Surface & Coatings Technology 307 (2016) 484–490

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Surface & Coatings Technology

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Structure and corrosion properties of the two-step PEO coatings formed

on AZ91D Mg alloy in K2ZrF6-based electrolyte solution
Zeeshan Ur Rehman, Seong Hun Shin, Imad Hussain, Bon Heun Koo ⁎
School of Materials Science & Engineering, Changwon National University, Changwon 641-773, Republic of Korea

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

Article history: In this work, PEO (plasma electrolytic oxidation) coatings were produced on AZ91D magnesium alloy using two-
Received 13 June 2016 step PEO (plasma electrolytic oxidation) technique. Microstructure and phase composition of the two-step coat-
Revised 8 September 2016 ings were analyzed using SEM, and XRD, respectively. From the microstructural analysis, it was found that the
Accepted in revised form 15 September 2016
microstructural features of the primary coatings significantly influenced the properties of the secondary step
Available online 16 September 2016
PEO coatings. Further, it was found from the structural analysis that unlike the primary coatings, discharge chan-
Keywords:
nels in the secondary coatings are directional in nature. From the XRD patterns, major phases in the coating were
Two-step PEO coating detected as ZrO2, MgO and Mg2SiO4 along with some minor phases. Due to the excellent structural properties of
K2ZrF6 the coatings obtained through secondary step process, hardness and corrosion results of the coatings were signif-
AZ91D icantly improved. The highest corrosion resistance measured through potentiodynamic experiment was found as
Discharges ~505.3 × 103 Ω/cm2, with the hardness value for the same specimen as ~1170.24 HV.
Hardness © 2016 Elsevier B.V. All rights reserved.
Corrosion

1. Introduction
Since last decade, PEO is established as an effective method to pre-
pare protective coatings on light metals (Al, Mg, and Ti) and their alloys
which generally have poor corrosion resistance and wear properties [1–
5]. PEO also referred as micro-arc oxidation and spark anodizing is a
technique of producing ceramic coatings on the surface of light metals
using high voltage power in an electrolyte solution. Hard crystalline
oxide coatings are produced as a result of PEO processes due to the
high temperature of more than 1000 °C at local sites of the coatings.
PEO offers an attractive combination of wear resistance, corrosion resis-
tance, mechanical strength, interfacial adhesion, and thermal properties
[6–9].
However, the coatings produced by PEO process are usually coarse
and porous, which degrade their tribological and corrosion perfor-
mance. In addition, to obtain PEO coating with excellent properties usu-
ally long processing time is needed which considerably increase the
ultimate cost of the product. Therefore, in order to cope with the short-
comings of the PEO coatings exploring new techniques remained the
persistent demand of the researchers.
Until now several post-PEO coating methods have been applied to
enhance the corrosion and other related properties by improving the
structural aspects of the coatings. For instance, sol-gel technique, dip-
ping process, electrodeposition, electrophoretic and electroless
⁎ Corresponding author.
E-mail address: bhkoo@changwon.ac.kr (B.H. Koo).
deposition techniques are a few among the others that were applied
for the depositing secondary layer on the coated substrate [10–18].
However, the aforementioned post-PEO techniques were primarily
aimed at sealing the defects-like pores and cracks of PEO coatings
with a very thin and weak top finishing layer. It was noticed that by ap-
plying such methods, mechanical properties of the coating surface were
significantly affected.
Therefore, a few research groups adopted a new approach called
two-step or sequential PEO method to obtained hard and non-porous
top layers on the primary PEO coatings while minimizing the total pro-
cessing time as much as possible. Two-step PEO approach was primarily
used by researchers to understand the transport and coating growth
phenomena during the PEO process [19–22]. However, recently several
authors have reported significant improvement in the coating micro-
structure and corrosion protection of the substrate material by using
two-step PEO process. For instance, Kang et al. investigated the micro-
structural characteristics of the sequential coatings and deposited
Mg2Zr5O12 and ZrO2 based secondary coatings on AZ91 alloy using acid-
ic K2ZrF6 electrolyte solution [23]. Likewise, Tsunekawa et al. carried out
the two-step coating on titanium alloy in acidic K2ZrF6 solution for 100 s
and found that porosity and mechanical properties were significantly
enhanced with second step process [24]. Furthermore, Feryar et al.
treated AZ31 magnesium alloy in acidic K2ZrF6 based electrolyte solu-
tion and recorded large increase (244 Ω/cm2 → 141 K Ω/cm2) in the cor-
rosion resistance [25].
Although these handful reports about two-step coatings on magne-
sium and other alloys predicted the enhancement of anticorrosion and

http://dx.doi.org/10.1016/j.surfcoat.2016.09.030
0257-8972/© 2016 Elsevier B.V. All rights reserved.
 Z.U. Rehman et al. / Surface & Coatings Technology 307 (2016) 484–490
mechanical properties, However effect of various additives, alkalinity,
processing time and various other phenomena involve in the two-step
coating are still needed to be investigated.
Consequently, in this work, two-step PEO process was carried out on
AZ91D specimens under an optimized hybrid voltage. AZ91 samples
were first coated in alkaline silicate solution for various processing
time. The as prepared samples were than processed in the K2ZrF6-
based electrolyte solution for constant processing time. The present
work investigates the effect of the initial processing time on the struc-
ture, mechanical and electrochemical properties of the two-steps PEO
coating.
2. Experimental details
2.1. Specimens pre-treatment and electrolytes
Commercial AZ91D (Al 9.1 wt.%, Zn 0.85 wt.%, Mn 0.27 wt.%,
Fe ≤ 0.02 wt.%, others ≤ 0.01 wt.%, Mg balance), was cut into coupons
of working area ~ 9.5 cm2. Before the PEO process, samples were
polished with SiC paper (up to grade 2000) followed by washing in de-
ionized water and decreasing in ethanol. Two different electrolytes
were used in the experiment respectively named as solution-1 and so-
lution-2. Solution-1 was composed of N2SiO3·10H2O 12 g/l, NaOH
3.5 g/l, Na2SiF6 0.3 g/l, and solution-2 was composed of K2ZrF6 6 g/l,
Na2SiO3·10H2O 12 g/l, NaOH 3.5 g/l, Na2SiF6 0.3 g/l.
2.2. PEO coating deposition by primary and secondary step
The PEO process was conducted by means of an external power sup-
ply with a maximum power of 20 kW, under hybrid voltage source of
200 AC and 260 DC volts for various time intervals. Voltage was main-
tained constant while current was allowed to vary through the experi-
ment. Primary step coating was carried out in a solution-1 while the
secondary step process was carried out in solution-2. In the primary
step, specimens were put into the solution-1 for 5, 15 and 30 min oxida-
tion. Consequently, the coated specimens were referred as P1, P2 and
P3. The samples were than taken out from solution-1, for cleaning and
drying. In the second step, all the specimens P1, P2, P3 were oxidized
in solution-2 for constant 10 min duration. The corresponding
Primary (a) 5min
Coating
Post PEO (d) 10min
Coatings
Fig. 1. Surface morphology of coatings a–c) primary step coatings in solution-1, d–f) secondary step coating in solution-2.
485
secondary step coatings were referred as PP1, PP2 and PP3 respectively.
Temperature of the both the electrolyte solutions was maintained
below 25 °C during the process by adjusting a cool water flow.
2.3. Coating characterization
Phase composition of the coatings was investigated by means of X-
ray diffraction (XRD), using Cu Kα source. Microstructure of the surface
and cross sections of the samples was examined by scanning electron
microscope (SEM). Porosity and pore size of the coating were obtained
from the microstructure of the coatings using ImageJ analysis software.
Hardness of the coatings was measured on 10 different places by a
VLPAK2000 Mitutoyo hardness test machine using Vickers-type indent-
er under constant loading/unloading rates of 0.025 mN/s with holding
time of 5 s at maximum load.
Electrochemical corrosion test of the PEO-coated specimens was
performed by Solartron Electrochemical Testing System (1280B) with
a conventional three electrodes; Ag/AgCl electrode as reference and
platinum plate as a counter electrode. Samples as working electrode
were immersed into the electrolyte of 3.5 wt.% NaCl. Potentiodynamic
polarization test was conducted from 4.0 V below the OCP to 2 V
above the OCP at a scan rate of 1 mV/s. The specimens were mounted
in the electrochemical cell so that the surface area (0.75 cm2) could be
contacted with the test solution. Corrosion potential and corrosion cur-
rent density were obtained through the linear analysis of Tafel approx-
imation using IVman Tafel analysis software. All the experiments were
carried out at room temperature.
3. Results and discussion
3.1. Microstructure
Fig. 1(a–f) shows surface morphologies of the coatings formed by
the primary and secondary step PEO process. The surface of the primary
step coatings (P1, P2, and P3) has numerous pores, cracks and nodules
distributed randomly through the surface area. Most of these pores
are located at the centers of the pan-cake structures.
The lowest average pore size was recorded for P1 and PP2 as
shown in Fig. 2a. The individual pore size for P1 was lying in the
(b) 15min (c) 30min
Craters
(e)10min (f)10min
Craters
486 Z.U. Rehman et al. / Surface & Coatings Technology 307 (2016) 484–490
Fig. 2. a) Individual pore size of the primary and second step PEO coatings b) porosity of the primary and second step PEO coatings c) crater size of the primary and second step PEO
coatings.
range of 4.4–26.2 μm which was decreased to the range of 9.0–17.3 μm
after secondary step. Likewise, the pore sizes for P1 and P2 was lying in
the range of 6.1–30.5 μm and 7.1–30.4 μm respectively. After secondary
step the size of the pores in P2, P3 reduced to the range of 6.0–22.2 μm
and 8.5–13.6 μm for PP2 and PP3 respectively.
The decrease in the pore size after secondary step occurred due to
the excellent blockage of the discharge channels by the coating material.
However, the average area covered by these pores is even more impor-
tant than the individual pore size. The area occupied by these pores (po-
rosity) is shown in Fig. 2b. It can be seen that 5.6% of coatings area is
occupied by the pores in P2 specimen, however the porosity decreases
to 1.2% after secondary step. This suggests the significant influence of
the primary coatings structure on the structural features of the second-
ary step coatings. This can be attributed to the fact that the surface out-
lets of the discharge channels in the primary coatings, offer immediate
and directional routes to the plasma species produce in the secondary
step. Contrary to the metastable discharge channels in the primary coat-
ings produced by the repeated micro-arcs, here in case of secondary
process the existing stable discharge channels through the primary
coatings provide an easy and stable medium for the electrolyte and sub-
strate species to react as illustrated in Fig. 4(a, b). That's why the poros-
ity decreases with secondary step process after repeated sintering
process of the coating material in the discharge channels. In addition
Primary (a) 5min
Coating
Post PEO (d) 10min
Coatings
Fig. 3. Cross-section morphologies of the coatings prepared (a–c) primary step coating in solution-1 (d–f) secondary step coating in solution-2.
to the structural features, the choice of electrolyte in the secondary
step process has also a significant influence on the final coating struc-
ture. For instance, Arrable et al. obtained coating porosity ~30% using
phosphate and silicate-based electrolyte in the secondary process
while Zang et al. obtained significant decreased in the porosity by
using fluoride-based electrolyte solution in the secondary process [20,
19]. Therefore, decrease in the porosity and defects can be credited to
the secondary step process as well as the choice of electrolyte
composition.
Furthermore, it can be observed from Fig. 2c that the size of the pan-
cakes (craters) significantly increased after secondary step coatings. The
crater size for the primary coating was in the range ~ 34.5–58.6 μm
which increased to the values in the range ~69.4–81.0 μm. The largest
crater size was recorded for PP2 coating. Since PP2 was obtained by sec-
ondary step coating on the highly porous coating P2. Coating with such
high porosity as mentioned earlier could allow the uniform occurrence
of micro-arcs and flow of transport species across the primary coating.
Such a stable and uniform flow of coating material caused efficient
sintering and the formation of larger craters.
Besides this, the secondary coating on P3 cause increases in the pore
size and porosity in the PP3 coating as can be seen in Fig. 1f. This can be
attributed to the blocking effect of primary thick pre-layer. The primary
P3 coating due to high thickness could not allow the transport species
(b) 15min (c) 30min
(e) 10min
(f) 10min
AZ
 Z.U. Rehman et al. / Surface & Coatings Technology 307 (2016) 484–490 487

Discharge sparks

Discharge channels
(a) Substrate

Primary coating pores

(b)

Fig. 4. Schematic illustration of the discharges in a) primary step and b) secondary step coatings.

effectively and thus causes intensive and unstable discharges. As a result
of such a violent and intensive process, coating material possibly could
not be able to fill up the large size pores.
Cross sections of the primary and secondary coatings are shown in
Fig. 3(a–f). Evidently, the secondary coatings have two layers structure,
the outer and the inner layer. The outer and inner layers are produced
by the secondary and primary step process respectively. A line is
drawn to clarify the inner and outer layer.
Thickness of both outer and inner layers is shown in Fig. 5b. The
outer layer is thicker than the inner layer for all coatings, suggesting
the effectiveness of the secondary step process. It is believed that unlike
primary coatings where the discharge channels originated randomly,
discharge channels in the secondary step process are patterned by the
pore network in the primary coatings. Therefore, the discharge channels
grow in a directional pattern instead of a randomly dispersed way. Un-
like the primary coatings, there cannot be seen any connected or
branched discharge channels in the secondary step coatings as illustrat-
ed in Fig. 4(a, b). Notably, PP2 has the largest outer layer thickness. This
can be attributed to the highly porous P2 coating that provides large
number of stable transport routes to the electrolyte and magnesium
ions to react during the secondary process. The fixed and defined
discharge channels (enclosed by the squares in Fig. 3(d, e, f)) causes ef-
ficient electrochemical and physiochemical process, with excellent
growth rate as for PP2 specimen. However, the porous surface layer of
the primary coating can be easily damaged by the secondary coating
and thus led to a decrease in the inner layer as reported by Zhang et
al. [19]. Due to the well-ordered second step process, the outer layer
has dense structure than the inner layer, which is in agreement with
the results reported by R. Arrable [20]. However, due to the large thick-
ness of the P3 coating, the electrolyte species and substrate could not
find continuous transport medium, as a result, violent and random reac-
tion initiates which damage the inner layer as seen in Fig. 3f.
The average thickness of the primary coatings and secondary coat-
ings is shown in Fig. 5a. It can be seen clearly that the secondary step
coatings have high thickness values than the primary step coatings.
Though the primary step and secondary step coatings have a difference
in processing time, however, nature of the process is more important at
this point. For instance, P2 with PP1, was treated for the same period of
time, however, PP1 have maximum thickness value, due to the second-
ary step process. Thus, it can be infer that the secondary coatings have
superior growth properties than the primary step process subject to
the optimum process conditions.

Fig. 5. Inner and outer layer thickness of secondary coating. b) Average thickness of primary step and second step coatings.
488 Z.U. Rehman et al. / Surface & Coatings Technology 307 (2016) 484–490

3.2. Phase analysis

Fig. 6 shows XRD pattern of the secondary PEO coatings, produced

on samples (P1, P2 and P3). XRD peaks were identified using high
score plus software. All the patterns primarily, include peaks of Mg,
ZrO2, MgF2, Mg2SiO4 and MgO. The MgO peak is relatively stronger
than any other peak, suggesting the maximum amount of the respective
phases. From the XRD pattern, it can also be observed that the intensity
of silicate and zirconate peaks is decreased for PP3 specimens. This ob-
servation qualifies the findings of structure analysis where it was ob-
served that PP3 has significant defects in the inner layer. The absence
of coating material due to defects and cavities in PP3 leads to decrease
in the intensity. Furthermore, the presence of ZrO2 and MgF2 peaks in
the coatings confirms the involvement of K2ZrF6 in the thermo-chemi-
cal reactions during the secondary PEO process. The possible mecha-
nism for the formation of Zr-F-O-Mg complexes can be interpreted as
follows, at first, the reaction between K2ZrF6 and NaOH occurs in the
electrolyte:

K2 ZrF6 þ 4NaOH→ZrðOHÞ4 þ 2KF þ 4NaF ð1Þ Fig. 7. Hardness of primary and secondary step coating.

Zr(OH)4 is the colloidal particle, whose isoelectric point is 6.8, which

means that Zr(OH)4 is electropositive of the form (ZrO2+, [ZrO(OH)]+ SiO2 þ 2MgO→Mg2 SiO4 ð8Þ
etc.), for the electrolyte pH b 6.8, and Zr(OH)4 is electronegative of the
form ([ZrO(OH)3]−, [ZrO(OH)4]2 − etc.) for the electrolyte pH N 6.8 Mg2þ þ 2 F−1 →MgF2 ð9Þ
[26]. Due to highly alkaline electrolyte solution (pH N 12) used in this
experiment, Zr(OH)4 colloidal particle have electronegative forms. Since all quantity of the K2ZrF6 cannot be converted to colloidal par-
There electronegative particles move toward the anode surface because ticles Zr(OH)4, therefore, the direct decomposition of the K2ZrF6 could
of the strong electrical field between anode and cathode, where several also provide the way for ZrO2 formation. The following reactions repre-
chemical reaction occurs as presented below [27,28]. sent the formation of ZrO2 through the direct decomposition of the
K2ZrF6.
ZrðOHÞ4 →ZrO2 þ 2H2 O ð2Þ
K2 ZrF6 →2 Kþ þ ZrF6 2− ð10Þ
The formation of MgF2 and Mg-Si-O based complexes are simply oc-
curred from the direct and indirect reaction of the anion and cations due ZrF6 2− þ 4OH− →ZrO2 þ 6F− þ H2 O ð11Þ
to high temperature and electric field. The possible reactions are as
under [29,30].
3.3. Hardness
Mg2þ þ 2OH− →MgðOHÞ2 →MgO þ H2 O ð3Þ
Hardness profile of the coatings is shown in Fig. 7. The hardness of
2− þ the coatings can be related to intrinsic (bonding strength) as well as ex-
SiO3 þ 2H →SiO2 þ H2 O ð4Þ
trinsic properties (structural properties). As discussed earlier, the outer
layer of the coating after the secondary step is very dense and almost
SiO3 2− →O2 þ 2SiO2 þ 4e− ð5Þ
free of defects. Such promising structural properties can be attributed
to the improved hardness values of the secondary step coatings. In addi-
2SiO3 2− þ 2Mg2þ →Mg2 SiO4 þ SiO2 ð6Þ
tion, the presence of zirconia-based phases considerably added to the

SiO3 2− þ 2Mg2þ þ 2OH− →Mg2 SiO4 þ H2 O ð7Þ

Fig. 6. X-ray diffraction patterns of primary and second step coated AZ91 Mg alloys. Fig. 8. Potentiodynamic polarization curves of primary and secondary step coating.
 Z.U. Rehman et al. / Surface & Coatings Technology 307 (2016) 484–490 489

Table 1
Potentiodynamic polarization results of the primary and secondary coatings on AZ91D.

Coating codes Processing time (min) βa βc Ecorr Icorr Rp

(mV/dec) (mV/dec) (V) (A/cm2) (Ω/cm2)

Bare-AZ91 48.9 108 −1.53 75E−6 195.12

P1 One step (5 min) 40.4 73.8 −1.39 904E−9 12.5 × 103
P2 15 min 47.3 67.4 −0.97 281E−9 42.90 × 103
P3 30 min 44.7 50.6 −0.46 62.4E−9 165.22 × 103
PP1 Two step (10 min) 43.8 42.7 −0.73 935E−9 10.04 × 103
PP2 – 42.2 55.5 −0.29 60.8E−9 172 × 103
PP3 – 29.6 43.2 −0.34 15.1E−9 505.3 × 103

hardness of secondary step coatings. From Fig. 7 hardness of the PP1
specimen, with a total processing time of 15 min is measured as
1170.24 HV which is double to that of P2, prepared for the same pro-
cessing time, however through one step process only. The highest hard-
ness was measured for PP2 (primary coating time = 15 min, secondary
coating time = 10 min). The highest hardness values of the PP2 speci-
men can be attributed to the defects-free outer and inner layer struc-
ture. The snaps of the Vickers indentations are shown in Fig. 7, with
their respective measurements. It can be observed carefully that the in-
dents on the PP3 and PP1 caused the material removal and crack respec-
tively. However, the indents on the PP2 coating have no crack or other
effects suggesting the excellent bonding qualities and densification
properties of the coating formed on PP2. Furthermore, from the hard-
ness graph, it can be observed that as the primary step processing
time increases the difference between the hardness of the primary coat-
ings and secondary coatings decreases. This could be possible due the
defects produced in the inner layer after secondary step coatings on a
long time primary coatings as discussed earlier. Therefore, to control
the defects in the inner layer and obtain high hard coatings, primary
processing time must be limited to 15 min in further experimental
work.
3.4. Corrosion properties
Fig. 8 shows potentiodynamic polarization curves of the specimens
for one and two-step PEO coatings in 3.5 wt% NaCl solution. Corrosion
potential (Ecorr), corrosion current density (Icorr), and anodic/cathodic
Tafel constant (βa and βc) were derived using IVMAN 1.3 Tafel analysis
software. All the resultant corrosion parameters are given in Table 1. In
general, the high corrosion potential and/or low corrosion current den-
sity indicates superior anti-corrosion properties. To compare the speci-
mens in detail, corrosion potential (Ecorr = 1.53 V) and corrosion
current density (Icorr = 75.01 μA/cm2) of the uncoated AZ91D substrate
were also measured as shown in Fig. 8, this is similar to those found in
the literature. Generally, a significant increase in the corrosion resis-
tance of all the coatings was recorded. However, samples with second-
ary step coatings were found to have the highest corrosion resistance.
Corrosion potential (Ecorr) of P1 was ~− 1.39 V, while after secondary
coating a significant increase the corrosion potential was recorded
equal to ~− 0.73 V. Similarly, Ecorr of P2 was improved from − 0.97 V
to −0.28 V. This substantial increase in the corrosion potential of the
specimens after secondary step suggests the efficient blocking role of
the secondary coatings. The secondary coatings due to their high com-
pactness effectively resisted the flow of corrosive solution to reach the
substrate surface. From the polarization curves, it can be examined
that Ecorr for PP3 is slightly decreased. This might happen due to the
large internal cavities that allowed the corrosion solution to initiate cor-
rosion. In addition, as reported elsewhere, corrosion is considerably in-
fluenced by the phase distribution of the coatings. Hence, the presences
of stable species such as MgF2 and ZrO2 in the coating layers contributed
to prevent corrosion by resisting against thermochemical corrosion pro-
cess. Furthermore, by careful inspecting the polarization curves of spec-
imens P1, P2, P3, there exit current oscillation in the anodic branch
(encircled). Such oscillations are caused by the passivation re-
passivation due to pitting corrosion. However, there can be seen no
such oscillation in the anodic curves of the specimens PP1, PP2, PP3 ver-
ifying the absence of pitting corrosion in the secondary step coatings.
Highest corrosion resistance was found for PP2 equal to ~505.3 Ω/cm2
which is 4 times higher than corrosion resistance reported by Feryar
et al. [25]. The excellent corrosion properties of the PP2 sample can be
attributed to the dense structure and defects-free coating layers as
discussed earlier. Obviously coating with such a high corrosion resis-
tance will impart significant protection properties to the AZ91 magne-
sium alloy.
4. Conclusion
Two-step PEO coatings were formed successfully on AZ91 magne-
sium alloy in K2ZrF6-Na2SiO3·10H2O-based electrolyte solution. The
surface porosity was significantly reduced by the second step coatings
from 5.6% to 1.2%. The discharge channels due to the secondary step
process were found to be initiated from the pores and weak zone on
the primary coating surface. From the phase analysis, MgF2 and ZrO2
phases were identified in the second step coating, together with MgO
and Mg2SiO4 phases. Highest hardness ~1170.24 HV and corrosion re-
sistance ~505.3 Ω/cm2 were found for the sample with primary coating
time ~15 min and secondary step coating time ~10 min. Further, it was
observed that the second step coating on thick primary coatings
(30 min) could damage the primary coating layers and thus result in
the deterioration of the coating properties. Therefore, to obtain coating
with excellent properties the total optimum time for further experi-
ments is suggested as 25 min (primary step = 15 min, secondary
step = 10 min).
Acknowledgments
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIP) (No.
2011-0030058).
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