Research Article

Cite This: ACS Sustainable Chem. Eng. 2018, 6, 10960−10968

Bioinspired Slippery Zinc Phosphate Coating for Sustainable

Corrosion Protection
Tengfei Xiang,† Shunli Zheng,‡ Min Zhang,§ Hisham Rabia Sadig,† and Cheng Li*,†
†
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, 29 Jiangjun Avenue, Jiangning
District, Nanjing, Jiangsu 211106, China
‡
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798,
Singapore
§
School of Mathematics and Computational Science, Anqing Normal University, 1318 Jixian north road, Yixiu District, Anqing,
Anhui 246000, China
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ABSTRACT: In this work, a slippery zinc phosphate coating composed

with homogeneous pores was successfully fabricated by a facile method
which was inspired by nepenthes pitcher plants. The as-prepared coating
exhibited superhydrophobicity with a large water contact angle (WCA) of
156.6° after modification with fluoroalkylsilane (FAS) ethanol solution. A
slippery surface with highly water-repellency was achieved by completely
filling the Krytox 100 lubricant into the pores. Generally, based on the
stable and low-volatile lubricant, a slippery surface can provide a better
corrosion resistance than that of superhydrophobic surface for metals.
Herein, this novel slippery coating also displayed an efficient and
sustainable anticorrosion performance. The corrosion resistance was
enhanced by 7 orders of magnitude compared with that of bare mild steel
substrate. More importantly, the corrosion inhibition efficiency of this
coating is still higher than 99.99% even after immersion in NaCl solution
for 6 weeks, demonstrating an excellent long-term stability for corrosion protection. The coating has great potential to be used
as antibacterial, anti-icing and water harvesting films.
KEYWORDS: Slippery surface, Phosphate coating, Superhydrophobic, Corrosion resistance

■ INTRODUCTION
Corrosion occurrence is a big issue in the world, which
undermines the global economy and environment. Many
industries including automobiles, marine and pipeline are
suffering from corrosion severely.1−4 Especially for many future
materials which cannot be replaced because of the cost
consideration and a long service time requirement. Thus, the
knowledge and technology for sustainable corrosion protection
is in great demand. Generally, a coating is used for isolating the
bulk materials from corrosive attack.5−12 However, some
coatings based on organics are not environmentally friendly.
Besides, it would accelerate the corrosion rate when the
coating is broken.13,14 Thus, a green coating with long-term
stability is urgent to be developed.
In recent years, large numbers of novel materials have been
developed which were bioinspired from lotus leaves, rose petals
and nepenthes pitcher plants.15−19 As one of the brilliant
plants, nepenthes pitcher plants use its special structure to
lock-in a medium liquid to protect surface.20 The well matched
solid and liquid surface energies combining with a rough
structure, generate a stable state in which the liquid fills the
structure and the liquid forms a perfect overlying film.21
Bioinspired from nepenthes pitcher plants, Aizenberg and her
co-workers first fabricated a slippery liquid infused porous
surface (SLIPS), which shows superior liquid repellency with
self-healing property.19 More significantly, they made a
definition of the requirements to form a defect-free slippery
surface.
First of all, the infused liquid must wick into and adhere
within the substrate stably. This requirement can be satisfied
by using a micronano structure combining with chemical
affinity for the liquid. For the liquid with a long-term storage, a
semiclosed porous structure is a better choice rather than an
opened porous structure. Second, the chemical affinity
between the substrate and the infused liquid should be higher
than that between the external liquid and the substrate (a
lower total energy is the preferred wetting state). To satisfy this
requirement, the total interfacial energies of the substrate that
are entirely wetted by the immiscible test liquid A (EA = RγS‑A
+ γA), or a lubricating liquid B with El (El = RγS−B + γB‑A + γA)
or without E2 (E2 = RγS−B + γB) a fully wetted immiscible test
liquid standing on top of it should meet the following
relationship:19,22
Received: May 22, 2018
Revised: June 29, 2018
Published: July 1, 2018

© 2018 American Chemical Society 10960 DOI: 10.1021/acssuschemeng.8b02345

ACS Sustainable Chem. Eng. 2018, 6, 10960−10968
ACS Sustainable Chemistry & Engineering
ΔE1 = E1 − EA < 0 (1)
ΔE2 = E2 − EA < 0 (2)
where R is the roughness of the substrate, γS‑A, γS−B, γB‑A, γA,
and γB represent the surface energies of the solid−liquid A
interface, solid−liquid B interface, liquid A-liquid B interface,
liquid A-vapor interface, and liquid B-vapor interface,
respectively. And the third requirement is that the infused
liquid and the tests liquids must be immiscible. The last two
requirements can be gratified by using low surface tension
perfluorinated liquids with low-volatilility as the infusion oil
which is immiscible with most of liquids and therefore can
form a slippery interface on the substrate (ΔE1 < 0, ΔE2 < 0).
Most of the porous structures fabricated on metals were
based on layered double hydroxide (LDH), anodic aluminum
oxide (AAO) and nanoparticles.23−29 However, the metals
which can be used to fabricate LDH and AAO directly are
limited. Besides, the incorporation of nanoparticles into the
coatings should be demonstrated weak adhesion between
substrate and particles. Thus, a coating can be used to fabricate
on metals by chemical conversion or other means with high
adhesion is in urgent need. Zinc phosphate (ZP) coating, a
traditional green corrosion-resistant conversion coating,30−36
which owns a special semiclosed porous structure and a large
adhesion with substrate, is an excellent candidate coating to
offer a large space to store the infused liquid. Compared with
other porous coatings, phosphate coating can be fabricated on
metals with high adhesion quickly, and the pores can be
controlled easily by changing the parameters of the phosphate
reaction. Followed by surface functionalization to match with
the chemical nature of the infused lubricant, a stable slippery
surface can be formed. To date, even though numerous
scientists have studied the corrosion resistance of ZP coating,
few researchers investigated the anticorrosion performance of a
slippery ZP coating and its long-term stability. In this work, we
first fabricated a ZP coating based on Zn−Ni (ZN) coating
and then infiltrated nonvolatile and immiscible lubricant to
generate slippery surface. Then, we focus on study the
corrosion protection performance of the slippery surface.
■
EXPERIMENTAL SECTION
Materials and Chemicals. Mild steel (composition in wt %: C ≤
0.1, Mn ≤ 0.5, P ≤ 0.035, S ≤ 0.035, with the rest being of Fe) was
cut into 5 × 2 × 0.1 cm as substrates, the composition of ZN plating
bath was given in our previous works.6,37 Briefly, it contains 35 g·L−1
boric acid (H3BO3), 75 g·L−1 zinc chloride (ZnCl2), 110 g·L−1 nickel
chloride hexahydrate (NiCl2·6H2O), 35 g·L−1 ammonium chloride
(NH4Cl), 200 g·L−1 potassium chloride (KCl), 20 g·L−1 potassium
citrate monohydrate (K3C6H5O7·H2O) and 0.1 g·L−1 sodium
dodecylbenzenesulfonate (C18H29NaO3S). The pH of bath plating
was kept at 5.0−5.5, which was adjusted by hydrochloric acid (HCl)
and sodium hydroxide (NaOH). Zinc dihydrogen phosphate
(Zn(H2PO4)2·2H2O), phosphoric acid (H3PO4), nickel nitrate
hexahydrate (Ni(NO3)2·6H2O), manganese nitrate dihydrate (Mn-
(NO3)2·2H2O), sodium chloride (NaCl), ethanol and the plating
chemicals were all analytical pure grade and purchased from Nanjing
Chemical Reagent Co., Ltd., China. Fluoroalkylsilane (FAS) was
obtained from Sigma-Aldrich. Lubricant (Krytox 100) was offered by
Dupont. All the chemicals were used without any further treatment.
Self-made deionized water was used in the experiment process.
Fabrication of ZP Coating. Before electroplating, the substrates
were degreased, acid pickled and activation first. The details also can
be seen in our previous works.6,37 After that, the ZN coating was
deposited under the current density of 4 A·dm−2 at 35 °C for 20 min
by a direct current power supply, the plating bath was stirred at a
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speed of 200 r·min−1 during the plating process. Subsequently, the ZN
coating was immersed into the 100 mL phosphate solution which
contains 40 g·L−1 Zn(H2PO4)2·2H2O, 20 g·L−1 H3PO4, 4 g·L−1
Ni(NO3)2·6H2O and 11 g·L−1 Mn(NO3)2·2H2O for 3, 5, and 10
min, respectively. The pH was kept at 1−2. The temperature of the
solution was kept by a water bath at 40 °C. Finally, the sample was
cleaned by deionized water and dried in air, and the ZP coating was
obtained.
Sample Modification and Lubricant Infusion. For a perfect
wettability by the lubricant, ZP coating was first modified by FAS
solution (10 mM FAS of ethanol solution) for 30 min and then dried
at 70 °C for 2 h in an oven. Afterward, 20 μL lubricant Krytox 100
was homogeneously infused into the phosphate coating by a spin-
coater with a speed of 2000 r·min−1. After infusion, these samples
were placed vertically at ambient environment for 12 h to drain off the
excess liquid. For a better readability, the total abbreviation was
summarized here. ZN and ZP coating represent Zn−Ni and Zinc
phosphate coating (based on Zn−Ni coating), respectively. MZP
stands for the modified zinc phosphate coating, SZP on behalf of the
slippery zinc phosphate coating while after the lubricant infused into
the modified ZP coating.
Characterization. The morphologies and elemental compositions
of samples were observed by a field emission scanning electron
microscope (FE-SEM, S-4800, Hitachi, Japan) equipped with an
energy dispersive spectroscopy (EDS). The structure of ZN and ZP
coatings were detected by an X-ray diffraction (XRD, D8 Advance,
Bruker, Germany) using filtered Cu Kα as a radiation source (λ =
0.15406 nm) at a scanning rate of 4°/min from 10° to 90° of 2θ. The
water contact angle (WCA) and contact angle hysteresis (CAH) was
measured by a contact angle meter (SL200B, Solon Tech., China)
with a 6 μL deionized water droplet. Five different positions on each
sample were tested to obtain the average WCA value.
The corrosion resistance of samples was evaluated by electro-
chemical impedance spectroscopy (EIS) and potentiodynamic
polarization curves in 3.5 wt % NaCl solution (pH 5.9) using an
electrochemical workstation (CHI 750C, Shanghai Chenhua Instru-
ment Corporation, China) at room temperature. Before testing, the
samples were immersed into NaCl solution for 30 min to obtain
stable open circuit potentials. The measurements were performed
with a standard three-electrode system, a saturated calomel electrode
(SCE) and a platinum (Pt) electrode were acted as a reference
electrode and a counter electrode, respectively. The tested sample
with an exposed area of 1 cm2 was used as the work electrode. The
corrosion potential (Ecorr) and corrosion current density (Icorr) can be
acquired from the potentiodynamic polarization curves (scanning rate
of 1 mV·s−1) using extrapolation method. The EIS was carried out at
the open circuit potential from 10−2 Hz to 105 Hz with a sinusoidal
perturbation signal of 5 mV amplitude.
■
RESULTS AND DISCUSSION
Surface Morphologies of Samples. To investigate the
effect of phosphating time on the morphologies of ZP coating,
the coating formed with different reaction time were detected.
As shown in Figure 1 (a), the ZN coating exhibited a flat and
dense structure composed of “sand-like” substances with an
average diameter about 500 nm. After immersion into the
phosphate solution for 3 min, the ZP coating showed a
“honeycomb” hierarchical structure which can be seen in
Figure 1 (b), and the “cells” were consisted with homogeneous
nanopores which like flower petals with a diameter of 250 nm.
While prolonging the reaction time to 5 min, the size of the
nanopores showed an expanded trend and the diameter is
about 300 nm, the depth of these pores looks deeper.
However, when the reaction time reached 10 min, the pores
transferred to collapse. This phenomenon may be related to
the ZP coating formation process. During the formation of ZP
coating, the crystals would be extruded with each other, and
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4H2O. Moreover, a low peak of Zn3(PO4)2·4H2O and

Mn2Zn(PO4)2 also can be detected. However, when the
reaction time was increase to 10 min, another two peaks
appeared in 35.9° and 74.3° which consist with (NiHPO4)·
3H2O (JCPDS No. 39-0706) and Ni7P3 (JCPDS No. 03-
1101). That may be related to that once the zinc phosphate
coating was dissolved, the surface is progressively enriched in
Ni by a dissolution-redeposition process with a consequent
potential shift toward more anodic potentials,33−35 and as a
result, some compounds which containing Ni formed, not zinc
phosphate coating. This was in keeping with the morphological
changes. Thus, in this work, we only focus on researching the
ZP coating with the reaction time of 5 min (a better phosphate
coating). To confirm the composition of ZP coating, EDS was
applied to monitor the elements of coating. Mn element can be
seen in Figure 2 (b) with a low content, which is fitted well
with the XRD consequence. As a whole, the ZP coating was
mainly composed of Zn3(PO4)2·4H2O.
Surface Wettability. The chemical affinity can be
evaluated by the surface wettability. Figure 3 exhibited the
Figure 1. Surface morphologies with different magnification of (a)
ZN coating, (b), (c), and (d) ZP coating generated with 3, 5, and 10
min, respectively.

the pores may be broken in this process, especially for the

hydrogen escaping.31,38 Another reason is that the ZP coating
would be dissolved in the phosphate solution after the
substrate was covered by the coating completely for a long
time.33,34
Surface Composition of Samples. XRD technique was
used to detect the surface composition of ZN and ZP coatings.
As depicted in Figure 2 (a), the peaks in the position of 42.8°,
62.3°, 78.7°, and 89.4° are corresponding to the (411), (600),
(721), and (811) planes of γ-Ni5Zn21 (JCPDS No. 06-0653),
several Fe peaks can be seen in ZN coating demonstrating that Figure 3. Contact angle images of 6 μL water droplet on (a) ZN
the substrate can be detected. After reacted in the phosphate coating, (b) ZP coating, (c) MZP coating, and (d) SZP coating. (e)
solution with different time, some new peaks appeared. It can Images of the slippery process with 6 μL water droplet on SZP
be seen that after reacting for 3 min, three weak peaks were coating.
generated in the position of 9.7°, 19.4° and 31.3° which
corresponding to the (020), (220), (241) planes of Zn3(PO4)2· images of 6 μL water droplets on the as-prepared coatings. It
4H2O (JCPDS No. 37-0465). While prolong the reaction time, can be seen that the WCA of ZN coating is about 85.2°, which
these peaks intensity become sharper, demonstrated a better may be related to the surface roughness and passivation. While
phosphate coating. Besides, there is a peak in 46.8° also after phosphating treatment, water droplet spread on the
matches well with the position of (371) plane of Zn3(PO4)2· surface quickly and permeated through the surface, and the

Figure 2. (a) The XRD patterns of ZN coating reacted in the phosphate solution with different time, (b) the EDS spectra of ZN coating after
reacted in phosphate solution for 5 min.

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Figure 4. Electrochemical impedance spectroscopy (EIS) measured in 3.5 wt % NaCl solution. (a) Impedance (|Z|) and (b) phase of Bode plots
for bare mild steel, ZN, ZP, MZP, and SZP coatings. (c) and (d) the equivalent circuits for the four coatings and mild steel substrate, respectively.
(e) Resistance of the barrier layer for samples obtained from modeling results.
WCA sharply decreased to 0°. The porous structure of ZP
coating must be responsible for the superhydrophilicity. After
decorating with FAS, the water droplet can stay on the surface
with a minimized contact area with WCA about 156.6°, as
shown in Figure 3(c). The change of the microstructure can be
ignored because the FAS was only as a subnanometer
layer.39,40 The superhydrophobicity of MZP coating was result
from the “air cushion” due to the trapped air among the porous
structure.40−42 Moreover, the WCA decreased to 122.8° after
infusion of the Krytox 100, as shown in Figure 3(d). The
Krytox 100 exhibits a low surface tension about 16−20 mN
m−1 while water owns about 72.5 mN m−1 at 26 °C.25 Thus,
combining with the rough structure, it meets the second
requirement very well. The water immiscible lubricant would
completely occupy the pores of MZP coating because of the
well chemical affinity, leaving no space for air. Therefore, the
contact interface transferred from the solid−air−water state to
solid-lubricant-water state. Moreover, water can slide off from
the coating with a low CAH about 8° revealing superior water
repellency. The sliding process can be seen in Figure 4 (e),
which were obtained from video shots and showed a slow
sliding velocity on this coating.
■ CORROSION RESISTANCE
Corrosion Protection Performance of Samples. As an
effective and powerful measurement, the EIS technique was
used to evaluate the anticorrosion performance of samples. EIS
experiments were all conducted in 3.5 wt % NaCl aqueous
solution. The Bode-module and Bode-phase plots can be seen
in Figures 4 (a) and (b). As a general rule, a larger |Z| in low
frequency indicates a better corrosion resistance.40 Herein, it
can be observed that the |Z| of SZP coating is the largest, and
there is no doubt that the value of bare mild steel is the lowest.
Besides, the |Z| of ZP coating is larger than that of ZN coating
which means that the phosphate coating can provide a better
corrosion protection for mild steel in the NaCl solution.
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Moreover, the MZP coating can offer further corrosion
protection compared with ZP coating, with a larger value of |
Z| in low frequency. From the Bode-phase plot, the SZP
coating exhibited an extremely wide and high phase angle in a
very broad frequency domain, suggesting that a highly stable
and compact coating was provided by the SZP coating.43,44 As
for the phase plots of these coatings, the large phase angle peak
could indicate the interaction of two time constants.44
According to previous works,40−42 the charges transferred in
coatings system should pass the solution-coating and coating-
substrate interface during the process of electrochemical test.
Therefore, an equivalent circuit as shown in Figure 4 (c) was
used to fit the EIS results of the coating. Where Rs on behalf of
the solution resistance, Rc represent the coating resistance, Rct
corresponds to the charge transfer resistance of the interface of
coating and substrate while the Cdl means the capacitance of
double electrode layer. The CPEc was used to replace the
coating capacitance due to the distribution of relaxation times
resulting from different degrees of heterogeneities at the
electrode surface.45 The CPE can be mathematically expressed
as below:45,46
ZCPE = [Q 0(jω)n ]−1
Where Q0 is a proportionality factor, j is an imaginary unit
(3)
while ω is an angular frequency (ω = 2πf), n is an adjustable
parameter with the value always between −1 for a prefect
inductor and 1 for a perfect capacitor. With regard to the bare
mild steel, there is only a thin passive oxide layer as the barrier
layer, so the corrosive ions can penetrate into substrate easily.
Thus, the equivalent circuit in Figure 4 (d) can be used to
fitting the EIS result of bare mild steel. The barrier layer
resistance (approximate to the Rct) of each coating were
obtained from the fitting results and showed in Figure 4 (e).
The Rbarrier of bare mild steel is 613.9 Ω cm2 while the value for
ZN coating is 5047 Ω cm2 which means the ZN coating can
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Figure 5. (a) The potentiodynamic polarization plots of samples, (b) the corrosion current density calculated from the plots.
further protect mild steel from corrosion. In the meantime, the
ZP and MZP coatings also show better corrosion resistance
than ZN coating. Most importantly, the SZP coating displayed
an unbelievable corrosion resistance and the Rct is as large as
1.091 × 1010 Ω cm2, which is 5 orders of magnitude higher
than that of MZP coating. The above results fit well with those
of Bode-module and Bode-phase plots. As a consequence, the
SZP coating demonstrated a fantastic anticorrosion perform-
ance.
Potentiodynamic polarization (Tafel) method was further
adopted to quantitative estimate the anticorrosion performance
of samples. The corrosion potential (Ecorr) and corrosion
current density (Icorr) were calculated from the plots by
extrapolation method. As can be seen in Figure 5 (a), the plots
of bare mild steel, ZN, ZP, and MZP coatings were all
exhibited a lower cathodic slope than anodic slope, which
means that the Ecorr changed slowly with the increasing
potential, it implies that the coatings and the bare mild steel
were protected from the hydrogen evolution reaction.46
Besides, the Ecorr of ZN, ZP and MZP is lower than that of
bare mild steel, indicating that these coatings protected
substrate from corrosion by cathodic protection and would
sacrifice themselves first.47 The Ecorr of ZP and MZP coatings is
higher than that of ZN coating must be related to the
phosphate film and the trapped air among the porous
structure, respectively.38,48 While after infusing lubricant into
the modified phosphate coating, the Ecorr transferred toward to
positive direction, revealed a lower corrosion probability.29 In
addition, the Icorr of samples were calculated and displayed in
Figure 5 (b). The bare mild steel showed the largest Icorr
(9.209 × 10−5 A cm−2), demonstrating the fastest corrosion
rate.49 It can be also found that the Icorr of ZN and other
coatings were lower than that of bare substrate. Excitingly, the
Icorr of SZP is dramatically decreased to 1.927 × 10−11 A cm−2,
revealing an extremely low corrosion rate.
The corrosion inhibition efficiency was calculated by the
following equation:50
Ei = (Icorr b − Icorr c)/Icorr b × 100%
(4)
where Icorrband Icorrcare the corrosion current density of bare
substrate and coated samples, respectively. It can be calculated
that the Ei of ZN, ZP, MZP, and SZP coatings is about 85.31%,
92.61%, 99.47%, and 99.99%, respectively, as shown in Figure
5 (b). These results were coincident with the above resistance
values, indicating that the corrosive ions are strongly restrained
by the protective property of coatings.
Corrosion Inhibitive Mechanism. As can be seen in
Figure 6 (a), the thickness of the MZP coating is about 1.5 μm,
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Figure 6. (a) and (b) are the cross section images of MZP and SZP
coatings, the images on top right corner are those with high-resolution
while the bottom left corner images are the coatings immersed in
water. (c) and (d) are the schematic illustrations of MZP and SZP
coatings tested in 3.5 wt % NaCl solution.
and the morphology still kept porous. When immersing the
coating into water, a white layer appeared, demonstrated the
existing of the air layer. In Figure 6 (b), the morphology of this
coating cannot be seen clearly because it was filled with
lubricant, it protected the coating very well even immersing
this coating into water. Thus, based on the FESEM images, the
WCH, XRD, EDS results as well as the corrosion resistance
results, the corrosion inhibitive mechanism for the coatings can
be proposed. The ZP coating was almost composed of
Zn3(PO4)2·4H2O which has very low conductivity, the
corrosive ions can hardly transferred freely.51,52 Moreover,
the micro galvanic corrosion can only occur among the
phosphate pores separately.53 Furthermore, the transport of
oxygen to substrate is hindered by the protective phosphate
coating between the substrate and the electrolyte due to the
homogeneous porous structure.54 Thus, the corrosion
resistance of ZP coating is higher than that of ZN coating.
With regard to the MZP coating with superhydrophobicity [as
shown in Figure 6 (a)], a large amount of air trapped inside the
unique structure as the “air cushion” can minimize the contact
area between NaCl aqueous solution and the coating, thus
preventing the NaCl solution penetrating into the surface.10,11
Second, the “capillarity” acts as a critical role in the protection
process,50 the corrosive ions of Cl− can be repelled by the
Laplace pressure. Third, the FAS and air layers own high
potential and large impedance, which can result in a well
anticorrosion performance.40 For the SZP coating, the
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Figure 7. (a) WCA of SZP coating immersion in 3.5 wt % NaCl solution for different time. (b) and (c) are the corresponding impedance (|Z|) and
phase of Bode plots. (d) Resistance of the barrier layer obtained from modeling results.

Figure 8. Potentiodynamic polarization plots of SZP coating immersed in 3.5 wt % NaCl solution for different time and (b) the corrosion current
density calculated from the plots.

lubricant would fill the pores and the air must be pushed out,
as shown in Figure 6 (b). The lubricant can serve as a barrier
layer to prevent the corrosive ions permeating into
substrate.23−27 The lubricant Krytox 100 is very stable in
aqueous solution and immiscible with water, therefore, it can
provide a superior corrosion protection for the mild steel
substrate.
Sustainable Corrosion Protection. For most of super-
hydrophobic coatings, they cannot offer sustainable protection
for substrate due to its brittle special structure. When the
structure was broken, it can become a pass route for corrosive
ions and accelerate the corrosion rate. In addition, the “air
cushion” will be depleted with a long time and could not
provide as a protection layer.55,56 Thus, it is a challenge for the
superhydrophobic coating to keep its superhydrophobicity
when immersion in aqueous solution for a long time. As an
alternative coating, lubricant-infused slippery coating exhibits a
better stability in aqueous solution.19 As shown in Figure 7 (a),
the SZP coating exhibited a large contact angle of 118.4 ± 4.1°
even after immersion in NaCl solution for 6 weeks, which is
10965
only 4.4° lower compared with that before test, demonstrating
an outstanding stability.
To illustrate the sustainable protection performance of SZP
coating, electrochemical measurement was also applied. As can
be seen in Figure 7 (b), the value of |Z| in low frequency
decreased with increasing of the immersion time. Meanwhile,
the Bode-phase plots were also presented a declined trend. The
phase angle sharply decreased in the middle frequency domain
after immersion for 4 weeks for the SZP coating, which
demonstrated that the anticorrosion performance was
decreased with a long immersion time. That likely due to
the lubricant being partly removed from the substrate because
of the positive spreading coefficient of lubricant in aqueous
solution,57 and part of the lubricant may be dissolved in the
water limitedly given its relatively low viscosity, making the
lubricant layer thinner.58−60 Thus, the corrosive ions can
penetrate into the coating/metal interface easier from the tip
or the edge of the phosphate coating and result in the decrease
of phase angle.61 Also, the barrier resistance was also fitted by
the same equivalent circuit in Figure 4 (c). Even after
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immersion for 6 weeks, the Rbarrier can still keep as large as
5.339 × 108 Ω cm2, much higher than that of MZP coating of
about 3 orders of magnitude. The corresponding results can be
seen in Figure 7 (d). As a result, the above results indicated
that SZP coating has a remarkable sustainable corrosion
protection performance for the bare mild steel substrate.
The Tafel plots of SZP coating after immersion in 3.5 wt %
NaCl solution for different time were shown in Figure 8 (a). It
can be found that the Ecorr shifted to negative position after
immersion in NaCl solution, indicating that the corrosion
would occurs easily. However, with the increasing immersion
time, the Ecorr of the coating had a slight rise, a thin lubricant-
water layer would be generated between the coating and
solution,57 and thus the corrosion potential increased. The Icorr
of samples were calculated and displayed in Figure 8 (b).
There is no doubt that the Icorr increased after immersion in
NaCl solution. However, the value is still far less than that of
MZP coating even after immersion for 6 weeks (1.373 × 10−10
A cm−2). The Ei of the immersed samples were all higher than
99.99%. It can be concluded that the SZP exhibited a glaring
sustainable corrosion protection performance.
■
CONCLUSIONS
We have developed a novel slippery zinc phosphate coating on
mild steel substrate successfully by a simple and environ-
mentally friendly method. The morphology of this coating was
investigated and showed a homogeneous porous structure. The
XRD and EDS results demonstrated that the coating was
mainly composed of Zn3(PO4)2·4H2O. It showed super-
hydrophobicity with a WCA of 156.6° after modification
with the low surface energy material of FAS. When infusing the
lubricant into the surface, the WCA decreased to 122.8°. Even
though the WCA decreased, the anticorrosion property was
increased sharply due to the excellent water-repellency of
lubricant. The corrosion resistance of SZP coating was
significantly enhanced by 5 orders of magnitude compared
with that of MZP coating. After immersion this novel SZP
coating into NaCl solution for 6 weeks, it still exhibited a
superior anticorrosion performance with corrosion inhibition
efficiency higher than 99.99%. This novel coating will be of
great significance to retard the long-standing corrosion
problem and will enlarge the application of engineering metals.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +86-25-52112902; fax: +86-25-52112626; e-mail:
licheng@nuaa.edu.cn.
ORCID
Cheng Li: 0000-0002-4251-1824
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank the project funded by the Priority Academic
Program Development (PAPD) of Jiangsu Higher Education
Institutions and the Funding of Jiangsu Innovation Program
for Graduate Education (No. KYLX16_0340).
■
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10968 DOI: 10.1021/acssuschemeng.8b02345

ACS Sustainable Chem. Eng. 2018, 6, 10960−10968