already been PEO coated was sub-
jected to electrodeposition in a solution bearing 0.06M Zhang et al. [428] performed two coatings processed subse-
NH4H2PO4, 0.1M Ca(NO3)2 and 10 ml.lit−1 H2O2 at 4 V for 2 h. quently by means of plasma electrolytic oxidation on AZ91HP
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Fig. 56. Surface morphology of magnesium after various treatments: a) UPEO, b) UPEO-NaOH (1 mol.lit−1), c) UPEO-NaOH (2 mol.lit−1), d) UPEO-NaOH
(3 mol.lit−1), e) UPEO-NaOH (1 mol.lit−1)-SCA, f) UPEO-NaOH (2 mol.lit−1)-SCA and g) UPEO-NaOH (3 mol.lit−1)-SCA [392].
alloys. The first electrolyte contained NaOH, H2O, KF and coatings which were already deposited on magnesium alloys
Na2SiO3.9H2O while the second electrolyte contained [399]. It was reported that corrosion resistance was signifi-
C6H18O24P6, HF, H3BO3 and hexamethylenetetramine. It was cantly improved after formation of an organic sealing layer
stated that the final coating had anions of the both electrolytes. (2–5 µm in thickness) on PEO coatings. This was due to diffu-
Deposition on the sample which was initially coated in solution sion of sealing agents into pores of PEO coatings and creation
No.2 and then in solution No.1 was, in fact, a competition of physical bonds. Consequently, it may be expected that fewer
between dissolution of the primary film and formation of the defects exist on surface of the double-layer film compared with
secondary film. Voltage and increase in mass over time plots the unsealed PEO coating.
showed that the older film dissolved in the critical stage of Liang et al. [391] formed duplex PEO/DLC coatings on
anodizing. The new film formed in 1 min. The whole process AM60B magnesium alloys by combining MAO and filtered
including dissolution of the primary film and formation of the cathode arc deposition. In fact, PEO layer was incorporated as
new film lasted 12 mins. an intermediate film to provide hardness and load capacity in
Multi-immersion techniques under low pressure was used magnesium alloys to produce Ti-doped films with approximate
elsewhere in order to form an organic sealing layer on PEO thickness of 1.5 µm. According to the results, duplex MAO/
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Fig. 57. SEM micrographs of a) WE42, b) WE42-PEO, c) WE42-PEO/PLLA and d) bending crack on the surface of the WE42-PEO/PLLA after 3 points bending
test [393].
DLC coatings considerably enhanced wear behavior of pores, Lu et al. [393] showed that duplex PEO/PLLA films on
samples. WE42 alloys may also provide suitable adhesion between the
Han et al. [429] used high-intensity pulsed ion beam coating and substrate. Alabbasi et al. [432] reported that appli-
(HIPIB) with ion current density of 200A.cm−2 and 1 to 5 shots cation of PLLA coatings on PEO films not only improves resis-
to improve corrosion resistance. SEM micrographs showed that tance against general corrosion, it also enhances local corrosion
a greater area was re-melted with increase in shot numbers. Yet, resistance. In fact, PEO/PLLA samples did not show any sign
re-melting due to HIPIB did not affect the existing phases. EIS of local corrosion after being exposed to simulated body fluid
results, however, indicated improvement of corrosion resistance (SBF) for 100h; whereas, local corrosion occurred in merely
caused by re-melting of the compact inner and top layers. PEO-coated samples after 48 h of exposure to SBF.
Silane treatment on metallic surfaces is among effective, Creation of a propolis layer on PEO films was studied else-
non-toxic, non-polluting, convenient and cheap techniques to where. The PEO coating produced on Mg-2wt% Zn-0.24wt%
be used for improving corrosion resistance [430]. Formation of Ca alloy was placed in a propolis-bearing solution. The process
a Silane layer on PEO-coated pure magnesium samples after was comparable to sol-gel deposition technique. Initially, 0.8 g
hot alkali pretreatment in solutions with different NaOH propolis was solved in 50 ml ethylacohol. This Bath was heated
concentrations was investigated. KH550 (γ-aminopropyl up to 40 °C. Then, 0.5 g polylactic acid was solved in 50 ml
triethoxysilane) as silnae coupling agent, ethanol and water choloroform and added to the propolis solution to increase
were used to form a layer on ultrasonic plasma electrolytic viscosity. The coated sample was placed into the solution and
oxidation films (volume ratio was 1:9:1). After alkali treatment, dried for three times. It was seen that the new layer formed on
samples were subjected to silane hydrolysis and then placed in the PEO coating effectively filled pores and hence improved
an oven to obtain the final cured films. According to SEM corrosion resistance [433].
micrographs, pores were filled better in samples that were pre- Increase in resistance against wear and corrosion was also
treated in solutions with high concentrations. Hence, corrosion obtained by application of (Ti:N)-DLC/PEO films on AZ80
resistance was also more improved [392]. magnesium alloys [434].
Poly-L-latic acid was used to improve corrosion resistance Today, magnesium alloys are widely used in body implants.
of PEO films by forming an extra layer similar to sol-gel tech- In vitro bioactivity may be improved by proper coating process
nique. It was observed that PEO/PLLA coatings on WE42 so that magnesium implants are protected against fast in
magnesium alloys improved corrosion resistance [431]. In addi- vivo corrosion and degradation [435,436]. Among silicate
tion to reduction of corrosion rate due to sealing of surface biomaterials which are known to be suitable for repairing bone
ARTICLE IN PRESS
tissues [437,438], akermanite (Ca2MgSi2O7) with adjustable position on phases, morphology and corrosion properties may
mechanical properties and corrosion rate has gained attention in be explained by contribution of electrolyte compounds in the
recent years. Use of nano-structured akermanite coating on coating and their effect on the governing electrical conditions.
PEO films was investigated by Razavi et al. [439]. They pro- Among electrical parameters, application of bipolar currents at
duced akermanite powder through sol-gel process in a solution high frequencies generally improves corrosion resistance. It
containing magnesium nitrate hexahydrate (Mg(NO3)2.6H2O), was also expressed that, almost in every case, application of
tetraethyl orthosilicate ((C2H5O)4Si, TEOS) and calcium nitrate PEO coatings led to considerable improvement of corrosion
tetrahydrate (Ca(NO3)2.4H2O). After drying of the solution, resistance. Tribological properties of coatings which mainly
residuals were ball-milled. The suspension required for electro- depend on the constituent phases were also discussed, although
phoretic process was obtained by addition of 10g nano- only a few studies were conducted in the field. Similarly, elec-
structured akermanite to 100 ml methanol. It was stated that trolyte composition was paid the most attention in literature. It
corrosion resistance and in vitro bioactivity of magnesium was reported that use of bipolar currents leads to better prop-
alloys improved after formation of the duplex coatings. There- erties of coatings.
fore, it can be used in manufacture of biodegradable bone It was revealed by studying biomedical properties of PEO
implants. films on magnesium that, porosity may have favorable or unfa-
Diamond-like carbon (DLC) films are known for their high vorable consequences. In fact, porosity is not desirable when
hardness and excellent wear and corrosion resistance. These high corrosion resistance is required. However, pores improve
films are applied on other types of materials to improve prop- growth of hydroxyapatite on surface and increase adhesion by
erties [440,441]. Also the possibility of achieving proper adhe- mechanical locking. It was also realized that different factors
sion between DLC films and magnesium alloys using an affect corrosion resistance of surfaces formed for biomedical
intermediary PEO layer was confirmed [442]. Yang et al. [443] purposes. These factors include operational parameters such as
synthesized (Si:N)-DLC coatings with Si3N4 on PEO-coated applied current density, applied voltage and deposition dura-
AZ80 alloys by means of ion beam deposition. Wear resistance tion. Besides, electrolyte chemical composition and post-
of coatings was reported to be higher than uncoated magnesium treatments influence corrosion resistance of coatings. Several
alloys. strategies have been proposed for improvement of corrosion
resistance and growth of hydroxyapatite on PEO-coated mag-
7. Conclusion and outlooks for future studies
nesium alloys. The strategies were mainly use of different addi-
The present article provides a comprehensive review around tives which improve growth of hydroxyapatite as well as
different properties, effective parameters and improvement corrosion resistance and also operation of post-treatments such
strategies regarding of plasma electrolytic oxidation films on as sealing and application of a second layer of hydroxyapatite.
magnesium substrates. Mechanisms of coating formation According to understandings obtained in the present work,
studied with different methods such as voltage–time plots, one may suggest some outlooks for future studies. It was men-
optical emission spectroscopy, acoustic emission spectroscopy tioned earlier that a comprehensive mechanism around forma-
and electrical properties measurement were discussed. Accord- tion of PEO coatings has not yet been proposed. Since
ingly, it can be stated that mechanism of PEO coating formation discharge phenomenon which occurs during the PEO process is
consists of complex thermo-chemical, electrochemical, chemi- a function of complicated mechanisms, exact and precise
cal and thermal processes. Oxide film formation, dissolution of research methods would be required in study of PEO coatings
primary film and gas evolution on anode surface constitute the formation mechanism. A future outlook, hence, can be mecha-
main processes in plasma electrolytic oxidation. The overall nism of PEO coatings fabrication study by precise methods.
mechanism of PEO coatings fabrication includes general anod- Regarding biomedical properties of PEO coatings on magne-
izing, spark anodizing, micro arc anodizing and arc discharge. sium substrates, it was observed that corrosion resistance of
In the beginning of the process, growth direction is mainly substrates improved by applying PEO films. However, the
outward; while, it then becomes dominantly inward. Studies on improvement is still not high enough so that coated pieces could
corrosion behavior of PEO coatings on magnesium alloys were be used for clinical biomedical purposes. Therefore, another
critically reviewed. Morphology, defects and chemical compo- outlook could be improvement of corrosion resistance through
sition are the most important factors in corrosion properties. other means. Authors believe that duplex PEO coatings may
Considering the significant effect of applying parameters in provide sufficient corrosion resistance for biomedical applica-
PEO deposition process on corrosion properties, it is essential tions. Yet, further study in the matter is inevitably required. It
to control these parameters in order to obtain coatings with was stated that second-layer coating methods may be employed
desirable properties. Effect of each parameter (including to improve corrosion resistance of PEO coatings for clinical
coating electrolyte, electrical parameters, process duration and applications. These methods improve corrosion resistance of
substrate condition) on corrosion properties, reasons of effec- PEO coatings through sealing of pores. However, evolution and
tiveness and proposed optimal conditions were addressed in a release of hydrogen weakens bonds between the PEO film and
separate sector. Electrolyte chemical composition is the most substrate which needs to be attended in future studies. Another
studied parameter and is known as the most important factor in issue is that most of implants are used in body joints where
achieving coatings with desirable properties. Due to the nature there is constant stress; however, most of studies that addressed
of PEO coating process, high effectiveness of electrolyte com- biomedical properties were carried out in normal situations.
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Plasma electrolytic oxidation of magnesium and its alloys: Mechanism,

Article · March 2017

Ghasem Barati Darband Mahmood Aliofkhazraei

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1. Introduction corrosive media [7–14]. A proper surface treatment may

3Mg 2 + + 2 PO43− → Mg3 ( PO4 )2 (8)

Fig. 4. Schematic of different approaches to study plasma electrolytic oxidation mechanism.

the beginning due to primary discharges which have extremely

Fig. 8. Schematic of the coating process during PEO treatment [73].

Fig. 14. Diagram of the development of microdischarge with a mobile liquid

are in accordance with Simescu et al. [86] Considering these

interface. Outward diffusion of magnesium ions along with

Fig. 17. Mott–Schottky plots of magnesium alloy AZ91D substrate in PEO

Fig. 19. Effective parameters in corrosion resistance of PEO coatings.

and KF by bipolar current mode. High polarization resistance

G. Barati Darband et al. / Journal of Magnesium and Alloys ■■ (2017) ■■–■■

Under constant voltage conditions: 375 V, frequency:

In addition, optimum values of parameters in the process

4.1.4. Effect of oxidation time on corrosion resistance

Mg-Al-Zn alloys is greatly dependent on aluminum content in

4.3. Biomedical properties of PEO coatings on magnesium

Fig. 36. Effects of various parameters on biomedical properties.

Fig. 42. Coatings surface morphology, a) uncoated magnesium and b) coated

growth increases at higher phosphate concentrations [287]. It

4.3.7.4. Post-treatment. Oxide films produced on magnesium

pores still existed on the surface after deposition of zirconia

used for the synthesis of MgO–Ag nanocomposite

Hap additive cause the better corrosion resistance

Improve in biological properties of MAO coating

the PEO process suggests that the process can be

Albumin act as inhibitor and improve corrosion

in SBF solution was observed with the sample deposited by a

Sol-gel treatments after PEO process to enhance coatings

improve corrosion resistance of PEO coatings, produced in a

enhanced corrosion resistance of magnesium in SBF solution.

Zhang et al. [301] fabricated PEO coatings in a phosphate-

Mg2SiO4, Anatase, Rutile,

coatings on implants [304–306], a TiO2 film was deposited on

the porous PEO coating by means of sol-gel immersion process

MgO, MgSiO3, and

and annealing in order to improve corrosion resistance and

reduce exposure to the SBF solution. It was revealed that

surface pores on PEO process were suitable sites for growth of

performance of alloy was enhanced. According to the obtained

Applied current density = 3, 5 A/dm2

current density to decrease down to one-third of the original

Frequency: 1000 Hz duty cycle:40%

Frequency: 600 Hz duty cycle:8%

applied voltage: 300 V

applied voltage: 400 V

applied voltage: 500 V

that deposition of electrolyte species in pores is controlled by

temperature and duration of process [31]. As an alternative for

alkaline solutions, sol-gel post-treatment can be used to reduce

thesized PEO coatings on AM50B and AM60B magnesium

alloys. In order to achieve better corrosion resistance, samples

were post-treated by immersion into alkaline phosphate and

silicate solutions as well as sol-gel to seal coating pores.