Corrosion Science 173 (2020) 108741

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Sealing of PEO coated AZ91magnesium alloy using solutions containing T

neodymium
Luca Pezzatoa,*, Riccardo Babbolina, Pietrogiovanni Cerchiera, Marco Marigoa, Paolo Dolcetb,
Manuele Dabalàa, Katya Brunellia,c
a
Department of Industrial Engineering, University of Padua, Via Marzolo 9 35131 Padova, Italy
b
Department of Chemical Science, University of Padua, INSTM, UdR Padova and ICMATE-CNR, Padova, Italy
c
Department of Civil, Environmental and Architectural Engineering, University of Padova, Via Marzolo 9, 35131 Padua, Italy

A R T I C LE I N FO A B S T R A C T

Keywords: In this work, PEO coatings were produced on AZ91 magnesium alloy, and a sealing treatment was successively
Plasma electrolytic oxidation performed with solutions containing Nd sulfate salt, recovered by magnets scraps, to produce a Nd-based con-
Sealing version coating on the surface.
Magnesium alloy For PEO process was employed a basic solution containing both silicates and phosphates as electrolyte, and
Neodymium
high current densities (0.5 A/cm2) and short treatment times (2 min) were used. Different parameters were
Recovery
tested for sealing treatment. In detail, the concentration of the salt (6 or 12 g/l of NaNd(SO4)2) and the effect of
Conversion coating
H2O2 as accelerant were investigated. The conversion coating was produced by simple immersion in the Nd
sulfate salt solution, maintained at 50 °C for 30 min. The thickness, composition and morphology of the obtained
coatings were analyzed with SEM-EDS, XRD and XPS, whereas the corrosion performances were evaluated with
potentiodynamic polarization, EIS and OCV decay tests. An oxide ceramic coating of about 20 μm thick resulted
and all the samples treated with sealing process showed an increase in the corrosion resistance depending on the
salt concentration. Moreover, the addition of hydrogen peroxide, which acts as accelerant in the formation of the
protective layer, allowed to obtain the best results, decreasing the corrosion current density of the sealed samples
of two orders of magnitude, in comparison with the untreated ones and producing a sealing layer on the surface
more uniform and adherent to the substrate. The increased corrosion performances of the sealed samples can be
due to the sealing of the pores that characterized PEO coatings and to the presence in the external layer of
protective compounds such as Nd2O3, as evidenced by XRD and XPS.

1. Introduction functionalization of the coating with proper compounds [5]. In PEO

One of the main problems limiting the industrial application of
magnesium alloys is the poor corrosion resistance caused by the high
chemical activity of magnesium and by the characteristics of the natural
oxide film on its surface [1]. In order to enhance the corrosion prop-
erties of magnesium alloys a lot of surface treatments can be performed
and, among these, Plasma Electrolytic Oxidation (PEO) is one of the
most promising. Studies on PEO technology started since the 1970 and
in the last two decades PEO found several applications in the field of
surface engineering [2]. Nowadays, PEO is a consolidated surface
treatment to improve the corrosion and wear resistance of magnesium
alloys and the research is focusing on the definition of the best elec-
trolyte to maximize the corrosion resistance [3], on the use of the
coatings on biodegradable magnesium alloys [4] and on the
process, as described by Barati Darband et al. [6] a plasma discharge
occurs leading to the partial fusion of the oxide film and, consequently,
to the formation of an extremely adhesive oxide coating on the sub-
strate. PEO process derived from traditional anodizing, working with
the same experimental setup, but the oxide layer is formed at higher
voltages and current densities. The main advantages in the use of PEO
in comparison with traditional anodizing are, as stated by Blawert et al.
[7]: the increased corrosion and wear performances of the samples and
the more environmental friendly nature of the electrolyte.
However, PEO coatings are characterized by high porosity, as ex-
plained by Curran and Clyne [8]. This porosity usually does not allow
obtaining good protection against corrosion, and a sealing treatment is
always necessary to acquire on PEO samples an acceptable resistance
against corrosion. The sealing treatment can be performed in different

⁎
Corresponding author at: Via Marzolo 9, 35131 Padova, Italy.
E-mail addresses: luca.pezzato@unipd.it, lucapezzato@virgilio.it (L. Pezzato).

https://doi.org/10.1016/j.corsci.2020.108741
Received 15 July 2019; Received in revised form 29 January 2020; Accepted 11 May 2020
Available online 21 May 2020
0010-938X/ © 2020 Elsevier Ltd. All rights reserved.
L. Pezzato, et al.
ways: with simple boiling water, with particles to functionalize the
coating giving to it some particular properties, such as antibacterial or
antifouling properties, as described by Cerchier et al. [9,10], or also
performing conversion treatments on the surface in order to introduce
in the coating compounds that can increase the corrosion resistance. In
literature can be found examples about sealing the pores of PEO coat-
ings with rare-earth based conversion coatings: Pezzato et al. [11]
proposed a La-based sealing treatment and found that the La(OH)3
protective layer increased the corrosion resistance of the samples;
Mohedano et al. [12] and Mingo et al. [13] studied a Ce-based sealing
treatment and the results showed an increase in the corrosion proper-
ties of the sealed samples thank to the presence of CeO2 and Ce2O3.
Mohedano et al. [14] found than the accumulation of CeO2 on the
surface of PEO coated LPSO Mg-Y-Zn alloy partially blocked the coating
pores and cracks, improving also the passivity of PEO layer.
As a matter of fact, rare-earth based conversion coatings were
widely studied in literature and usually are applied to the magnesium
alloy substrate by simple immersion in the solution containing the salt,
at proper temperature and with proper additives. For example, Rudd
et al. [15] found that the immersion of magnesium alloy in cerium,
lanthanum and praseodymium-containing solutions led to a significant
increase in the corrosion resistance of magnesium in a pH 8.5 buffer
solution. Yang et al. showed that the immersion in La(NO3)3 solution
produced a coating that provided good corrosion protection on the
Mg–8Li alloy [16] and the immersion in a mixed solution of La(NO3)3
and Na2MoO4 increased remarkably the corrosion resistance of AZ31
magnesium alloy [17]. Lin et al. [18] obtained a dual Ce-La rare-earth
film that improved the corrosion resistance of AZ63 magnesium alloy.
However, large part of the works reported in literature employed
solution containing Ce or La, whereas only few works reported the
possibility to produce Nd-based conversion coating on magnesium al-
loys. In detail, Jin et al. [19] produced a conversion coating on AZ91
alloy using solution containing Nd(NO3)3 and H2O2 obtaining a
4−5 μm thick coating that increased the corrosion resistance of about
one order of magnitude. Cui et al. [20] obtained similar results on AZ91
magnesium alloy employing a Nd(NO3)3 solution and obtaining a dry-
mud coating, mainly composed by Nd2O3. Also Zhao et al. [21] ob-
tained a Nd2O3 coating, with the typical dry mud morphology that
improved the corrosion properties of AZ31 alloy; moreover, they de-
scribe the role of H2O2 as accelerating agent, providing OH− groups
that can be employed during the formation of the coating.
As described, all the researches focused on the use of Nd nitrates to
produce conversion coating, whereas the use of neodymium sulphates
solution in production of conversion coatings was never reported in
literature and no works regarding the use of Neodymium-based solu-
tions to seal the pores of PEO coatings can be found. Moreover, con-
sidering the fact that rare earths metals supply is critical, the use of
Neodymium sulphates, recovered from permanent magnets scraps, to
produce conversion coatings can be very useful in an idea of circular
economy.
In this work, a Nd-based sealing post-treatment, performed starting
from neodymium sulphates solution (recovered from permanent
magnet scraps), for PEO coatings deposited on AZ91 magnesium alloy
was developed. The corrosion properties and the surface modification
produced by the sealing process on the PEO treated samples were in-
vestigated.
2. Experimental
AZ91 samples (nominal composition reported in Table 1) were used
as substrate for PEO coatings.
Standard metallographic techniques were applied to polish the
samples before the PEO treatment with a grinding step with abrasive
papers (500, 800, 1200 and 4000 grit) and a polishing step with clothes
and diamond suspensions (6 μm and 1 μm). After the polishing step the
samples were degreased using acetone in ultrasound. Polishing was
2
Corrosion Science 173 (2020) 108741
Table 1
Chemical composition of AZ91 magnesium alloy (wt%).
Mg Al Zn Si Mn Fe Cu
90.8 8.5−9.5 0.45−0.90 0.35 0.18 0.014 0.003
performed in order to uniform the superficial conditions of each sample
before PEO treatment. The electrolyte employed in the PEO process was
constituted by an aqueous alkaline solution containing 50 g/l of
Na2SiO3, 40 g/l of NaOH and 50 g/l of Na5P3O10.
A TDK-Lambda DC power supply of 400 V/8 A capacity was used for
the PEO treatment. During the treatments, the substrate worked as
anode and the cathode was a carbon steel mesh. Treatments were
performed in galvanostatic mode working at high current densities for
short treatment times. In detail, the current density was fixed at 0.5 A/
cm2 and the samples were treated for 2 min. The composition of the
electrolyte and the electrical parameters employed in PEO process were
chosen, in accordance with previous work of the authors [11], in order
to obtain a coating about 20 μm thick. Deionized water was employed
to wash the samples after the treatment. The samples were successively
dried with compressed air. The sealing treatment was performed
leaving the sample in an aqueous solution containing Nd salts at 50 °C
for 30 min and testing different conditions. In detail, NaNd(SO4)2, with
the concentration of 6 g/l and 12 g/l was used. The effect of addition of
20 mL/L of H2O2 to the sealing solutions was also investigated. Bath
composition and concentration were chosen on the base of literature
works that employ neodymium nitrate as precursor salt [19,20]. Hy-
drogen peroxide was added as accelerant for the reaction, and the de-
position process follows the model proposed by Zhao et al. [21]: there is
an initial stage with the reactions 1–3 and a second stage where the
reactions 4 and 5 occur with the formation of the Nd conversion layer.
In fact, considering that the solubility product of Nd(OH)3 is lower than
Mg(OH)2 when the solution is rich of OH− ions, Nd(OH)3 precipitates
from the solution and deposits on the surface of magnesium alloy. The
drying process produces the transformation of Nd(OH)3 in Nd2O3 that
constitutes the conversion layer.
Mg → Mg 2 + + 2e− (1)
2H2 O + 2e− → H2 ↑ + 2OH− (2)
H2 O2 + 2e− → 2OH− (3)
Nd3 + + 3OH− → Nd (OH )3 ↓ (4)
Mg 2 + + 2OH− → Mg (OH )2 ↓ (5)
The NaNd(SO4)2 was recovered by NdFeB “end of life” permanent
magnets by a process that allowed to obtain a high purity salt. First the
magnets were leached in H2SO4, and subsequently, by adding NaOH to
the leaching solution, the salt precipitated. The obtained precipitate
was washed in alcohol and then dried at 60 °C. The XRD-analysis evi-
denced the presence of Nd salt, in the form of NaNd(SO4)2 %H2O
Fig. 1. X-ray diffraction patterns for NaNd(SO4)2%H2O.
L. Pezzato, et al. Corrosion Science 173 (2020) 108741

(Fig. 1). Nd salt was chosen rather than other rare earth salts with the
purpose of re-using this recovered compound, considering that rare
earths are considered critical elements for the supply [22].
The cross sections of the PEO treated samples were cut, mounted in
epoxy resin and polished. The analysis of the morphology, composition,
thickness, adhesion and microstructure of the coatings were performed
with a Cambridge Stereoscan 440 scanning electron microscope,
equipped with a Philips PV9800 EDS analyzing both the surface and the
cross sections of the samples.
A Siemens D500 X-ray diffractometer with a nickel-filtered Cu-Kα
radiation source (λ =0.15405 nm), operating at 40 kV and 30 mA was
used to analyze the different phases into the coating and to analyze the
salt recovered from the permanent magnets.
A Perkin-Elmer Φ5600ci spectrometer was used to perform XPS
analysis working with non-monochromatic Al radiation (1486.6 eV) at
250 W. A working pressure < 5 ⋅ 10−8 Pa was employed. The binding
energy (BE) of the Au4f7/2 line at 83.9 eV with respect to the Fermi
Fig. 2. Voltage vs Time plot recorded during PEO process.
level was assumed for the calibration. The standard deviation for the BE
values was 0.15 eV. For the C1s line of carbon the BE value of 284.6 eV
was assigned to correct the reported BE for the charging effects. [23] regional instability caused by breakdown also a large release of oxygen
Survey scans (187.85 pass energy, 1 eV/step, 25 ms per step) were is produced (sparking stage). In the last stage the voltage remains stable
obtained in the 0–1300 eV range. After a Shirley type background (micro-arc stage). During this last stage the growth of the oxide ceramic
subtraction [24] the atomic composition, was evaluated using sensi- coating occurs. [30]
tivity factors supplied by Perkin [25]. The reference handbook [25], the
NIST XPS Database [26] and the references reported in [27,28] were 3.1. Corrosion resistance
employed to carry out the assignments of the peaks. Deconvolution of
the peaks was performed with XPSpeak 4.1 software. In order to qualitatively evaluate the corrosion behavior of the
Potentiodynamic tests, open circuit voltage (OCV) decay and elec- samples, potentiodynamic polarization tests were performed. The po-
trochemical impedance spectroscopy (EIS) at ambient temperature tentiodynamic polarization plots of untreated AZ91 sample, PEO
were employed to evaluate the corrosion resistance of the samples. treated and sealed treated samples are shown in Fig. 3.
An AMEL 2549 Potentiostat was employed for the electrochemical Considering the PEO samples and the ones sealed with neodymium
tests, performed in a solution 0.1 M Na2SO4 and 0.05 M NaCl, to si- sulfate salt, an improvement in the corrosion proprieties was always
mulate a moderate aggressive environment containing both sulphates observed, in comparison with the untreated sample. The addition of
and chlorides, in analogy with previous works of the authors on PEO H2O2 to the solution used for sealing processes influenced the corrosion
coatings [11]. A saturated calomel electrode was employed as reference properties of the obtained samples, in agreement with literature re-
electrode (SCE) and a platinum electrode as counter electrode. For the garding neodymium based conversion coatings. [21] In fact, the two
potentiodynamic polarization a scan rate of 0.5 mV s−1 was used. Be- samples sealed with the solution containing only the neodymium salt,
fore the test the samples were immersed for 1 h for OCV stabilization. A regardless the concentration used, showed similar corrosion behavior,
potential range from -2 to -0.8 V was scanned in the tests and each lower than PEO treated sample. Instead, the presence of hydrogen
measure was repeated three times in order to assure the reproducibility peroxide produced a remarkable increase in the corrosion properties,
of the test. Potentiodynamic polarization tests were performed only for with a shift to lower currents.
a qualitative analysis among the different samples, considering that no From the preliminary qualitative evaluation, the sample with the
quantitative evaluation on the corrosion rate can be performed on best corrosion performance resulted the one sealed with 12 g/l of NaNd
samples coated with a thick insulating and sealed film [29]. For a (SO4)2 and 20 mL/l of H2O2.
quantitative analysis electrochemical impedance spectroscopy (EIS) In order to better understand the corrosion behavior of the samples,
tests were performed. The EIS measurements were performed with a also EIS tests were performed. The fitting of the experimental data was
Materials Instrument Spectrometer coupled with the 2549 Potentiostat performed with Z-view software, using the equivalent circuits reported
at the value of the open circuit potential and the employed frequency in Fig. 4. Three equivalent circuits were employed in order to consider
range was 105 Hz-10-2 Hz with a perturbation amplitude of 10 mV. Z- the different protective layers present in the different samples. For
View software was used for the fitting of impedance spectra. Also in this untreated sample the R/CPE circuit was considered as only natural
case before the test the OCV was stabilized for 1 h and the measures
were repeated three times.
For the OCV decay test the samples were immersed and the OCV
stabilized for 1 h and after was recorded the OCV vs time plot for 4 h.

3. Results and discussion

The PEO treatments were performed in galvanostatic mode and

during the process a potential increase up to 300 V was observed, as
reported in the voltage vs time plot (Fig. 2).
The trend of the potential reported in Fig. 2 is typical for PEO
coatings. As a matter of fact, in the first stage (named also anodic stage)
the voltage linearly increases with time, corresponding to the tradi-
tional anodizing stage, with the formation of a very thin insulating film. Fig. 3. Potentiodynamic polarization plot of AZ91 magnesium alloy PEO coated
Then, the voltage exceeds the critical value: the production of a large at 0.5 A/cm2 and sealed with different concentration of NaNd(SO4)2, with and
number of dispersed discharge channels are observed due of micro- without hydrogen peroxide, at 50 °C for 30 min.

3
L. Pezzato, et al.
Fig. 4. Equivalent circuits employed for curve fitting for the untreated sample (A), PEO coated sample (B) and sealed samples (C).
oxide layer is present (Fig. 4a). The equivalent circuit reported in
Fig. 4b was used for PEO coated sample. This type of circuit was already
employed in literature to fit the data from PEO samples [11–13] for the
presence of two layers: an external porous layer and an internal layer,
often called barrier layer [30]. The circuit reported in Fig. 4c was used
for sealed samples, in agreement with literature [11,12], because
sealing with neodymium salts formed a third layer over those already
present.
In these equivalent circuits (see also [11–13]), the resistance of the
solution is represented by Re, the polarization resistance of the porous
layer by Rp, the polarization resistance of the barrier layer by Rb and the
polarization resistance of the sealing layer by Rs. In the case of the
untreated sample the polarization resistance of the natural oxide layer
is called Ro. This schematization was employed in order to consider the
formation of two different interfaces electrolyte-substrate. In detail, the
first interface is formed between the electrolyte and the external porous
layer (and is represented by Rp), whereas the second is formed between
the electrolyte into the pores and the internal barrier layer (and is re-
presented by Rs). As the measured capacitance is not ideal, CPEi instead
of capacitances were used in the equivalent circuit. The capacitance
values were calculated using the equation proposed by Brug et al. (6)
[31].
1 1 1 n−1
C = Qn ( + ) n
Re R
Nyquist impedance plots and the results obtained by the fitting of
the experimental data, are reported in Fig. 5 and Table 2, respectively.
The points in the graph represented the experimental data, whereas the
Fig. 5. Nyquist plot of AZ91 magnesium alloy PEO coated at 0.5 A/cm2 and
sealed with 6 g/l and 12 g/l of NaNd(SO4)2, with and without 20 mL/l of H2O2,
at 50 °C for 30 min.
Corrosion Science 173 (2020) 108741
continuous lines indicated the relative fitting. The agreement between
experimental values and the fitting ones were good, with a percentage
error for the single parameters between 0.5 and 1%.
In the sample treated with 6 g/l of NaNd(SO4)2 without hydrogen
peroxide, the value of Rs (the polarization resistance of the sealing
layer) was lower of two orders of magnitude than Rb (the polarization
resistance of PEO-coating). This suggested that corrosion resistance was
mainly due to the barrier layer and not to the sealing layer that, in this
case, did not contribute significantly to the corrosion resistance, prob-
ably for the poor adhesion between the sealing layer and the PEO
coating. The effects of the addition of H2O2 were evident comparing the
values of Rs (8254 Ω cm2 and 20 Ω cm2) at the same concentration of
6 g/l of Neodymium salt. The same conclusions can be drawn also
comparing data for 12 g/l of Neodymium salt, where Rs passed from
5356 Ω cm2 to 13931 Ω cm2 with the addition of hydrogen peroxide.
Moreover, a decrease in the capacitance values of the sealing layer Cs
was noted with the addition of hydrogen peroxide, indicating an in-
crease in the thickness of the sealing layer. The results showed that
hydrogen peroxide addition (20 mL/l) played a key role in the corrosion
protection given by the sealing layer and that an increase in the salt
concentration produced an increase in the corrosion protection.
The sample which showed the best performance was the one treated
with 12 g/l of NaNd(SO4)2 and 20 mL/l of H2O2. On this sample, the
PEO treated sample and the untreated one also OCV decay tests were
(6)
performed and the results can be observed in Fig. 6.
The results confirmed that the sample with the sealing layer ob-
tained with 12 g/l of neodymium sulfate and hydrogen peroxide was
the one with the best corrosion performances, in fact it was char-
acterized by the higher value of the OCV. Moreover, can be also ob-
served that the OCV value was more or less constant with time in-
dicating that the sealing layer did not degrade during the immersion
time.
3.2. Surface analysis
All the obtained samples were observed at SEM. The images of the
surface and the cross section of the sample PEO treated before the
sealing process can be observed in Fig. 7. It can be noted the typical
porous surface that characterizes this kind of coatings [30], with the
presence of a uniform coating about 20 thick.
After the sealing treatment in all cases (but in particular when H2O2
wasn’t added) some salt powder remained scattered on the samples’
surface. This can be seen in the backscattered electrons micrographs
(Figs. 8 and 9) as lighter zones of “spongy” appearance.
In Fig. 8a it can be seen that using 6 g/l of NaNd(SO4)2 some zones
were not even coated, and the layer was not adherent to the PEO-
coating below: in fact, after cutting the cross-section and polishing it,
the neodymium layer detached and it was not observed by SEM
(Fig. 8b). This poor adhesion can explain the corrosion behavior
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L. Pezzato, et al. Corrosion Science 173 (2020) 108741

Table 2
Equivalent circuit data for samples sealed with NaNd(SO4) with and without hydrogen peroxide at 50 °C for 30 min, after PEO treatment.
Untreated PEO 6g/l Nd 6g/l Nd + H2O2 12 g/l Nd 12 g/l Nd + H2O2

2
Re [Ω cm ] 23 24 25 24 25 25
Ro o Rp [Ω cm2] 148 1489 560 264 212 550
Rb [Ω cm2] – 2672 2800 1200 2324 3240
Rs [Ω cm2] – – 20 8254 5356 13931
Qo o Qp [F cm−2 Hz1-n] 7.90 × 10−6 6.20 × 10−5 3.34 × 10−6 2.13 × 10−5 1.77 × 10−5 1.31 × 10−5
no o np 0.96 0.86 0.80 0.73 0.88 0.81
Co o Cp [F] 5.4 × 10−6 2.1 × 10−5 3.15 × 10−7 1.25 × 10−6 6.1 × 10−6 1.9 × 10−6
Qb [F cm−2 Hz1-n] – 1.36 × 10−5 6.52 × 10−6 9.00 × 10−6 2.57 × 10−5 6.89 × 10−5
nb – 0.83 0.90 0.72 0.64 0.65
Cb [F] – 2.6 × 10−6 2.5 × 10−6 3.35 × 10−7 4.1 × 10−7 2.22 × 10−6
Qs [F cm−2 Hz1-n] – – 3.50 × 10−5 6.00 × 10−6 2.00 × 10−6 1.20 × 10−6
ns – – 0.84 0.64 0.73 0.77
Cs [F] – – 7.8 × 10−6 4.1 × 10−8 5.1 × 10−8 5.3 × 10−8
Chi square 0.0001 0.0003 0.0003 0.0004 0.0006 0.0001

zones probably the conversion coating did not take place well, and
some sulfur compounds remained after the end of the treatment.
From SEM observation (Fig. 8 and 9) the conversion layer seemed to
be on the top surface and not completely penetrated into the pores that
characterize PEO coating.
The X-ray diffraction (XRD) analysis performed on the sample
treated with 12 g/l of the salt and 20 mL/l of hydrogen peroxide are
shown in Fig. 10.
This analysis showed, besides the usual compounds due to the PEO-
layer, in accordance with the composition of the electrolyte and of the
substrate, the presence of Nd2O3 formed on the surface during the
Fig. 6. OCV decay evolution for the sample with the best corrosion perfor-
sealing process.
mances, the sample PEO treated and the untreated one. The sample obtained with Nd salt that exhibited the best corrosion
properties (12 g/l of NaNd(SO4)2 and 20 mL/l of H2O2 at 50 °C for
30 min) was also analyzed with XPS spectroscopy, to determine the
previously reported where the contribution of the sealing layer to the
chemical nature of the elements constituting the surface, their relative
corrosion resistance resulted low for this sample, with a resistance si-
amount and their oxidation state. Also the sample PEO treated without
milar to the one of the PEO treated sample. Adding 20 mL/l of hydrogen
the Nd-based conversion coating was observed in order to evaluate the
peroxide, it became uniform and adherent, as shown in Fig. 8 c–d.
possible differences in comparison with the Nd-containing samples.
Even in sample treated only with 12 g/l of neodymium salt the
Table 4 reports the detailed composition of the two surfaces. In both
“spongy” zones were present, and on the cross-section micrographs
samples, the principal component was oxygen (about 50 % at.), due to
(Fig. 9b) can be seen that the sealing layer was detached again. Adding
the oxidative plasma PEO process, and carbon, due to the surface
20 mL/l of hydrogen peroxide, the sealing layer became uniform on the
contamination. The other elements were present only in minor amount,
surface and all the surface was coated (Fig. 9c) and more adherent to
mostly < 5 %, with the only exception of sodium and magnesium in the
PEO-coating (Fig. 9d). This well-distributed layer can be related with
“PEO” sample. The sample sealed with Nd salt contained 1.8 % at. of
the higher corrosion performance of this last sample.
Nd.
On the surface three zones were distinguishable: scale zones (4),
Considering first the sample without Nd, the spectra are reported in
darker zones (5) and “spongy” zones (6). Energy-dispersive X-ray
Fig. 11
spectroscopy (EDS) analyses were performed both on the surface and
The Mg2s peak (Fig.11a) is formed by the overlapping of two
the cross sections of the Nd-coated samples, and the results are reported
components, the lower one corresponding to MgSiO3 and Mg Al2O4 and
for the sample treated with 12 g/l of the salt and 20 mL/l of hydrogen
the main one originated from MgO. The P 2p peak (Fig.11b) presents
peroxide (Fig. 9c-d) in Table 3 . The dry mud zones resulted to be
only one contribution (splitted into the two 2p3/2 and 2p1/2 compo-
composed mainly by Nd and O, whereas the darker zones contained
nents), compatible with the presence of magnesium phosphate Mg
higher amounts of PEO-coating elements, such as Mg, Si and P. The
(PO3)2 seen by XRD. Similar to the phosphorous region, the Si 2p region
“spongy” areas were richer in S than all other surface’s zones: in these

Fig. 7. SEM images of the surface (A) and the cross section (B) of the sample PEO treated without the sealing.

5
L. Pezzato, et al. Corrosion Science 173 (2020) 108741

Fig. 8. Scanning electron micrographs (backscattered electrons) of the surface and cross section of sealing coatings formed on AZ91 magnesium alloy with 6 g/l of
NaNd(SO4)2 (A-B), adding 20 mL/l of H2O2 (C-D), performed at 50 °C for 30 min.

(Fig.11c) is also composed of a single component, compatible with the Table 3

presence of enstatite MgSiO3. In the case of the O1s region (Fig.11d), Quantitative results (wt%) of EDS analysis of the cross-sectioned surface layers.
the peak is complex, comprising (at least) three components. The main O% Na% Mg% Al% Si% P% S% Nd% Zn%
component, centred at about 531 eV, is due to the presence of magne-
sium oxide MgO. The peak at 532 ev ca. is connected to the presence of 1 – – 90.40 8.82 – – – – 0.78
mixed Mg-Si and Mg-P oxides. The rest of the components convoluting 2 40.78 23.16 12.78 1.37 10.36 11.28 – – –
3 47.71 6.36 5.85 0.54 3.90 15.71 – 19.93 –
in the final peak shape are likely due to the presence of carbon species
4 13.89 3.84 1.93 – 1.85 1.42 5.51 71.55 –
(possibly carbonate) with different degrees of oxidation, covering for 5 35.40 7.77 7.08 – 4.06 2.95 8.63 34.11 –
the high amount of revealed carbon. 6 43.84 8.18 2.86 0.47 1.87 2.29 14.28 26.21 –
The spectra for the sample sealed with 12 g/l of NaNd(SO4)2 and
20 mL/l of H2O2 at 50 °C for 30 min are reported in Fig. 12 and Fig.13.
Considering the Mg2s peak (Fig. 12a) in the Nd containing sample component describing the MgO is in this case quite weak, in accordance
the peak is fitted with a single component, corresponding to oxidized with a lower overall Mg content. Alumina and silicate/phosphate spe-
magnesium species. For both P and Si (Fig.12b and 12c), the analysis of cies, plus possibly additional oxides of iron and copper, give rise to the
the 2p regions leads results similar to the pristine case, in which the main component. Interestingly, no high lying component is found.
signals of Mg(PO3)2 and MgSiO3 were found. In the “PEO-Nd” sample The Nd3d region (Fig.13) presents the typical features of Nd2O3,
the O1s region (Fig.12d) is quite different from the pristine sample. The with the main 3d5/2 feature centred at 981 eV, and an energy-loss peak

Fig. 9. Scanning electron micrographs (backscattered electrons) of the surface and cross section of sealing coatings formed on AZ91 magnesium alloy with 12 g/l of
NaNd(SO4)2 (A-B), adding 20 mL/l of H2O2 (C-D), performed at 50 °C for 30 min.

6
L. Pezzato, et al. Corrosion Science 173 (2020) 108741

magnesium alloy after PVD deposition of Nd and the formation of a

diffusion layer with Nd oxide. Birbilis et al. [33] showed that the nat-
ural oxide layer formed on Mg-Nd alloy was more protective than the
one formed in an alloy without neodymium and Takenada et al. [34]
demonstrated that the corrosion resistance was improved by the surface
oxide layer consisting of both Mg and Nd. Moreover, Nd3+ ions are able
to reduce the corrosion rate in chloride environment, as evidenced by
Martinez de la Escalera et al. [35], and this can also explain the increase
in the corrosion properties of the sealed samples studied in this work
considering that the testing electrolyte contain chlorides.

Fig. 10. X-ray diffraction patterns for the samples of AZ91 magnesium alloy
4. Conclusions
treated with PEO process, then sealed in an aqueous solution with 12 g/l of
NaNd(SO4)2 and 20 mL/l of H2O2 at 50 °C for 30 min.
In this work, the effect of a sealing treatment performed using Nd-
based solutions on PEO coated AZ91 Mg alloy was studied. The solution
Table 4 employed for the sealing treatment contained neodymium sulfate. This
XPS quantitative results (at%) of elements constituting the surface of the un-
salt was recovered by leaching of “end of life” permanent magnets in an
sealed PEO sample and of the sample sealed 12 g/l of NaNd(SO)2 and 20 mL/l of
idea of circular economy. All the sealed samples were characterized by
H2O2 at 50 °C for 30 min.
improved corrosion performances if compared with the PEO treated
Sample C O Na Mg Al Si P S Fe Cu Nd ones. The use of the hydrogen peroxide played a key role in the for-
mation of the sealing conversion coating. In fact, its addition in the
PEO-Nd 25.7 49.3 3.7 1.7 2.8 3.3 3.3 3.7 3.3 1.4 1.8
PEO 14.5 49.6 22.4 7.3 – 1.3 4.9 – – – – electrolyte remarkably increased the adhesion of the coating and acted
as accelerant for the deposition reaction. In detail, the best corrosion
resistance was obtained for the sample with 12 g/l of NaNd(SO4)2 and
about 3 eV towards lower energies. This confirm the results of the XRD 20 mL/l of H2O2. The sealing layer resulted adherent and uniform on
analysis where the neodymium oxide was found on the sealed surface. the surface in the samples treated with hydrogen peroxide in the so-
Considering the previously reported results it can be summarized lution. The PEO coating resulted constituted by magnesium oxides, si-
that the sealing layer, mainly constituted by Nd2O3, produced a re- licates and phosphates whereas the sealing layer was mainly composed
markable increase in the corrosion resistance. This improvement in the by Nd2O3. The increased corrosion performances of the sealed samples
corrosion properties can be first of all ascribed to the physical barrier can be ascribed both to the physical barrier given by the sealing layer
that the sealing layer produced against the external environment, as and to the fact that the presence of neodymium oxide increase the
was found in previous works with other kind of rare-earth based sealing protection of the oxide layer.
treatments [11–14]. However, the increase in the corrosion resistance
can be also linked with the fact that an oxide layer containing Neody-
mium oxides is more protective than one that do not contain Nd, thanks Data availability
to the increased passivity. This fact is in accordance with the results
found by other researches on magnesium alloys. In detail, Levy et al. The raw/processed data required to reproduce these findings cannot
[32] found increased corrosion performances of biodegradable be shared at this time as the data also forms part of an ongoing study

Fig. 11. High resolution XPS Mg2s (a), P2p (b), Si2p (c) and O1s (d) regions for the sample PEO treated without sealing treatments.

7
L. Pezzato, et al.
Fig. 12. High resolution XPS Mg2s (a), P2p (b), Si2p (c) and O1s (d) regions for the sample PEO treated and sealed sealed with 12 g/l of NaNd(SO4)2 and 20 mL/l of
H2O2 at 50 °C for 30 min.
Fig. 13. High resolution XPS Nd3d region for the sample PEO treated and
sealed sealed with 12 g/l of NaNd(SO4)2 and 20 mL/l of H2O2 at 50 °C for
30 min.
CRediT authorship contribution statement
Luca Pezzato: Conceptualization, Methodology, Investigation,
Formal analysis, Data curation, Writing - original draft. Riccardo
Babbolin: Investigation. Pietrogiovanni Cerchier: Conceptualization.
Marco Marigo: Investigation. Paolo Dolcet: Investigation, Data cura-
tion. Manuele Dabalà: Resources, Supervision, Funding acquisition.
Katya Brunelli: Writing - review & editing, Supervision, Visualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
ICMATE-CNR (Padova) is gratefully acknowledged for financial
support and provision of XPS equipment. The authors would like to
thank Prof. S. Gross (ICMATE-CNR) for the helpful discussion.
8
Corrosion Science 173 (2020) 108741
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.corsci.2020.108741.
References
[1] G. Song, A. Atrens, D.St. John, X. Wu, J. Nairn, The anodic dissolution of magne-
sium in chloride and sulphate solutions, Corr. Sci. 39 (1997) 1981–2004.
[2] F.C. Walsh, C.T.J. Low, R.J.K. Wood, K.T. Stevens, J. Archer, A.R. Poeton, A. Ryder,
Plasma electrolytic oxidation (PEO) for production of anodised coatings on light-
weight metal (Al, Mg, Ti) alloys, Trans. Inst. Met. Finish. 87 (2009) 122–135.
[3] J. Liang, P. Bala Srinivasan, C. Blawert, M. Störmer, W. Dietzel, Electrochemical
corrosion behavior of plasma electrolytic oxidation coatings on AM50 magnesium
alloy formed in silicate and phosphate based electrolytes, Electrochim. Acta 54
(2009) 3842–3850.
[4] A. Santos-Coquillat, M. Esteban-Lucia, E. Martinez-Campos, M. Mohedano,
R. Arrabal, C. Blawert, M.L. Zheludkevich, E. Matykina, PEO coatings design for
Mg-Ca alloy for cardiovascular stent and bone regeneration applications, Mat. Sci.
Eng. C 105 (2019) 110026.
[5] B. Mingo, Yue Guo, A. Nemcova, A. Gholinia, M. Mohedano, M. Sun, A. Matthews,
A. Yerokhin, Incorporation of halloysite nanotubes into forsterite surface layer
during plasma electrolytic oxidation of AM50 Mg alloy, Electrochim. Acta 299
(2019) 772–788.
[6] G. Barati Darband, M. Aliofkhazraei, P. Hamghalam, N. Valizade, Plasma electro-
lytic oxidation of magnesium and its alloys: mechanism, properties and applica-
tions, J. Magnes. Alloy. 5 (2017) 74–132.
[7] C. Blawert, W. Dietzel, E. Ghali, G. Song, Anodizing treatments for magnesium al-
loys and their effect on corrosion resistance in various environments, Adv. Eng.
Mat. 8 (2006) 511–533.
[8] J.A. Curran, T.W. Clyne, Porosity in plasma electrolytic oxide coatings, Acta Mater.
54 (2006) 1985–1993.
[9] P. Cerchier, L. Pezzato, K. Brunelli, P. Dolcet, A. Bartolozzi, R. Bertani, M. Dabalà,
Antibacterial effect of PEO coating with silver on AA7075, Mat. Sci. Eng. C 75
(2017) 554–564.
[10] P. Cerchier, L. Pezzato, E. Moschin, L.B. Coelho, M. Olivier, I. Moro, M. Magrini,
Antifouling properties of different Plasma Electrolytic Oxidation coatings on 7075
aluminium alloy, Int. Biodeterior. Biodegradation 133 (2018) 70–78.
[11] L. Pezzato, K. Brunelli, R. Babbolin, P. Dolcet, M. Dabalà, Sealing of PEO coated
AZ91 magnesium alloy using la-based solutions, Int. J. Corros. 2017 (2017).
[12] M. Mohedano, C. Blawert, M.L. Zheludkevich, Cerium-based sealing of PEO coated
AM50 magnesium alloy, Surf. Coat. Tech. 269 (2015) 145–154.
[13] B. Mingo, R. Arrabal, M. Mohedano, Y. Llamazares, E. Matykina, A. Yerokhin,
A. Pardo, Influence of sealing post-treatments on the corrosion resistance of PEO
coated AZ91 magnesium alloy, App. Surf. Sci. 433 (2018) 653–667.
[14] M. Mohedano, P. Perez, E. Matykina, B. Pillado, G. Garces, R. Arrabal, PEO coating
with Ce-sealing for corrosion protection of LPSO Mg-Y-Zn alloy, Surf. Coat. Tech.
L. Pezzato, et al.
383 (2020) 125253.
[15] A.L. Rudd, B.C. Breslin, F. Mansfeld, The corrosion protection afforded by rare earth
conversion coatings applied to magnesium, Corr. Sci. 42 (2000) 275–288.
[16] L. Yang, J. Li, X. Yu, M. Zhang, Z. Huang, X. Huang, Lanthanum-based conversion
coating on Mg–8Li alloy, App. Surf. Sci. 255 (2008) 2338–2341.
[17] L. Yang, J. Li, C. Lin, M. Zhang, J. Wu, Study of molybdenum/lanthanum-based
composite conversion coatings on AZ31 magnesium alloy, App. Surf. Sci. 257
(2011) 2838–2842.
[18] C. Lin, C. Changguol, W. Ningning, W. Jimin, D. Ling, Study of cerium and lan-
thanum conversion coatings on AZ63 magnesium alloy surface, Rare Metal Mat.
Eng. 44 (2015) 333–338.
[19] G. Jin, Y. Yang, X. Cui, E. Liu, Z. Wang, Q. Li, Chrome-free neodymium-based
protective coatings for magnesium alloys, Mater. Lett. 65 (2011) 1145–1147.
[20] X. Cui, G. Jin, Y. Yang, E. Liu, L. Lin, J. Zhong, The formation of neodymium
conversion coating and the influence of post-treatment, App. Surf. Sci. 258 (2012)
3249–3254.
[21] D. Zhao, D. Zhang, Y. Liu, G. Hu, Y. Gou, F. Pan, Neodymium-based conversion
coating on AZ31 magnesium alloy, Rare Metal Mater. Eng. 46 (2017) 289–295.
[22] Z. Sun, Y. Xiao, H. Agterhuis, J. Sietsma, Y. Yang, Recycling of metals from urban
mines-a strategic evaluation, J. Clean. Prod. 112 (2016) 2977–2987.
[23] M.P. Seah, D.S. Briggs, J. Practical Surface Analysis, Auger and X-ray Photoelectron
Spectroscopy, 1st edition, Wiley, 1990.
[24] D.A. Shirley, High-resolution X-ray photoemission spectrum of the valence bands of
gold, Phys. Rev. B 5 (1972) 4709–4714.
[25] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, J. Chastain, Handbook of X-
Ray Photoelectron Spectroscopy, Perkin Elemer Corp, Eden Prairie, Minnesota,
USA, 1992.
Corrosion Science 173 (2020) 108741
[26] X-ray Photoelectron Spectroscopy Database 20, Version 3.0, Gaithersburg.
[27] A. Glisenti, A. Frasson, A. Galenda, M.M. Natile, Au/CeO2 supported nanocatalysts:
interaction with methanol, Nanosci. Nanotechnol. Lett. 2 (2010) 213–219.
[28] M.M. Natile, F. Tomaello, A. Glisenti, WO3/CeO2 nanocomposite powders: synth-
esis, characterization, and reactivity, Chem. Mater. 18 (2006) 3270–3280.
[29] L. Pezzato, M. Rigon, A. Martucci, K. Brunelli, M. Dabalà, Plasma Electrolytic
Oxidation (PEO) as pre-treatment for sol-gel coating on aluminum and magnesium
alloys, Surf. Coat. Technol. 366 (2019) 114–123.
[30] C. Blawert, P. Bala Srinivasian, Plasma electrolytic oxidation treatment of magne-
sium alloys, in: H. Dong (Ed.), Surface Engineering of Light Alloys, Woodhead
Publishing Limited, 2010, p. 114.
[31] G.J. Brug, A.L.G. van den Eeden, M. Sluyters- Rehbach, J.H. Sluyters, The analysis
of electrodes impedances complicated by the presence of a constant phase element,
J. Electroanal. Chem. Lausanne (Lausanne) 176 (1984) 275.
[32] G. Levy, E. Aghion, Effect of diffusion coating of Nd on the corrosion resistance of
biodegradable Mg implants in simulated physiological electrolyte, Acta Biomater. 9
(2013) 8624–8630.
[33] N. Birbilis, M.A. Easton, A.D. Sudholz, S.M. Zhu, M.A. Gibson, On the corrosion of
binary magnesium-rare earth alloys, Corr. Sci. 51 (2009) 683–689.
[34] T. Takenaka, T. Ono, Y. Narazaki, Y. Naka, M. Kawakami, Improvement of corro-
sion resistance of magnesium metal by rare earth elements, Electrochim. Acta 53
(2007) 117–121.
[35] D.M. Martinez de la Escalera, J.J. Ramos-Hernandez, E. Porcayo-Palafox,
J. Porcayo-Calderon, J.G. Gonzalez-Rodriguez, L. Martinez-Gomez, Effect of Nd3+
ion concentration on the corrosion resistance of API X70 Steel in Chloride-Rich
Environments, Adv. Mater. Sci. Eng. Int. J. (2018).