Journal of Hazardous Materials 377 (2019) 142–151

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Polydopamine modified polyaniline-graphene oxide composite for T

enhancement of corrosion resistance
⁎
Ning Yanga,b,c, Tao Yangd, Wei Wanga,b,c, Huaiyin Chena,b,c, Weihua Lid,
a
Institute of Oceanology, Chinese Academy of Sciences, Qingdao, 266071, PR China
b
Open Studio for Marine Corrosion and Protection, Pilot National Laboratory for Marine Science and Technology, Qingdao, 266000, PR China
c
University of Chinese Academy of Sciences, Beijing, 100039, PR China
d
College of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai, 519082, PR China

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

Keywords: In this study, the composite of two-dimensional graphene oxide (GO) nanosheets and button-shaped polyaniline
Polydopamine (PANI) was synthesized and further modified by polydopamine (PDA). The obtained PDA-PANI-GO composite
Polyaniline was used to enhance the corrosion protection ability of nontoxic water-based alkyd varnish (WAV). The chemical
Graphene oxide composition, functional groups and surface morphologies of GO, PANI-GO and PDA-PANI-GO composites were
Alkyd varnish
characterized by XRD, FT-IR XPS and SEM. The anticorrosion performance was demonstrated by electrochemical
Electrochemical measurements
Corrosion resistance
impedance spectroscopy measurements and polarization tests. Due to the physical barrier effects and surface
hydrophobicity of PANI-GO composite, the approaches of the caustic substances to the surface of the metal was
inhibited, while the highly adhesive PDA molecules reinforced compatibility between fillers and WAV. As re-
sults, PDA-PANI-GO composite introduced WAV enhanced corrosion prevention performance. Under the optimal
conditions, where the ratio of PDA to PANI-GO was kept at 2:1, the impedance values increased by over two
orders of magnitude compared with bare steel.

1. Introduction
Corrosion leads to multitudinous potential security matters and
pollution issues simultaneously costing extraordinary losses of eco-
nomics every year. Corrosion products contain quantities of heavy
metals, such as chromium and nickel, which negatively affect people's
health in rather small amounts [1]. Among all the treatments used to
slow corrosion damage to materials, organic coating is a very com-
monly used approach depends primarily on its high cost performance
and excellent corrosion resistance [2,3]. Its working mechanism can be
generalized as mechanically isolating materials from the aggressive
corrosive substances. The most commonly used organic coatings in-
clude epoxy, acrylics, urethanes, et cetera. However, organic solvent-
based coatings consist of liquefying agents that are meant to release
contaminative volatile organic compounds (VOCs) into atmosphere
during production, transportation and use [4–6]. The toxic VOCs are
associated with many health risks and environmental problems, for
instance, respiratory diseases and ozone depletion [7]. Environmental
protection department of many countries have established regulations
to limit the emissions of VOCs [8–10]. To reduce the environmental
impacts and lower toxicity releasing, eco-friendly water-based coatings
with low content of VOCs have become the leading anticorrosion
methodology [11,12]. Due to their susceptibility to environmental
conditions, it is difficult for traditional water-based coatings to achieve
ideal effects of corrosion protection [13,14]. Therefore, enhancing the
resistance to corrosion of water-based coatings is a situation demanding
prompt solution. Alkyd resin, with good comprehensive performance,
ample resources in raw material, low cost and low toxicity, is one of the
most extensively used organic coatings, accounting for about 25% of all
coatings in recent years [15]. Deficiencies of alkyd varnish show up
mainly in low hardness, lacking weather resistant and poor corrosion
resistance [16]. Meanwhile, alkyd resin molecular structures consist of
ester groups, hydroxyl groups, carboxyl groups and unsaturated double
bonds which lead to the supreme versatility for alkyd resin to be
modified by reacting with various functional monomers [17].
Graphene, a monolayer layer of sp2-hybridized carbon atoms ar-
ranged in a two-dimensional hexagonal lattice, has been touted as one
of the strongest known materials [18]. Graphene presents many striking
characteristics like size effects [19], hydrophobicity [20] and con-
ductivity [21]. A variety of functional groups such as hydroxyl, car-
bonyl, and carboxyl groups distribute on surfaces and edges of gra-
phene [22]. In order to improve the mechanical strength as well as the

⁎
Corresponding author.
E-mail address: liweihua@qdio.ac.cn (W. Li).

https://doi.org/10.1016/j.jhazmat.2019.05.063
Received 17 July 2018; Received in revised form 3 April 2019; Accepted 25 May 2019
Available online 28 May 2019
0304-3894/ © 2019 Elsevier B.V. All rights reserved.
N. Yang, et al.
corrosion protection ability of coatings, many attentions have been paid
to use graphene as reinforcement [23]. A physical insulation layer can
be formed by filling the stacking graphene nanosheets into flaws of the
coating or superimposing these nanosheets in the coating, the surface
energy of the coating decreased while the hydrophobicity of the coating
enhanced, the migration of the corrosive substances to the metal sub-
strate could be hindered effectively [24]. In addition, the electrical
conductivity of coatings can be improved due to the appearance of
these graphene, electrons transferred from the anodic sites of the metal
to the coating rapidly, the precipitations of the metal ions could be
prevented and the formation of rusts could be hindered. Graphene was
added into waterborne polyurethane composite coating, the antic-
orrosion mechanism was also proposed, that is, the movement of the
polymer chain in the coating can be limited by steric effect of the
graphene, the permeability of corrosive substances decreased and the
corrosion resistance of the coating was significantly improved [25,26].
Whereas, recent advances showed that there is a lack of compatibility
between graphene and resins, which has restricted the application of
graphene in coating industry [27]. Due to the functional groups on the
surfaces and edges of the nanosheets, graphene oxide (GO) is now
proved to be an important functionalized graphene derivative with
extraordinary performances [28]. Ramezanzadeh et al. [29] prepared
graphene oxide/polyurethane coating, covalent bonds formed between
polyisocyanate with graphene oxide, the corrosion resistance was
greatly improved by adding 0.1 wt% GO in polyurethane coating.
Krishnamoorthy et al. [30] found that by adding graphene oxide in
alkyd resin as fillers and the obtained composite coating was char-
acterized by acid immersion test, electrochemical measurements and
antibacterial test. The results show that the composite coating had good
acid resistance performance and could inhibit the growth of Escherichia
coli, Staphylococcus aureus and Pseudomonas aeruginosa. Though these
composites modified coatings present excellent functional character-
istics, the binding force of individual elements may not be strong en-
ough due to the linear polymer chains and eventually those factors lead
to unsatisfactory in corrosion protection performance [31].
The conducting non-linear polyaniline(PANI) and GO composites
have been applied in many aspects such as supercapacitors [32–34],
sensors [35–37], microwave absorption [38], electromagnetic absorp-
tion [39], attributes to their mechanical properties, electrorheological
performance and barrier performance [40]. Polydopamine shares si-
milar geometry with the main component of viscous proteins secreted
by molluscs, mussel, et cetera [41,42]. With plenty of functional groups,
polydopamine can undergo reactions organic polymers or biomolecules
to form organic polymer coatings or biomolecule coatings, further
functionalized the surface of the substrate [43–45]. Aisheng Huang’s
group [46] prepared highly stable GO-membranes by using poly-
dopamine (PDA) as a novel covalent linker. The aforementioned char-
acteristics are making PDA the perfect candidate to enhance the ad-
hesion between fillers and coatings, further improving the corrosion
protection performance of water-based alkyd varnish with PANI-GO
composite.
This study aims to provide a cost-effective way to improve the anti-
corrosion efficiency of environmentally friendly nontoxic WAV. The
PDA-PANI-GO composite was prepared by a facile method including
just mechanical mixing and stirring and then the above composite was
added into WAV to coat onto steel electrode (Scheme 1). The optimal
proportion between PDA and PANI-GO was explored while morpholo-
gical structures and compound identification of the obtained PDA-
PANI-GO composite were characterized by scanning electron micro-
scopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-
IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The an-
ticorrosion performance of PDA-PANI-GO composite introduced WAV
(PDA-PANI-GO/WAV) was examined by electrochemical corrosion
testing methods. In addition, the tape peeling and tensile test were
performed in order to characterize the mechanical durability and me-
chanical strength, and these tests are helpful for further exploration in
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Journal of Hazardous Materials 377 (2019) 142–151
practical applications of the coatings.
2. Experimental
2.1. Reagents and apparatus
Graphene Oxide (GO, purity > 96%) supplied by Leader Nano Tech
L.L.C. (Jining, China). Aniline and tris(hydroxymethyl) aminomethane
hydrochloride (Tris-HCl) were supplied by Aladdin Industrial
Corporation (Shanghai, China). Ammonium persulfate (APS), per-
chloric acid, concentrated hydrochloric acid and sodium chloride were
purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai,
China). Dopamine hydrochloride was supplied by Sigma-aldrich, Co.,
3050 Spruce Street, (St. Louis, Mo, USA). Alkyd varnish was purchased
from Lehua Inc. China. All the reagents were of analytical grade and
used without further process. Deionized (DI) water obtained from a
water purification device (Aquapro ultrapure water system, Ever Young
Enterprises Development. Co. Ltd., Chongqing, China) was utilized in
all experiments.
XRD tests were performed on an Ultima IV X-ray Diffractometer
(Rigaku Ltd., Japan); FT-IR spectroscopy was tested on a Tensor 27 FT-
IR spectrophotometer (Bruker Company, German) and XPS analysis was
conducted on a K-Alpha X-ray photoelectron spectrometer (Thermo
Fisher Scientific, China). SEM was examined using JSM-6700 F machine
(JEOL, Tokyo, Japan).
The working electrodes were custom-made by Q235 steel with a
working area of 1 cm2 in the process of electrochemical corrosion tests.
Prior to use, all samples were sequentially treated with emery paper
300, 500, 1000 grits. After washed by ultrasonic cleaner for 5 min in the
absolute ethanol solution, the samples were rinsed in acetone for
10 min. The coating was coated on the pre-treated electrode samples by
a spin coater (KW-4A/5 spin coater, the Institute of Microelectronics,
Chinese academy of sciences, China), and the thickness of coating was
obtained using EC-770 coating thickness gauge (Yuwese Company,
Shenzhen, China).
All the electrochemical measurements were carried out using CHI
604E electrochemical workstation (Shanghai CH Instrument Company,
China). The water contact angles of the samples were operated on a
JC2000C goniometer and the tape-peeling test was performed by a
perpendicular scratches knife (QFH-HG600, Guangdong) and a
Permacel P99 tape. The tensile test was performed on the MTS
810 Material Test System Rack.
2.2. Synthesis of PANI-GO composite
GO powder was mixed with 100 mL of 1.0 M HClO4 solution in ul-
trasonic stirrer for 30 min until mixture became stable and uniform.
Aniline (5 mmol) was then added in the above mixture. 10 mL of 1.0 M
HClO4 within 0.76 g of APS was rapidly added into the above solution
to start the polymerization reaction. The reaction was continued for 6,
12, 18, 24 h at room temperature. The solid product was obtained after
centrifugal separation and rinsed by DI water and absolute ethanol.
Finally, the emerald precipitate was air-dried and grounded. By chan-
ging the reaction time, different morphology of PANI-GO composites
can be obtained [47].
2.3. Synthesis of PDA-PANI-GO composite
Tris-hydrochloride (Tris-HCl) buffer solution was prepared and the
pH of the buffer solution was adjusted to 8.5. The as-prepared PANI-GO
composite was dissolved in the buffer solution under continuous stir-
ring. After that, dopamine was added into the mixture to start self-
polymerization [41]. The ratio of PDA to PANI-GO in the system was
kept at 1:4, 1:2, 1:1, 2:1 and 4:1, respectively.
N. Yang, et al.
Scheme 1. The schematic illustration of preparation and coating process for PDA-PANI-GO/WAV.
2.4. Preparation of PDA-PANI-GO/WAV
1 mL (1 mg/mL) PDA-PANI-GO aqueous suspension was mixed with
10 g WAV (additive/coating = 0.01 wt %) and then stirring con-
tinuously till acquired a homogeneous mixture. The obtained coating
was coated on pre-treated electrode samples, air dried for 72 h and then
coated again. This process was repeated three times to keep the coating
thickness at about 100 ± 0.5 μm. The pure WAV, PDA/WAV and PANI-
GO/WAV were prepared by same method.
2.5. Electrochemical measurements
After immersion of the electrodes for 7 days, the electrochemical
impendence measurements and polarization tests were performed in
3.5% NaCl solution. A three-electrode system was assembled by a silver
chloride reference electrode, a platinum counter electrode and the
Q235 steel working electrode [48]. The open circuit potential (OCP)
measurement was carried out until the potential value remained un-
changed to create a system that was not affected by irrelevant factors.
Then alternating current impedance tests were performed at certain
corrosion potential with frequency range from 0.01 Hz to 105 Hz. Fi-
nally, potentiodynamic polarization tests were implemented within the
voltage range of ± 300 mV relative to OCP.
3. Results and discussion
3.1. Morphology of the GO, PANI-GO and PDA-PANI-GO composite
The surface morphologies of PANI-GO composites prepared with
different reaction times were obtained by SEM with working distance of
7.8 mm and accelerating voltage of 3.0 kV values at room temperature
are shown in Fig. 1 [49,50]. PANI grew into uniform button-shaped
bulges with diameter about 50 ± 5 nm. A few bulges distributed on the
slight wrinkles of the GO nano-layer surface after 6 h (Fig. 1a) and 12 h
(Fig. 1b) of the reaction. By extending the polymerization time to 18 h,
more uniformly and densely arranged structure emerged (Fig. 1c).
Continuing increasing the reaction time to 24 h, the composites grew
into a disorganized cylinder structure, as shown in Fig. 1d. By modeling
lotus leaf with hierarchical micro-nano surface structure, regularly ar-
ranged surface bulges can effectively decrease the surface energy,
thereby improving the corrosion resistance of the GO fillers [51].
Therefore, 18 h-grown PANI-GO composites was selected to further
modification.
Fig. 2 shows comparison between surface morphology of the
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Journal of Hazardous Materials 377 (2019) 142–151
unmodified GO and PDA-PANI-GO composite and high-magnification
SEM image of button-shaped bulge was inserted in Fig. 2b. The PDA
formed into a translucent film covering the surface of PANI-GO com-
posite. The addition of PDA had little effect on formation of the hier-
archical micro-nanostructures [52].
3.2. XRD spectrum of the GO, PANI-GO and PDA-PANI-GO composite
The typical structural evolution during the composite synthesis was
investigated by XRD. As illustrated in Fig. 3, the intense and sharp peak
at 2θ = 11.8° of GO corresponds to an interlayer distance of 0.753 nm
[53]. This value can be assigned to the (001) reflection peak, depending
on the method of preparation and on the number of layers of water in
the gallery space of the GO. In the case of PANI-GO, the peak of GO
stacking disappeared and two new peaks of PANI-GO centered at 19.8°
and 26.03°, which are the characteristic Bragg diffraction peaks of PANI
indicating the GO had almost no aggregation and was fully used as the
substrate of PANI nano-bulge to produce hierarchical nanocomposites
[54]. The PDA with amorphous structure cannot be displayed by XRD
and the successful synthesis of PDA was certificated by the following
characteristic tests.
3.3. FT-IR spectrum of the GO, PANI-GO and PDA-PANI-GO composite
The structural characteristics of the composites were investigated by
FT-IR spectrum as shown in Fig. 4. The FTIR spectrum of GO (Fig. 4a)
with main peaks at 3428 cm−1 (—O—H stretching), 1647 cm−1 (—C]
O stretching), 1406 cm-1 (CeOH bending), 1205 cm-1 (epoxide CeOeC
stretching and C(O)−OH bending), and 1096 cm-1 (—C—H stretching)
provides evidence of the hydroxide groups, carboxyl groups and ep-
oxide groups. Comparing with the FT-IR spectrum of PDA-PANI-GO and
PANI-GO, a new weak absorption band at 1586 cm-1 and a strong ab-
sorption band at 1490 cm-1 are associated with the C]C stretching
vibration in quinoid and benzenoid aromatic rings, respectively. And
conjugation moves absorptions of the υ(C]O) to lower wave numbers
and eventually merged with υ(C]C). The peaks at 1310 cm-1 and
1246 cm-1 in Fig. 4b are assigned to the characteristic peak of the NeH
bending vibration corresponding to the aromatic secondary amine in
PANI-GO [50]. While in Fig. 4c, the red shift of the NeH bonds
(1373 cm-1 and 1301 cm-1) in PDA-PANI-GO caused by steric hindrance
of the molecular chains of the PDA approved the successful synthesis of
PDA-PANI-GO [55–57].
N. Yang, et al. Journal of Hazardous Materials 377 (2019) 142–151

Fig. 1. SEM images of PANI-GO with polymerization time = 6 h (a), 12 h (b), 18 h (c), 24 h (d).

3.4. XPS spectrum of the GO, PANI-GO and PDA-PANI-GO composite

To provide further evidence for the formation of PANI-GO and PDA-

PANI-GO composites, the samples were characterized by XPS with
monochromatic Al Kα radiation at 1486.8 eV, as shown in Fig. 5a. The
XPS band of the C1s core level of GO was deconvoluted into four
components (Fig. 5b); that is, the sp2 carbon (284.8 eV), CeOH or α-C
in –C−COOH (286.3 eV), OeC]O (290.09 eV) [58–60]. This also
confirmed the existence of carbonyl, carboxyl acid and hydroxyl groups
in the GO sheets, which was in good agreement with the FT-IR results.
After the synthesis of the PANI-GO, the C1s spectrum (Fig. 5c) revealed
a new peak at 286.0 eV, corresponding to the amide carbon in CeN and
the peak at 290.1 eV may be assigned to the presence of HOeC]O
[61]. Compared with the PANI-GO, the peak at 287.44 eV in the final
target composite indicates the presence of NeC]O, which confirms the
polymerization of PDA introduced the N-heterocycle onto the na-
nosheets (Fig. 5e) [62]. This result is consistent with that of FT-IR
Fig. 3. The typical XRD patterns of GO (a), PANI-GO (b) and PDA-PANI-GO (c).
spectrum. Meanwhile, there is a larger quantity of oxygen in PDA-PANI-
GO, which belongs to the hydroxyl groups of PDA. Additionally, the
high-resolution N1s spectra can be deconvoluted into one peak locating 3.5. Electrochemical measurement
at 399.8 eV assigning to pyridinic N, which widely exist in PANI and
PDA (Fig. 5d, 5f) [57,63]. EIS measurements were used to evaluate the anticorrosion perfor-
mance of coatings. Bare steel electrode, steel electrodes coated with
pure WAV, PDA/WAV, PANI-GO/WAV and PDA-PANI-GO/WAV were
taken measurements orderly for comparison. All the EIS tests were

Fig. 2. SEM images of pure GO (a) and PDA-PANI-GO (b). Insert: magnification of one PDA-PANI-GO button-shaped bulge.

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the deviation of the electrode potential is called polarization. Polar-

ization curve described the relationship between current density and
potential, is one of the most utilized methods for determining corrosion
rate [67,68].
Polarization curves in Fig. 6b indicate the corrosion potentials
ranked by numerical value from smallest to largest: steel electrode with
PDA-PANI-GO/WAV, PANI-GO/WAV, PDA/WAV, WAV and bare steel
electrode. The extrapolation of the linear Tafel regions was calculated
by CHI 604E electrochemistry software. The results of corrosion current
density and protection efficiency (η) in Table 1 are consistent with the
above conclusions [69].
The efficiency of decreasing corrosion rate can be described as
protection efficiency, expressed by formula [70,71]:

0
icorr − icorr
η= 0
× 100
icorr

0
Fig. 4. FT-IR spectrum of GO (a), PANI-GO (b) and PDA-PANI-GO (c). Where icorr and icorr are corrosion current density values of the bare steel
electrode samples and coating samples.
Based on the above-mentioned results, PDA-PANI-GO/WAV has
performed in 3.5 wt % NaCl solution after 7 days immersion at room
shown superior performance of corrosion prevention. The goal now is
temperature [64].
to extend the above results to explore the exact ratio of PDA to PANI-
As Nyquist plots shown in Fig. 6a, in compared with that of the bare
GO which maximizes corrosion protection ability of PDA-PANI-GO/
electrode, the capacitive arc diameters significantly increased. The
WAV. Five kinds of the composites containing ratio of PDA and PANI-
impedance values at low frequency of 0.01 Hz (|Z|0.01 Hz) of bare steel
GO from 1:4, 1:2, 1:1, 2:1 to 4:1 are selected as samples. EIS mea-
electrode, steel electrodes with pure WAV, PDA/WAV, PANI-GO/WAV
surements and potentiodynamic polarization measurements were also
and PDA-PANI-GO/WAV are 6.64 × 102 Ω cm2, 5.83 × 103 Ω cm2,
applied to characterize electrochemical performance of PDA-PANI-GO/
1.95× 105 Ω cm2, 6.162 × 105 Ω cm2 and 8.485 × 105 Ω cm2, re-
WAV with different proportions of PDA-PANI-GO. In Fig. 7a, with in-
spectively. It was not reaching the maximum value until PDA-PANI-
creasing of PDA and PANI-GO ratio, the diameter of the semicircle in
GO/WAV covered on the electrode surface, directly reflected the ex-
Nyquist plot increased at first and then decreased, reaching a maximum
cellent anticorrosion performance of PDA-PANI-GO filler.
when ratio of PDA to PANI-GO was kept at 2:1. Further increased the
Potentiodynamic polarization measurements were used as supple-
content of PDA, capacitive arc diameters was instead of continually
mental evidence to verify whether or not PDA-PANI-GO can sig-
increased, slightly decreased. The exact |Z|0.01 Hz value of PDA-PANI-
nificantly enhance corrosion resistance of the WAV. Corrosion rate,
GO/WAV with ratio of PDA to PANI-GO from 1:4, 1:2, 1:1, 2:1 to 4:1
another way to characterize corrosion protection performance, depends
are 5.298 × 105 Ω cm2, 5.7716 × 105 Ω cm2, 7.0595 × 105 Ω cm2,
on the absolute value of the corrosion potential and corrosion current
9.4069 × 105 Ω cm2 and 8.485 × 105 Ω cm2, respectively. The fitting
density [65]. When corrosion occurs, currents flow through electrode
results of Tafel plots in Fig. 7b and Table 2 support the above results.
and lead to a deviate of the potential from the equilibrium value
The corrosion potentials, corrosion current density and protection ef-
[28,66]. As a result, the irreversible electrode reactions cause the
ficiency of PDA-PANI-GO/WAV reached the best when ratio of PDA to
rusting of the material. Due to current passing through the electrode,
PANI-GO was kept at 2:1. This is because a certain amount of PDA can

Fig. 5. XPS spectra of GO, PANI-GO and PDA-PANI-GO (a) and the corresponding high resolution C1s spectrum of GO (b), C1s spectrum and N1s spectrum of PANI-
GO (c, d) and PDA-PANI-GO (e, f).

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Fig. 6. Nyquist plots (a) and Tafel plots (b) of bare steel electrode, steel electrodes coated with pure WAV and WAV with different fillers.

Table 1 Table 2
The fitting data of Tafel plots for electrode without fillers and with pure WAV, The fitting data of Tafel plots for electrode coated with PDA-PANI-GO/WAV
PDA/WAV, PANI-GO/WAV, and PDA-PANI-GO/WAV. having different ratio of PDA to PANI-GO.
Fillers Ecorr(mV) icorr (μA βa(mV/dec) βc(mV/dec) η(%) Ratio of PDA to Ecorr(mV) icorr (μA βa(mV/dec) βc(mV/dec) η(%)
/cm2) PANI-GO /cm2)

Blank −565 385.7 6.598 3.465 — Pure AV −498 89.7 5.039 5.184 —
WAV −498 89.7 5.039 5.184 76.74 1:4 −482 22.1 4.364 6.978 75.36
PDA/WAV −495 43.6 10.008 7.678 88.70 1:2 −425 18.3 4.917 5.081 79.60
PANI-GO/WAV −385 34.2 4.785 6.182 91.13 1:1 −387 12.6 5.031 4.938 85.95
PDA-PANI-GO/ −244 5.99 4.473 6.051 98.45 2:1 −245 1.48 4.827 5.268 98.34
WAV 4:1 −299 3.70 4.493 7.982 95.88

evenly cover the surface of PANI-GO while excessive PDA is unable to

play a role in improving compatibility.
To simulate electrical characteristics, equivalent circuit analysis was
used to analyze the EIS data [72,73]. The equivalent circuit model R(Q
(R(QR))) is shown in Fig. 8, where Rs (Ω cm2), defined as solution re-
sistance, keeps a fixed value in the same reaction solutions. In actual
situations, Rs would slightly changes according to different conditions.
Rigorous operation makes the change as small as possible and little
effect would be exerted on the experimental results. Rct and Rc (Ω cm2)
represents charge transfer resistance of the electrode interface and
coating resistance, that varies inversely with corrosion rate. Cc (F
cm−2) refers to coating capacitance. Cdl (F cm−2) indicates constant
phase elements (CPE) of the electrode/solution interface, which models
the behavior of a double layer. CPE is an ideal equivalence element of
the capacitor, presenting capacitive behavior in inhomogeneous elec-
trodes.
The impedance of the CPE is calculated by following equation [70]:
ZCPE=Y0−1(jω)-n
where Y0 is proportionality factor, j is the imaginary unit, ω is radian
frequency, n (0 < n < 1) is CPE exponent, which describes an ideal
capacitor in the case of n = 1 while describes a pure resistor in the case
of n = 0 [74]. The related data was shown in Table S1 and Table S2
(Supporting Information). The sum of Rct and Rc indicate the total
impedance of the coating system, showing the corrosion protection
performance of the coatings.
The corrosion protection mechanisms of pure WAV and WAV with
PDA-PANI-GO composite were shown in Fig. 9a and 9b.
The addition of PDA-PANI-GO composite exhibits excellent che-
mical properties that combined two advantages: 1) the π-electron
backbone and amino groups of polyaniline and oxygen-containing
functional groups of two-dimensional graphene oxide nanosheets
compound together with strong covalent bonds, presenting striking
barrier and active inhibition properties [74,75]; 2) highly reactive and

Fig. 7. Nyquist plots (a) and Tafel plots (b) of bare steel electrode coated with fillers having different ratios of PDA and PANI-GO.

147
N. Yang, et al.
Fig. 8. The equivalent circuit diagrams of bare steel electrode (a) and steel electrode coated with PDA-PANI-GO/WAV (b).
adhesive PDA that wrapping on the PANI-GO surface greatly reinforce
the adhesion and compatibility of fillers and coatings (Fig. 9c) [41].
As shown in Fig. 9a, due to the low surface tension of the WAV, the
coating prone to engender micro defects and shrinkage cracks during
curing process. In corrosive environment, caustic substances penetrate
coating easily through the micro defects and then corrode the substrate
badly [76]. The structure of PDA-PANI-GO composite is nano-layers
with uniform button-shaped bulges which providing physical barrier
effects and surface hydrophobicity (Fig. 9b). As a result, increased
difficulty of caustic substances to contact and corrode the materials.
Also, the composite with rigid structure and highly adhesive PDA could
fill the defects and cracks of pure WAV.
3.6. Contact angle test
In order to evaluate the surface hydrophobicity of the modified
coating, a contact angle meter with the syringe needle gauge of 27 G
and the droplet volumes of 2 ± 0.1 μm was used to measure contact
angle (CA) [77]. The static CA of the distilled water was measured
threefold repetition on the specimens using sessile drop measurement at
temperature of 23 °C ± 2 °C and humidity of 30 ± 2%. The static CA
of water on bare Q235 steel electrode surface was only 73.02°, as shown
in Fig. 10a. After the coverage of pure WAV on the steel electrode, the
corresponding CA value increased to 81.60° (Fig. 10b). While covering
the WAV with PANI-GO, the CA value increased to 98.93° (Fig. 10c).
With addition of PDA-PANI-GO, the surface hydrophobicity distinctly
improved CA value to 105.75° (Fig. 10d), attributing to the formation of
the hierarchical button-shaped PANI nano-bulges on the surface of the
GO-layers and the better compatibility of filler and coating that PDA
Fig. 9. The schematic illustrations of anti-corrosion mechanism of pure WAV (a) and PDA-PANI-GO/WAV (b) in corrosive environment and magnification of
molecular interaction of PDA-PANI-GO composite (c).
148
Journal of Hazardous Materials 377 (2019) 142–151
provided.
3.7. Visual Results of the corrosion test
Fig. 11 exhibits the digital images of bare Q235 steel electrode (a)
and steel electrode coated with PDA-PANI-GO/WAV (b) before and
after immersion in 3.5 wt% NaCl solution for 7 days. All the electrode
samples were custom-made with a working area of 1 cm2. The working
area of electrode samples were sequentially treated with emery paper,
and then washed in the absolute ethanol and acetone solution. After
soaking in NaCl solution for 7 days, no visible bubbling and peeling of
PDA-PANI-GO/WAV surface was seen [68]. The steel electrode re-
mained generally clean and glossy after scratching off the coating. The
slight discoloring of the electrode edges might be attributed to defects
caused by coating process [31]. As a contrast, the steel electrode
without coating presented multiple brown rust spots, indicating the
excellent anticorrosion performance of PDA-PANI-GO/WAV.
3.8. Tensile test
Tensile test is a commonly used method to study mechanical
strength of the coating [78–80]. Fig. 12 shows the stress-strain curves of
the pure WAV and PDA-PANI-GO/WAV. The tensile tests of the coatings
were measured at 5 mm/min strain rate with a load of 1 kN. The
maximum tensile strength of the coating introduced PDA-PANI-GO
composite was 83.0 MPa, about 63.9% higher than that of pure WAV.
Meanwhile, the maximum elongation at break increased by 47.1%
compared to pure WAV. The addition of PDA-PANI-GO composite of
coating makes the resistance to deformation and fracture greatly
N. Yang, et al.
Fig. 10. The contact angles of bare steel electrode (a), with pure WAV (b), with PANI-GO/WAV (c) and with PDA-PANI-GO/WAV (d).
Fig. 11. The digital images of bare steel electrode (a) and steel electrode with
PDA-PANI-GO/WAV (b) before and after immersing in 3.5 wt. % NaCl for 7
days.
enhanced under external forces.
3.9. Visual results of the tape-peeling test
Tape-peeling test was performed to assess the mechanical stability
and adhesion of the as-prepared PDA-PANI-GO/WAV to the metal
substrate according to ATSM D3359-97 [81]. The lattice patterns were
obtained by two perpendicular scratches and the pressure sensitive tape
was pressed onto the as-cut surface by fingers for 120 s to ensure good
contact, and then the tape was peeled off from the substrate. Fig. 13
exhibits the digital images of PDA-PANI-GO/WAV before and after
peeling off the tapes. As shown in Fig. 13b, no delamination or de-
tachment of the coating at the edges and within the square lattice was
observed and Fig. 13c shows no debris of the coating remained on the
tape. The coating-substrate adhesion is close to the 5A level according
149
Journal of Hazardous Materials 377 (2019) 142–151
Fig. 12. The stress-strain curves of the pure WAV and PDA-PANI-GO/WAV.
to ASTM D 3359-97 standard, indicating good adhesion between the
coating and the substrate.
4. Conclusion
A facile process was used to prepare PDA-PANI-GO composite for
enhancing corrosion protection performance of the water-based alkyd
varnish. Uniformly and densely button-shaped PANI bulges were
growing on the GO nanosheets and then the composites were covered
with PDA. The GO nanosheets enhanced strength of the coating and
provided impermeability and physical barriers, on which homogeneous
PANI bulges increased the path distance of the corrosive substances to
surface of the metallic subtract. Meanwhile, PDA, wrapping on the
PANI-GO surface, improved compatibility between alkyd varnish and
fillers. With synergy among three ingredients, anticorrosion ability
greatly improved by over two orders of magnitude. Thus, en-
vironmentally friendly non-toxic WAV could be transformed into a
prominent corrosion resistant coating by adding only 0.01 wt % of the
PDA-PANI-GO additives. This study is expected to reduce the corrosion
of metals especially for situations such as buildings and equipment in
N. Yang, et al.
Fig. 13. The digital images of the PDA-PANI-GO/WAV as-cut samples (a), samples after peeling off the tape (b) and detail of the tape peeling off from the samples (c).
coastal areas; as a result, the outcome of this study should reduce costs
for engineering construction and maintenance, and at the same time
reduce heavy metal toxics releasing.
Acknowledgments
This work was supported by National Science Fund for
Distinguished Young Scholars (No. 51525903), AoShan Talents
Cultivation Program Supported by Qingdao National Laboratory for
Marine Science and Technology (No. 2017ASTCP-OS09), Applied Basic
Research Programs of Qingdao (No. 17-1-1-98-jch), Applied Basic
Research Programs of Nantong (No. GY12016002), National Science
Fund for Young Scholars (No. 51701234), Key research and develop-
ment project of shandong province :2017GGX20101.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.jhazmat.2019.05.063.
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