Journal of Alloys and Compounds 834 (2020) 155210

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Journal of Alloys and Compounds

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

A stearic Acid/CeO2 bilayer coating on AZ31B magnesium alloy with

superhydrophobic and self-cleaning properties for corrosion
inhibition
Xiang Liu a, Tian C. Zhang b, Huaqiang He a, Like Ouyang a, Shaojun Yuan a, *
a
Low-carbon Technology & Chemical Reaction Engineering Lab, College of Chemical Engineering, Sichuan University, Chengdu, 610065, China
b
Civil and Environmental Engineering Department, University of Nebraska-Lincoln, Omaha, NE, 68182-0178, USA

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

Article history: Corrosion is one of the most challenging issues for the large-scale application of magnesium alloys.
Received 23 February 2020 Fabricating a superhydrophobic surface with a low-cost, easy-to-handle method is meaningful for anti-
Received in revised form corrosion protection of Mg alloys. In this study, a stearic acid/CeO2 bilayer coating was prepared on
4 April 2020
AZ31B Mg by a simple electrodeposition method combined with immersion in stearic acid solution. The
Accepted 14 April 2020
Available online 20 April 2020
growth traits of the coating with different electrodeposition current densities and time were evaluated,
which demonstrated that 60 min combined with 0.65 mA/cm2 is the optimal electrodeposition condi-
tion. Besides, the wettability, anti-corrosion ability, durability, chemical stability and self-cleaning
Keywords:
Superhydrophobic coating
properties of the coating were comprehensively investigated. The results showed that the as-prepared
Cerium oxide coating exhibited a good superhydrophobic and self-cleaning property with CA>158
and SA<2
.
Magnesium alloy Moreover, the coating demonstrated an improved anti-corrosion performance in 3.5 wt% NaCl solution
Anti-Corrosion and was quite stable in the atmosphere and in contact with pH droplets of 1e13.
Self-cleaning © 2020 Elsevier B.V. All rights reserved.

1. Introduction copper, magnesium oxide or hydroxide films formed on the sur-

faces are not dense and protective, making it easy for magnesium or
Magnesium, as the eighth richest element on the earth, has its alloys to corrode, especially in the moist and liquid environment
attracted tremendous attention of researchers due to its various containing corrosive ions such as chloride ions. Therefore, in order
advantageous properties such as high strength-to-weight ratio, low to protect the magnesium and its alloys from corrosion, to widen its
density (only 2/3 that of aluminum and 1/4 that of iron), efficient application and to extend its life span, it is imperative to depress
thermal conductivity and excellent electromagnetic shielding the contact between magnesium substrates and corrosive factors.
characteristics [1]. These favorable properties make magnesium a Based on that consideration, some researchers have been dedicated
perfect engineering material for various applications including to develop hydrophobic films on magnesium alloys with the
automobiles [2], aerospace components, and other high-tech application of Plasma Electrolytic Oxidation (PEO) technique in
electronic equipment such as computers and mobile phones [3]. recent years, which proved it an effective and meaningful way to
In addition, the inherent biocompatibility of magnesium alloys enhance the anti-corrosion ability of magnesium alloys by isolating
endows them great potential in medical application such as metal them with corrosive solution [6e8].
implant [4]. In addition, magnesium is easy to recycle and therefore Superhydrophobic surfaces having self-cleaning, anti-fouling
is valuable to the green and sustainable development of the in- and water-repellency advantages have aroused a lot interests of
dustries. However, magnesium is more active than iron, aluminum, researchers and also proved to be a promising method to reduce
copper, etc., with extremely negative electrode potential, that corrosion behaviors of all kinds metals such as coppers [9,10],
is 2.37 V and 1.63 V (vs. SCE) in 3 wt% NaCl, making it very aluminum alloys [11,12], galvanized steels [13], and magnesium
susceptible to corrosion [5]. Unlike the oxides film of aluminum or alloys [14e16]. With the properties of water contact angles greater
150
and low sliding angles, superhydrophobic surfaces are
generally fabricated by two steps. Firstly, rough surfaces with
* Corresponding author. micro/nano-structures are prepared. Secondly, low surface energy
E-mail address: [email protected] (S. Yuan).

https://doi.org/10.1016/j.jallcom.2020.155210
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210

materials are applied to modify the structures. Many methods have 2. Experimental section
been used to create superhydrophobic surfaces like chemical
etching [17e19], chemical deposition [16,20], sol-gel method 2.1. Materials
[21e24], nanocomposite [25e28], templating [29e31], anodic
oxidation [3,32,33], electrodeposition [34,35], hydrothermal The AZ31B Mg alloy used here was purchased from Hongdi
method [36], etc. For instances, Li et al. used the chemical deposi- Metal Material Co., (Dongguan, China) with a composition of Al
tion method to endow polymethyl methacrylate coating with 2.3e3.5%, Si 0.08%, Ca 0.04%, Zn 0.6e1.4%, Mn 0.2e1.0%, Fe 0.03%, Cu
superhydrophobicity [37]. Jiang et al. prepared titanium dioxide 0.01%, Ni 0.001% and balance Mg. Cerium nitrate hexahydrate
films via hydrothermal synthesis technique and then used them to (99.95%) was purchased from Aladdin (Shanghai, China) and used
synthesize superhydrophobic coating on AZ91D Mg alloys [38]. as received. The anhydrous ethanol, acetone, ammonium nitrate,
Ishizaki et al. formed a superhydrophobic surface on AZ31 Mg al- chloride sodium, chloride acid, sodium hydroxide, nitric acid,
loys by a simple immersion method combined with further modi- phosphoric acid, all of analytical grade, were purchased from
fication of fluoroalkylsilane [39]. The electrodeposition method has Kelong Chem. Co. (Chengdu, China) and used directly. The ultrapure
advantages of low cost, high efficiency, environmental protection water (18.25MU$cm) used throughout the experiments were pro-
and up-scaling potential in industries [34,40]. With the electrode- duced with a commercial reverse osmosis (RO) workstation
position method, it is easy to control the surficial morphology of (2YCG7-2-40L, purchased from Sichuan ZhuoYue Water Treatment
different materials by simply changing experimental factors, Equipment Co. Ltd).
through which superhydrophobic surfaces can be prepared with
more facile operations. For example, by changing the electrode- 2.2. Pretreatment of sample
position voltage and duration time, hierarchical surfaces of
different roughness covered by silica particles were obtained, The as-received AZ31B Mg alloys were cut into a round shape
which were superhydrophobic after being modified with a long with a diameter of 14 mm and a thickness of 2 mm by a wire-cut
alkyl-chained dodecyltrimethoxysilane [41]. By controlling the electric discharge machine. Then the round specimens were pol-
concentration of NiCl2$6H2O in electrolyte, the super-amphiphobic ished with metallographic sandpaper of 400-grit, 600-grit and
surfaces covered with the micro/nanoscale binary structures of 1200-grit successively to remove dirty and oxide layers on the
cauliflower-like clusters were successfully prepared on AZ91D Mg surfaces. After degreased by ultrasonic cleaning in acetone, ethanol
after modified with perfluorocaprylic acid [42]. and ultrapure water for 10 min respectively, the specimens were
These aforementioned methods have extremely enriched the dried by N2 and sealed in an airtight plastic bag for further use.
preparation of superhydrophobic surfaces and shed more lights on Before electrodeposition, the as-pretreated specimens were put
how to handle the metal corrosion problems, including magnesium into an acid solution containing 36% HNO3, 85% H3PO4, anhydrous
alloys corrosion. However, many of these methods involve expensive ethanol and ultrapure water in a volume ratio of 1:3:10:186 for
raw materials, special conditions, complicated fabricating processes 120 s at 25
C, so as to further remove the oxide layer and also lay a
or long-time processing procedures, which, to some extent, restrict foundation for electrodeposition.
their applications in practice. Moreover, some methods required
poisonous materials such as fluoride, thiolate, and hydrofluoric acid 2.3. Fabrication of superhydrophobic coating on AZ31B Mg
to achieve superhydrophobic surfaces, causing negative effects to the
environment. Thus, one of the existing knowledge gaps is how to Fig. 1 shows the two major steps to synthesize the stearic acid/
develop methods for fabrication of superhydrophobic surfaces with CeO2 bilayer-coated superhydrophobic coating formed on the
simple, low-cost and environmentally-friendly methods. Fortu- AZ31B Mg substrate. With the pretreated AZ31B Mg used as the
nately, by using an anodic electrodeposition method, a handy self- cathode and a platinum plate of 20  20 mm as the anode, a simple
healing superhydrophobic surface was prepared on Type 304 stain- two-electrode system supported by a direct-current supply (HAP
less steel [43]. Similarly, with a facile one-step cathodic electrode- DC POWER SUPPLY 03e100) was used to operate the electrode-
position method, a fluorine-free superhydrophobic surface was position process at 35
C. The distance of the two electrodes was
successfully formed on the aluminum substrate [44]. Though, while 2.5 cm. The electrolytes contained 3.25 g Ce(NO3)3$6H2O and 6.03 g
many methods are successful for fabricating superhydrophobic sur- NH3NO3 by using 500 ml ethanol water solution
faces on metals such as copper, aluminum and iron, they may fail (VCH3CH2OH:VH2O ¼ 7:3) as solvents, and only 50 ml electrolyte so-
when applied on Mg alloys for their much higher reactivity [45]. lution was used for one specimen. The cerium oxide film was
Therefore, it is worthwhile to fabricate superhydrophobic surfaces deposited on the magnesium alloy specimen by applying a current
on Mg alloys with simple, low-cost and environmentally-friendly density of 0.65 mA/cm2, 1.95 mA/cm2 and 3.25 mA/cm2, respec-
methods and give a solid evaluation to the coating. tively. During the electrodeposition process, it can be observed that
In this study, we developed a bilayer superhydrophobic surface the potential generally decreased at first and tended to stabilize
by a simple electrodeposition method to fabricate a rough petal- finally. Besides, different electrodeposition times ranging from
like nanosheets coating on AZ31B Mg followed by immersion of 5 min to 90 min were investigated. After the electrodeposition, the
stearic acid. We then used different electrodeposition currents and specimens were rinsed with copious anhydrous ethanol and then
time to reveal some of the growth traits of the coating and also to dried in a vacuum oven (DZF-6051, purchased from Shanghai
find out the best electrodeposition condition in our experiments. Hongdu Electronic Technology Co. Ltd) at 60
C for 60 min. Finally,
Besides, the associated properties of the coating, including self- the coated specimens were immersed in 0.05 mol/L stearic acid
cleaning, chemical stability, mechanical durability and anti- ethanol solution (50 ml) for 1 h and then rinsed with anhydrous
corrosion ability were comprehensively appraised. All the mate- ethanol. The superhydrophobic coating can be obtained after dried
rials applied here were green and cheap, and the whole synthesized at ambient temperature for 8 h.
process can be completed within hours. This study helps to fill the
aforementioned knowledge gap by developing a simple, inexpen- 2.4. Anti-corrosion performance of the superhydrophobic coating
sive and environmentally benign process to fabricate a super-
hydrophobic surface on AZ31B Mg, which is meaningful to promote The superhydrophobic specimens fabricated by electro-
the application of magnesium alloys. depositing for 60 min and modified with stearic acid were
 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210 3

Fig. 1. A schematic diagram of preparation process of the superhydrophobic coating formed on the AZ31B Mg substrate.

immersed in 3.5 wt% NaCl solution for 1, 6, 48, and 100 h separately monochromatic Al Ka X-ray source (1486.6 eV photons). The
before each of them was analyzed by Tafel polarization and elec- detailed procedures were described similarly in our previous study
trochemical impedance spectroscopy (EIS), then compared with [46].
the bare AZ31B Mg and cerium oxides coated specimens obtained
at the optimal electrodeposition condition but without modifica- 3. Results and discussion
tion with stearic acid. All the electrochemical measurements were
performed on a PARSTAR4000þ potentiostat/galvanostat analyzer 3.1. Surface characterization and wettability of the coatings
with a three-electrode corrosion cell (F500, purchased from Tianjin
ida Co., China). A saturated calomel electrode (SCE), the as- Fig. 2 shows that a rough surface coating was successfully
prepared sample with 1 cm2 exposed area, and a platinum plate formed regardless of the current density. The magnified pictures
were used as the reference electrode, the working electrode and the (a2, a3, b2, b3, c2 and c3) show that the coating surface is con-
counter electrode, respectively. The Tafel polarization from structed by a series of petal-like nanosheets. Nevertheless, the
±250 mV vs open circuit potential (OCP) at a scan rate of 0.67 mV/s coating fabricated with 0.65 mA/cm2 appears to be more complete.
with a step height of 2 mV and EIS at the frequency ranging from As seen in Fig. 2, more and wider cracks are found with an increase
100 Hz to 0.01 Hz with a sinusoidal signal amplitude of 10 mV were in the applied current density, which is negative to corrosion pro-
performed at the OCP after the samples were put into the corrosive tection. Therefore, the current density of 0.65 mA/cm2 was selected
solution for 1800 s. In corrosion tests, all EIS measurements were as a constant factor in the following study of electrodeposition
conducted 3e4 times for each coated sample to ensure the repro- time.
ducibility of results. The obtained impedance data was further In order to find out the effect of electrodeposition time on sur-
fitted by Zview software. The chi-square values obtained by fitting face wettability of coating, water contact angles of the as-prepared
the impedance spectra were less than 0.01 and the standard de- coatings electrodeposited for 5, 15, 30, 45, 60, 75, and 90 min were
viations of individual were controlled within 10%. measured before and after modification with stearic acid. As shown
in Fig. 3, after electrodeposition for 5 min, the coating exhibited
2.5. Analytical and characterization methods hydrophobicity with a water contact angle being more than 100

before modified with stearic acid. Interestingly, by increasing the
The surface morphologies of the as-prepared coatings at electrodeposition time, water contact angles of the as-synthesized
different conditions were observed by scanning electron micro- coating increased correspondingly. Moreover, when deposition
scope (SEM) imaging on a JEOL JSM-7610 SEM (Toyoko, Japan) time was over 45 min, the coating showed a superhydrophobic
equipped with an energy dispersive X-ray spectroscopy (EDS) property, and the water contact angles were up to 150
at the
accessory to analyze the elements. The chemical composition of the electrodeposition of 60 min, even without further modification of
coating after modification of stearic acid was determined by Fourier stearic acid. This may be attributed to the prepared nanosheet
transformation infrared spectrometer (FT-IR) (PerkinElmer, Spectro structures and the intrinsically hydrophobic property of CeO2 [47].
two) with a diamond universal ATR accessory. The crystalline Although the theory of superhydrophobic surface made only by
structure of various specimens was characterized by a DX2700 X- specific structures were proved to be true [48,49], more accurate
ray diffractometer (Haoyuan Instruments Co., Dandong, China) structures are usually required. Once the structures are broken,
with CueK radiation (k ¼ 1.5418 Å). Water contact angles with 5 mL they could fail to maintain the long-term stability of the hydro-
drops of ultrapure water were measured on a DM-501 goniometer phobicity if there is no further modification of low surface energy
(Kyowa Interface Science Co., Saitama, Japan), and the average materials. In view of this consideration, we proposed to modify the
values were calculated by testing at least three different positions surfaces with stearic acid. After the modification with 0.05 mol/L
of each sample. Surface composition and valence states of the stearic acid, all the coatings electrodeposited from 5 to 90 min
superhydrophobic coating before and after 100 h immersion in became superhydrophobic. Among them, water contacts angles
3.5 wt% NaCl solution were detected by X-ray photoelectron spec- increased with the deposition time, and reached the climax at
troscopy (XPS) on an Axis Ultra Has XPS spectrometer (Kratos 60 min, with static contact angles more than 158
and extremely
Analytical Ltd, Wharfside, Manchester, UK) by using a low adhesion force, as shown by the inserted snapshots in Fig. 3.
4 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210

Fig. 2. SEM images of the as-prepared coatings at different electrodeposition current densities: a1a3) 0.65 mA/cm2; b1b3) 1.95 mA/cm2; c1c3) 3.25 mA/cm2.

However, by extending the electrodeposition time to 75 min, the 34.4
, 36.6
, 47.8
, 63.1
, 69.9
, 72.5
and 77.8
, corresponding to
superhydrophobicity of the corresponding coatings began to the (100), (002), (101), (102), (108), (201), (004) and (202) of a-Mg
decline compared with that of the coatings at 60 min. In addition, (PDF#35e0821) from the AZ31B Mg substrate. Besides, the samples
despite the coating obtained at the deposit time from 15 min to with deposited coatings appear diffraction peaks at 28.5
, which
90 min showing high static water angles and relatively low adhe- can be attributed to the (111) of CeO2 (PDF#35e0824). With an
sion property, the coating fabricated from 5 min possessed rela- increase in the electrodeposition time, peak of the (111) CeO2 be-
tively high adhesion so that water droplets failed to fall down easily comes stronger, and peaks of (200), (220) and (311) CeO2 appears to
from the surfaces. be obvious after being electrodeposited for 60 min, indicating that
To analyze the above phenomena, XRD technique was used to the cubic fluorite CeO2 phase is the main composite of the as-
detect the crystalline structure of the as-synthesized coating with prepared coating. For further analysis, the crystalline sizes of the
electrodeposition time from 5 to 60 min. As shown in Fig. 4, all the coatings were calculated by the Scherrer equation D ¼ Kl/(bcosq)
samples including the bare AZ31B Mg and specimens fabricated for based on the (111) CeO2 diffraction peak, where Scherrer constant K
different electrodeposition times have diffraction peaks at 32.2
, is 0.89, wavelength of the X-ray l is 0.15418, diffraction angle q is

Fig. 3. Water contact angles of the coatings formed with different electrodeposition Fig. 4. XRD graphs of the bare AZ31B Mg and coated samples for different electro-
times, followed by modification with or without stearic acid; inserts are the snapshots deposition time: a) bare AZ31B Mg; b) 5 min; c) 15 min; d) 30 min; e) 45 min; g)
of the samples electrodeposited for 60 min followed by modification of stearic acid. 60 min.
 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210 5

about 14.25
, and b is the full width at the half maximum of the 289.5, 286.0, and 284.8 eV is contributed to the presence of OeC]
peak. As a result (seen in Table 1), the average crystalline sizes are O, CeO and CeC respectively [51,52], indicating successful modifi-
10 ± 1.6 nm, indicating that CeO2 may be nucleated in a short time cation of stearic acid. The Ce3d core-level spectrum can be fitted
during the electrodeposition process, and the electrodeposition with eight decomposition curves as depicted in Fig. 6(c), which is
time may have little influence on the grain size. owing to Ce 3d3/2 and Ce 3d5/2 species [53]. While the peaks of
To figure out the change of surface morphologies with the binding energy at 916.8, 907.1, 901.1888.2, and 882.3 eV are
electrodeposition time, the coatings electrodeposited for 5, 30, and attributed to Ce4þ 3d3/2, the peak at 898.6 eV is attributed to Ce4þ
60 min were observed by SEM before modification of stearic acid. 3d5/2 and peaks at 904.0 and 885.8 eV are owing to Ce3þ 3d3/2, Ce3þ
When the substrate was treated for 5 min, a coating with a cracked 3d5/2 respectively [54]. The above analyses demonstrate the coex-
and warped surface was formed (Fig. 5(a1)), which may be attrib- istence of compounds of Ce(IV) (CeO2) and Ce(III), which is
uted to the low thickness of the coating. Besides, some nanosheets consistent with the XRD analysis (Fig. 4). In addition, peaks at 904.0
were also grown on the surface (Fig. 5(a2)), giving a crucial struc- and 885.8 eV may be an indication of formation of cerium stearate
ture for superhydrophobic ability and thus, explaining the super- [44]. In Fig. 6(d), the infrared absorption peaks at wavelengths of
hydrophobic phenomenon after modification of stearic acid. After 2960 cm1, 2915 cm1, 2849 cm1, and 1465 cm1 are attributed to
electrodeposition for 30 min, the coating became denser and less CeH stretching vibration; the absorption peaks of 721 cm1
cracked (Fig. 5(b1)). Also, the nanosheet seemed to be thicker and appeared in the fingerprint area are due to the number of eCH2
some small round particles appeared on the surface (Fig. 5(b2)). greater than four, both indicating the successful modification of
With the electrodeposition time of 60 min (Fig. 5(c1)), the coating stearic acid on the surface. Consequently, the as-synthesized
obviously became much denser and more complete with the superhydrophobic coating is mainly composed of cerium oxides,
appearance of spherical deposits on the surface layer. Composed of and stearic acid has been successfully modified on the surface,
abundant tiny particles (Fig. 5(c2)), the nanosheets appeared to be presumably through physical adsorption and chemical reaction.
longer with a length around 1e3 mm. The thickness of the coating is
increased with the electrodeposition time as seen in Fig. 5 (a3c3), 3.2. Stability and durability
corresponding to 2.5, 7.0, 10.5 mm respectively. Therefore, with an
increase in electrodeposition time from 5 to 60 min, the coating Stability of the superhydrophobic coating was evaluated by tests
becomes denser and thicker, and 60-min electrodeposition time of exposure to air, contact with water droplets of different pH
seems to be the best option in these experiments. After modified ranging from 1 to 13 and immersion in 3.5 wt% NaCl solution.
with stearic acid (SA), the surface morphology of the coating Before the measurements of water contact angles, water droplets
changed little and still maintained a complete nanosheet-form were stabilized on the sample surface for around 15 s. Fig. 7(a)
structure as seen in Fig. 5(d1). This indicates that SA mainly plays displays that, despite a bit fluctuation during the process, contact
the role of reducing the surface energy while electrodeposited angles of the coupon were stably maintained more than 158

cerium oxides coating provides the evitable nano/microstructure. during the 60 days exposure to the air, indicating the super-
The good combination of these two factors is the key to achieve hydrophobic coating could remain its wettability in the atmosphere
superhydrophobic property [50]. Besides, the thickness of the for a long run. Fig. 7(b) shows the contact angles have little fluc-
bilayer coating increased by around 1 mm as seen in the cross- tuation and remain more than 155
when the coated sample sur-
sectional images Fig. 5(d2), which can be attributed to the suc- face contacts with droplets of pH from 1 to 7, indicting favorable
cessful coverage of SA on the surface. Generally, the modification of stability of the superhydrophobic coating in acid condition. As the
organic substance is beneficial to reduce the subtle flaws of the droplets turning from acidity to alkalinity, the contact angles show
coating and thus can enhance the barrier function for corrosion a downward trend. However, the coated coupon could still retain its
protection [39]. superhydrophobicity even in contact with water droplets at pH 13,
In view of the above analysis, the coating electrodeposited for indicating that the superhydrophobic coating also exhibits a rela-
60 min at the current density of 0.65 mA/cm2 after modification of tive stability in alkaline condition.
stearic acid is the best option. Fig. 5(e) shows the element com- Fig. 7(c) shows that when soaked for 6 h, the surface contact
positions of the electrodeposited compound on AZ31B Mg surface. angles are still as high as 160
. As soaking time extends to 12 h,
The atomic ratio of O/Ce close to 2 (66.38/32.53) indicates the superhydrophobicity of the coating shows a bit drop but remains
formation of the main composition CeO2 on the surface, which is up to 150
. With immersion time increased to 100 h, water contact
consistent with the XRD analysis (Fig. 4(60min)). angles on the surface declines gradually and is deprived of super-
XPS technique was utilized to further determine the chemical hydrophobicity due to the destructive attack of the corrosive me-
composition of the superhydrophobic coating. Fig. 6(a) shows that dium, which are consistent with that of the anti-performance tests.
chemical element of Ce, C and O are present on the super- This may be attributed to desorption of the stearic acid and the
hydrophobic coating. C1s spectrum can be fitted with three porous structure of the superhydrophobic surface, causing the in-
decomposition curves as showed in Fig. 6(b). Binding energy at vasion of chloride iron through air captured on the surface with the
immersion time prolonged. Fortunately, most areas of the coating
remained hydrophobic even after 100 h immersion, indicating
certain chemical stability.
Table 1
Crystalline sizes of the coatings electrodeposited for different times. Durability of the prepared superhydrophobic coating was car-
ried out by pushing the sample with a 50-g weight on the surface
Electrodeposition time (min) b (
) D (nm)
back and forth in a straight direction on the sandpaper of 600 grit.
5 0.781 10.391 Fig. 7(d) shows the wettability changes of the coupon with abrasion
15 0.963 8.428
distance from 0 to 240 cm. The water contact angles of the coating
30 0.812 9.995
45 0.760 10.679 decreases gradually with an increase in the abrasion distance,
60 0.734 11.057 indicting the damage of surface structure inch by inch. Before the
b ¼ the full width at the half maximum of the peak. D ¼ the average crystalline size,
coating was abraded for 140 cm, the surface was stably super-
calculated from the Scherrer equation D ¼ Kl/(bcosq), where Scherrer constant K is hydrophobic with water contact angles up to 150
. However, water
0.89; wavelength of the X-ray l is 0.15418; and diffraction angle q is about 14.25
. contact angles dropped below 150
with an increase in the abrasion
6 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210

Fig. 5. SEM morphology images and cross-section diagrams (a3, b3, c3) of the as-prepared coatings electrodeposited for different times at a current density of 0.65 mA/cm2: a1a3)
5 min; b1b3) 30 min; c1c3) 60 min; (d1 d2) the coating electrodeposited for 60 min and then modified with stearic acid (e) EDS spectra of the coating electrodeposited for
60 min, with the sampling location and mapping pictures of O, Ce, and Mg.
 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210 7

Fig. 6. XPS survey spectra of the superhydrophobic sample (electrodeposited for 60 min and modified with stearic acid): a) wide scan; b) C1s; c) Ce3d; and d) Fourier infrared
spectroscopy diagrams of the coating deposited for 60 min before and after modification of stearic acid.

distance, although the coating could maintained hydrophobic after shows the detailed polarization parameters. As shown in Table 2,
a wear distance of 240 cm on the surface of 600-grit sandpaper, the io of the superhydrophobic sample is more than two orders less
illustrating the mechanical stability of the coating needs to be than that of the bare magnesium, indicating the enhancement of
further strengthened in the future. Fig. 7(e) demonstrates that the the corrosion resistance. Although the current density of the
transition of coating from superhydrophobicity to hydrophobicity cerium oxides coated sample is also lower than that of the bare
after wear test is due to the change of surface structure from hi- magnesium, the superhydrophobic sample obviously shows better
erarchical nanosheets to relatively plain nanoparticles. corrosion protection performance. Even after 6 h immersion in
3.5 wt% NaCl solution, the current density of the coating has little
fluctuation. With the immersion time increased to 48 h, the cor-
3.3. Anti-corrosion performance
responding current density increased slightly, and corrosion effi-
ciency remained 89.63% close to that of cerium oxides coated
Tafel polarization enjoys a great popularity in evaluating the
sample, implying the relative stability of the superhydrophobic
instantaneous corrosion rate due to its convenience and quickness.
coating. However, as the immersion time up to 100 h, the current
The current density (icorr) and corrosion potential (Ecorr) detected
density increased a lot, which may be attributed to the pitting and
from Tafel polarizations usually imply the anti-corrosion perfor-
deterioration of the coating owing to the continuing attack by
mance of specimens. Generally, a lower icorr and a higher Ecorr are
corrosive iron Cl in the solution. This can be proved by the changes
related to a lower corrosion rate and so a better corrosion resis-
of the surface states detected by XPS technique as shown in Fig. 9.
tance. Undeniably, it is effective to compare the anti-corrosion
As shown in Fig. 9(a), while peaks intensity of Ce 3d and Ce 4d
performance of different samples by Tafel polarization, but note
decrease dramatically after 100 h immersion in the corrosive so-
that the corrosion rate of magnesium alloys evaluated by this
lution, the peaks of Mg 2p and Mg 1s are strong, indicating the
method may be larger [55]. Here, the inhibition efficiency h was
partly exfoliation of the coating and the formation of corrosive
calculated by the following equation [56]:
production including magnesium hydrate and magnesium oxides
as proved in Fig. 9(b) and (c). The peaks at 49.2 and 50.2 eV in Mg 2p
h ¼ (io - icorr)/io  100%
component spectra can be attributed to MgeOH and MgeO
respectively [57]. The peaks at 529.3, 531.0, 531.7, and 532.4 eV
where io and icorr denote the current density of the bare AZ31B Mg
are attributed to CeeO, MgeO, CeeOH and MgeOH respectively
and the superhydrophobic coupon in 3.5 wt% NaCl aqueous solu-
[58].
tion, respectively. Fig. 8 shows the polarization curves, and Table 2
8 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210

Fig. 7. Stability and durability of the superhydrophobic coating evaluated by the changes of water contact angles after different treatments: a) exposure to the atmosphere; b)
contact with droplets of different pH (1e13); c) immersion in 3.5 wt% NaCl solution; d) abrasion for different distances with 50-balance weight on the sandpaper of 600 grit; e) the
SEM image of the sample after abraded for 240 cm, insert is the corresponding optical photo.

Table 2
Tafel polarization parameters of the tested samples.

Sample Ecorr (V) icorr (A/cm2) h (%)

bare AZ31B Mg 1.585 4.71  104 e
cerium oxides coated 1.488 5.43  105 88.48
1h 1.372 1.14  106 99.76
6h 1.390 1.82  106 99.61
48 h 1.472 4.89  105 89.63
100 h 1.620 1.56  104 66.90

Ecorr ¼ the corrosion potential; icorr ¼ the corrosion current density; h ¼ the inhi-
bition efficiency, calculated from the equation h ¼ (io - icorr)/io  100% (see text for
definition).

low frequency are much larger than that of the bare AZ31B Mg as
well as the cerium oxides coated sample, an indication of better
corrosion resistance of the coupon with modification of stearic acid.
After immersed in corrosive solution for 48 h, the total resistance of
the coupon declined gradually, but was still more than one order of
magnitude higher than that of the bare magnesium, as seen in the
Fig. 8. Tafel Polarization curves of the bare AZ31B Mg, cerium oxides coated sample bode plots impedance diagram of Fig. 10(b). When the super-
without modification of stearic acid and the superhydrophobic specimens immersed in hydrophobic sample was exposed in 3.5 wt% NaCl solution for
3.5 wt% NaCl solution for 1, 6, 48, and 100 h.
100 h, the capacitance of the coating decreased a lot, and inductive
reactance was found in Nyquist plots graph (Fig. 10(a’)) and the
To further analyze the corrosion behavior of the samples, EIS bode plots of phase angles graph (Fig. 10(c)), indicating the occur-
was employed to the bare magnesium, cerium oxides coated rence of pitting corrosion the sample surface [59]. This may be
sample and the superhydrophobic coupon immersed in 3.5 wt% attributed to the destructive behaviors of Cl in the corrosive so-
NaCl solution for 1, 6, 48 and 100 h. As shown in Fig. 10(a), the lution. Despite the resistance decrease of the superhydrophobic
capacitance loop of the superhydrophobic sample both at high and specimen after 100 h immersion, the capacitance loop at high
 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210 9

Fig. 9. XPS survey spectra (aec) of the corroded position of the superhydrophobic sample after 100 h immersion in 3.5 wt% NaCl aqueous solution; (d) the real photo of the
superhydrophobic sample; inset (e) is corresponding to the bare AZ31B Mg sample.

frequency and total resistance of the coated coupon are still higher h ¼ (Rct - Rcto)/Rct  100%
than the pristine magnesium, exhibiting a better anti-corrosion
performance of the coated magnesium (Fig. 10(a’ and b)). where Rcto and Rct refer to the charge transfer resistance of the bare
To better conform the anti-corrosion performance of the AZ31B Mg and cerium oxides coated or the superhydrophobic
superhydrophobic sample in a quantitative way, two equivalent sample immersed in 3.5 wt% NaCl aqueous solution for different
circuit models were used to fit the EIS results. Generally, the times, respectively. As displayed in Table 3, Rct of the super-
capacitance loop at high or intermediate frequency domain is hydrophobic coupon is more than twenty times as large as that of
related to the outer layer and the electrochemical behaviors at low- the bare magnesium and also much larger than the Rct value of the
frequency region are attributed to the interface between coating cerium oxides coated sample. This confirms the necessity of the
and substrate [59]. As depicted in Fig. 10(d1 and d2), while model modification with steric acid and the importance of the composites
d1 is used to fit the EIS data with inductive loops, model d2 is coating applied on magnesium alloys for corrosion protection [61].
applied to fit the data with only capacitance loops. In the equivalent Interestingly, after 6 h exposure in 3.5 wt% NaCl solution, the Rct of
circuit models above, Rs stimulates the solution resistance; the the superhydrophobic sample slightly increased which can be
constant phase element (CPE) in replace of an ideal capacitance is attributed to the self-healing effects of cerium oxides [62,63] when
selected to compensate for non-homogeneity in the system due to corrosion occurs with the lasting exposure to the corrosive solution.
the rough or porous surface of the specimens [59]. CPEdl and Rct After 48 h exposure, the resistance of the superhydrophobic sample
stands for the electronic double-layer capacitance and charge- is close to that of the cerium oxides coated sample, similar to the
transfer resistance, respectively. L and R1 represent the inductive result of Tafel analysis. The obvious decrease of the corrosion
reactance and the relative resistance caused by the local corrosion resistance probably indicates that the corrosive solution has passed
in anodic region [60]. CPEc and Rc are adopted to fit the capacitance through the outer layer and gradually contacted with the substrate
and resistance of the superhydrophobic coating or other surficial [64], which can be due to the initial fading of the hydrophobic
oxides films. In order to understand better the corrosion resistance property as proved by the reduced water contact angles in Fig. 7(c).
of each sample, average values with error bar of Rct and |Z|f¼0.01Hz With an increase in the immersion time to 100 h, charge-transfer
(impedance modulus at low frequency of 0.01 Hz) were shown in resistance decreased to around 103 U cm2, but still many times
Fig. 10(e). The fitted parameters are listed in Table 3. h refers to the larger than Rct of the bare magnesium specimen. The reduce of the
inhibition efficiency and is calculated by the following equation Rct of the coated sample can be explained by the degradation of the
[10]: superhydrophobic coating and invasion of the chloride irons, which
was also confirmed by the wettability changes of the coating as
10 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210

Fig. 10. Nyquist plots (a) and bode plots (b, c) of the bare AZ31B Mg, cerium oxides coated sample without modification of stearic acid and the superhydrophobic specimen
immersed in 3.5 wt% NaCl solution for different times (solid lines are the corresponding fitting results). Inserted picture (a’) is the amplified Nyquist plots of the bare AZ31B Mg and
the superhydrophobic coating immersed for 100 h. (d1d2) the fitted equivalent circuits. (e) the standard deviation values of Rct and |Z|f¼0.01 Hz obtained via three parallel
experiments.

shown in the immersion test in 3.5 wt% NaCl aqueous solution corrosion performance remained a relatively good state, as
(Fig. 7(c)). The evident inductive reactance fitted by inductor L also proved by the inhibition efficiency h in Table 3. Also, the corrosion
indicates that the outer coating was broken and local corrosion protection performance tested by the Tafel polarization parameters
occurred at the interface between substrate and coating [59]. above basically agrees with that of EIS parameters, both indicative
Although the superhydrophobic coating was affected with the of relatively efficient anti-corrosion performance of the prepared
immersion time prolonged in the corrosive environment, anti- superhydrophobic coating.
 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210 11

Table 3
Fitted parameters of EIS spectrum of the samples tested.

bare AZ31B Mg cerium oxides coated 1h 6h 48h 100h

CPEc (U1 $cm2 $sn) e e 1.20  105 1.03  105 1.45  105 e
nc e e 0.87 0.86 0.75 e
Rc (U $cm2) e e 22086 21764 2636 e
CPEdl (U1 $cm2 $sn) 2.57  105 1.44  105 3.61  104 1.22  104 1.73  105 2.30  105
ndl 0.91954 0.88536 0.85 0.91 0.91 0.76818
Rct (U$cm2) 224 1908 7458 7597 1795 1096
L (H $cm2) 168.9 1295 e e e 2376
R1 (U$cm2) 180.7 1358 e e e 564.9
h(%) e 88.26 97.00 97.05 87.52 79.56
Chi-Square 0.01 0.002 0.0007 0.0006 0.0003 0.008

The standard deviation range for Rc, Rct and Rl value are between 1% and 6.3%, for CPE value is between 0.7% and 10%, for n value is between 0.1% and 3.8%. CPEdl ¼ constant
phase element in replace of the capacitance of electric double layer. Rct ¼ resistance of electric double layer. CPEc ¼ constant phase element in replace of the capacitance of the
as-prepared coating. Rc¼resistance of the as-prepared coating. L ¼ inductor used to fit the inductive reactance. R1 ¼ resistance occurring with the inductive loop. h ¼ inhibition
efficiency of the as-prepared coatings, calculated from equation h ¼ (Rct - Rcto)/Rct  100% (see text for definition).

Fig. 11. Optical photos of the self-cleaning tests of the bare AZ31B Mg (a1~a3) and the superhydrophobic coating (b1~b3).

3.4. Self-cleaning property of cracks. By electrodeposition at a current density of 0.65 mA/cm2

for 60 min (the optimal choice) and modification of stearic acid, the
Self-cleaning property of the bare AZ31B Mg and the super- as-prepared coating exhibited an excellent super-hydrophobicity
hydrophobic coating was also tested by spreading activated carbon with water contact angles more than 158
and extremely low
powder on the corresponding surface and then draining droplets adhesion ability. Moreover, the superhydrophobic coating showed
with a rubber-tipped dropper. As shown in Fig. 11, when water was a good stability in the atmosphere and in contact with droplets at
dropped on the bare magnesium alloy, carbon powder cannot be pH 1 to 13. Nevertheless, for real application, despite the obvious
washed away immediately due to the hydrophilicity of the surface. improvement of the corrosion resistance compared with the bare
When droplets were accumulated enough on the surface, the car- AZ31B Mg in 3.5 wt% NaCl solution, the long-term anti-corrosion
bon powder was just carried away by gravity of the water but a lot performance and the mechanical durability of the super-
of water and carbon powder were still left on the surface. In the hydrophobic surface need a further promotion.
case of the superhydrophobic coating, the carbon powder was
carried away as soon as the droplets drained off on the surface, Declaration of competing interest
indicting good self-cleaning property of the coating. This can be
well explained by the Cassie-Baxter model [65]. Generally, the air- The authors declare no competing financial interest.
cushion is formed on the surface due to micro/nanostructures of
the electrodeposited coating and thus reduces the contact area CRediT authorship contribution statement
between the water droplets and the coating, which allows water
droplets to easily roll off and carry away the dirt. Xiang Liu: Writing - original draft. Tian C. Zhang: Writing -
review & editing. Huaqiang He: Formal analysis, Methodology.
4. Conclusions Like Ouyang: Supervision. Shaojun Yuan: Funding acquisition,
Project administration, Resources, Supervision, Writing - review &
A stearic acid/CeO2 bilayer superhydrophobic coating was suc- editing.
cessfully fabricated on the AZ31B Mg by the combination of elec-
trodeposition and immersion method. During the Acknowledgements
electrodeposition process, a hierarchical nanosheets structure was
grown on the surface. With an increase in electrodeposition time The authors are grateful for the financial support of the National
from 5 to 60 min, the coating became denser and thicker regardless Natural Science Foundation of China (21676169, 21978182), the
12 X. Liu et al. / Journal of Alloys and Compounds 834 (2020) 155210

measurement of XRD and Raman spectra by the Institute of New alloy with enhanced corrosion resistance by combining micro-arc oxidation
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