Progress in Organic Coatings 128 (2019) 137–147

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Effect of self-assembled tetraaniline nanofiber on the anticorrosion T

performance of waterborne epoxy coating
⁎
Tong Liua, Jingyu Lia, Xiangyu Lib, Shihui Qiua, Yuwei Yea, Feng Yangb, Haichao Zhaoa,
a
Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials
Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, China
b
Shenyang University of Chemical Technology, Shenyang, 110142, China

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

Keywords: This work discusses the addition of tetraaniline based conducting nanofiber (TANF) on the anticorrosive
Self-assembly properties of waterborne epoxy coatings on Q235 mild steel. TANF was synthesized by self-assembly of tetra-
Tetraaniline aniline in 1 M HCl solution. The structure of TANF was characterized by the Fourier-transform infrared (FT-IR),
Nanofiber Raman, X-ray diffraction (XRD) pattern, UV–vis spectra and photoelectron spectroscopy (XPS), and the mor-
Epoxy coating
phology of TANF was used to investigate by scanning electron microscope (SEM) and scanning probe microscope
Anticorrosion
(SPM). The self-assembled TANF possesses excellent solubility, tiny nanofibrous structure and reversible redox
behavior, making it appropriate as a novel anticorrosive pigment for the waterborne coatings. Electrochemical
impedance spectroscopic (EIS), polarizing curves and scanning vibrating electrode technique (SVET) were used
to investigated the effect of TANF on the anticorrosion performance of epoxy coating. The results revealed that
the waterborne epoxy coating containing 0.5 wt% TANF exhibited improved corrosion resistance properties
compared to pure waterborne epoxy coating. The addition of electroactive TANI could facilitate to form a
passive metal oxide layer beneath the coating as proved by characterization of rust layers by X-ray diffraction
(XRD).

1. Introduction has poor corrosion protection performance due to the formation of

coating defects during water evaporation. One strategy to decrease the
Organic coatings are one of the most effective means to protect coating defects is to incorporate nanofillers or pigments for filling of
metal against corrosion due to the ease of formation of physical barrier pores and cavities inside the coating matrix. The effects of many na-
between metallic substrate and harsh environment [1,2]. However, nofillers on the corrosion resistance of waterborne coatings have been
environmental protection has become a major concern for traditional extensively investigated, such fillers include three dimensional nano-
solvent borne coatings since these normally contain high volatile or- particles (e.g. SiO2, TiO2, Al2O3, Fe3O4, ZnO), two dimensional na-
ganic compounds (VOCs). More and more stringent environmental nosheets (e.g. clays, graphene oxide, graphene), or one-dimensional
regulations remain the principal driver for the development of new nanofibers and nanotubes (carbon nanotube, nanorod) [13,14]. In this
technologies for reduction of VOC emissions [3–5]. Such new technol- regard, for the sake of avoiding the aggregation of nanosized fillers in
ogies include powder coatings, high-solid or nonsolvent coatings, wa- the interior of the coating, the proper chemical or physical modification
terborne coatings or UV-cured coatings [6–9]. is essential for improving the compatability and interface properties
Currently, a variety types of water soluble and dispersible polymeric between the nanofillers and coating matrix [8,9,12].
resins including epoxies, acrylics, polyurethanes, polyesters, alkyd re- Since DeBerry found that electro-deposited polyaniline (PANI)
sins have been developed for waterborne coating formulations, among could passivate the steel in strong acidic solution and enhance the
which epoxy waterborne coatings are the most studied primers due to corrosion protection performance, the utilization of conducting poly-
strong adhesion to the metallic substrate, low curing shrinkage and mers (CPs) as corrosion inhibits has remained one of the hottest re-
high chemical stability [10–12]. However, these coatings have been less search topics [15]. Conducting polymers can be directly eletrodeposited
accepted by industry. The reason is that film formation process is more on metallic substrate or as pigments to prepare composite coatings.
critical than for solvent-borne epoxy coatings, and the formed coating Many studies proved that organic coatings containing a small quantity

⁎
Corresponding author.
E-mail address: [email protected] (H. Zhao).

https://doi.org/10.1016/j.porgcoat.2018.11.033
Received 17 April 2018; Received in revised form 22 November 2018; Accepted 26 November 2018
0300-9440/ © 2018 Elsevier B.V. All rights reserved.
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

of conducting polymers can form passive film through isolation and solution, 300 mL of acetone and deionized water. Ammonium persul-
charge transfer mechanism [16–19]. The passive film can exert the fate (APS) (13.695 g, 40 mmol) in 150 mL 1 M HCl solution was added
coating with self-healing function and corrosion inhibition, which de- into the above-mentioned solution during 60 min with stirring in ice
pends on the densification property of the passivation film as proved by bath condition. After reacting for 3 h, the product was filtered to col-
scanning vibrating electrode technique (SVET) tests [13,20,21]. In lect. Then collected product was dedoped via dispersing in 50 mL of
terms of the current researches, the development of soluble substituted NH4OH and 500 mL of deionized water and stirred for 6 h. The product
CPs or processable nanostructured CPs (e.g. nanoparticle, nanofiber, was filtered and washed repeatedly with water until the filtrate became
nanotube) is a prerequistite for development of CPs based organic neutral. At last, the TANI was dried in a vacuum oven at 50 ℃ for 72 h.
coatings [22]. In our previous studies, we have synthesized water dis- FTIR of TANI: 748 (δC–H), 1303 cm−1 (υC–N), 1506 cm−1 (υC=C of
persible spherical PANI particles with an average diameter of 60–80 nm benzenoid ring), 3023 cm−1 (υC–H), 3373 cm−1 (υN–H) (Fig. A. 1).
by using polyvinylpyrrolidone as a stabilizer during the dispersion
polymerization. The incorporation of a small amount of nanoparticles 2.3. Synthesis of TANF
(0.5–2 wt%) in the coatings remarkably improved the corrosion pro-
tection performance of waterborne epoxy coating, among which the In a representative procedure, 4 mg of tetraaniline powder and
coating containing 1.0 wt% nanoparticle exhibited the best corrosion 20 mL 1 M HCl solution were mixed under ultrasonic irradiation for
protective effect owing to the redox catalytic properties and the in- 4 min [34]. The TANF slurry was obtained by centrifugation, and then
hibitory effect of doping ions [14,23]. We have also successfully pre- dried to a constant weight (38 ℃ for 72 h). The chemical formula of
pared water dispersible sulfonated PANI nanofiber with average dia- fully-doped TANF is 1/2 (Cl/N). The X-ray photoelectron spectroscopy
meter around 45 nm, length up to 750 nm and conductivity of 0.11 S/ (XPS) spectrum was shown in Fig. A. 2. Furthermore, the elemental
cm. The 0.5 wt% sulfonated PANI nanofiber could fill the pinholes and analysis of TANF and its molecular formula were displayed in Table A.
cracks in the coating and in the same time facilitated the formation of a 2. (TANF yield: 90%)
passive metal oxide layer to remarkably improve the corrosion pro-
tection performance [24]. A polypyyrole (PPY) colloid intercalted 2.4. Preparation of composite coatings blended with TANF
graphene (G) was also developed as nanoreinforcing filler for epoxy
base waterborne coating. It turned out that the 0.5 wt% G/PPY con- The coatings containing 0.5 wt% and 1.0 wt% of TANF and pure
taining composite coating exhibited a superior corrosion resistance in epoxy coating were prepared. In this procedure, the epoxy resin (E51),
3.5 wt% NaCl soulution compared to neat epoxy coating due to passive TANF and an appropriate amount of ethanol were mixed and dispersed
effect of PPY and impermeable property of graphene nanosheets [13]. by using a high-speed agitator for 3 h. After ethanol was removed by
Recently, supramolecular assembly has emerged as a promising rotatory evaporation method, waterborne epoxy curing agent (curing
technology for creating nanostructured materials with well-defined agent : epoxy resin = 146 : 100) was added with stirring. The Q235
morphology and molecular arrangement. A variety of π-conjugated steel electrodes were unoiled via ultrasonic vibration in absolute
molecules such as oligo(phenylevevinylene), oligothiophenes, oligoa- ethanol and polished by the sand papers of 400, 800 and 1200 grid.
nilines, substituted perylenes were assembled into many sorts of nano- Then, the composite coating mixture was coated on the electrode
structures through a series of nonconvalent interactions such as hy- working faces by a standardized bar coater. As a comparison, epoxy
drogen bonding, ionic interaction, π-π stacking and electrostatic in- coating without TANF was also prepared in a same method. The half-
teraction [25–27]. Among the family of π-conjugated molecules, tet- finished coatings were cured for 120 h under 25 ℃. The thickness of
raaniline (TANI) have been assembled into one-dimension nanowires, prepared film was governed by 20 ± 2 μm.
two-dimensions nanotubes, and three-dimension nano-flowers through
solvent exchange process assisted by doping acid such as HCl, HNO3, 2.5. Characterization
HClO4 and H2SO4 [22,28–31]. The aim of this research is to prepare
processable tetraaniline nanofiber and apply it as a pigment for the 2.5.1. Characterization of the prepared TANF
aqueous epoxy coatings. The effect of TANF on corrosion resistance of The scanning electron microscope (SEM) patterns of TANF and
resulting coating was evaluated by conventional electrochemical mea- coatings’ fracture surfaces were performed by S4800 (Japan) and the
surements such as electrochemical impedance spectroscopic (EIS), po- morphologies of TANF were also exhibited by the scanning probe mi-
larizing curve and scanning vibrating electrode technique (SVET). croscope (Dimension 3100, USA). The FT-IR, Raman and XRD spectra of
Corrosion mechanisms of TANF were investigated through the identi- nanofiber were measured on a NICOLET 6700 (USA), Via Reflex
fication of corrosion products beneath the coating by scanning electron (England) and D8 ADVANCE (Germany). The UV–vis data of nanofiber
microscopy (SEM) and X-ray diffraction (XRD). was recorded on Lambda 950 (USA). The precise conductivity of TANF
was obtained by four-point probe technique (CRESBOX, USA). The X-
2. Experimental ray photoelectron spectroscopy (XPS) pattern of nanofiber powder was
obtained by AXIS UTLTRA DLD (England).
2.1. Materials
2.5.2. Electrochemical tests of TANF composite coatings
4-aminodiphenylamine, ammonium persulfate (APS) and ammonia The cyclic voltammetry (CV), open circuit potential (OCP) and
solution were all provided by Aladdin Industrial Corporation. electrochemical impedance spectroscopy (EIS) data of TANF composite
Commercial E51 and matched waterborne amine curing agent were coatings were recorded by CHI-660E electrochemical workstation,
provided by Hangzhou Hummer Coating Glass Co. Ltd. Acetone, abso- three-electrode cell with the saturated calomel electrode (SCE) as re-
lute ethanol and hydrochloric acid were purchased from Sinopharm ference electrode and platinum plate as counter electrode. The EIS data
Chemical Reagent Co. Ltd. The Q235 mild steel electrodes were used as was collected in the range of 10−2–105 Hz and polarization curves were
the substrate in this work. measured from cathodic direction to the anodic direction
(Eocp ± 0.25 V) with the scan speed of 0.8 mV·s−1. Scanning vibrating
2.2. Synthesis of tetraaniline electrode technique (SVET) test instrument was from AMETEK (USA).
The microelectrode parameters have the amplitude of 30 μm vibrated
The tetraaniline was prepared according to the published literature and frequency of 80 Hz in perpendicular direction to the surface (scan
procedures [32,33]. In a typical procedure, 4-aminodiphenylamine area: 2000 μm × 2000 μm). Visible artificial defect (2 mm of scratch)
(11.04 g, 60 mmol) was dissolved in a mixture of 75 mL 1 M HCl was exposed the carbon steel substrate surface on the different coatings

138
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

Fig. 1. Schematic representation for preparation of TANF.

Fig. 2. Morphology of the TANF: (a, b) SEM images; (c) SPM image.

139
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

Fig. 3. (a) FT-IR (KBr), (b) Raman, (c) XRD pattern of TANF, (d) UV–vis spectra patterns of TANI and TANF.

Fig. 4. Cyclic voltammetry of TANF in 0.1 M H2SO4 solution (sweep speed:

50 mV s−1).
Fig. 5. UV–vis spectra of fracture surface: (a) pure epoxy; (b) epoxy/TANF0.5%;
by a knife. (c) epoxy/TANF1.0% coatings.

of TANF sample exhibited similar absorptions to those pronated PANI

3. Results and discussion
[34,35]. XRD patterns of TANF displayed the anticipative peaks (2θ ≈
20.27°), which was attributed to the periodicity parallel to the polymer
3.1. Synthesis and characterization of TANF
chain. The peak at 2θ ≈ 24.80° was ascribed to the periodicity per-
pendicular to the polymer chain (Fig. 3c) [36].
The typical synthetic route for TANF was represented in Fig. 1 [34].
UV-vis spectroscopy was used to verify the assembly process. TANI
SEM and AFM images showed that the nanofibers with high length-to-
showed light blue color in ethanol at a concentration of 0.1 mg/mL. It
diameter ratio are obtained (Fig. 2), and these fibers were up to dozens
exhibited absorption peaks at around 310 nm due to π-π* transition of
of micrometers with the diameter around 20 nm. As can be seen from
the benzene ring and absorption peak at 592 nm for the benzenoid to
FTIR spectra of TANF (Fig. 3a), the broad infrared absorption around
quinoid (πB-πQ) excitonic transition, implying weaker intermolecular
1100 cm−1 corresponded to NH stretching bands of a strong a sym-
interactions (Fig. 3d) [23]. For TANF, peaks at 302, 420 and 795 nm
metric inter-chain NH+⋯N hydrogen bond [35].The Raman spectrum

140
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

Fig. 6. SEM images of fracture surface for (a) pure epoxy, (b) epoxy/TANF0.5% and (c) epoxy/TANF1.0% coatings.

were attributed to the π-π* transition, the polaron→π* and π→polaron peaks at around 584 nm, which were related to π-π* transition and
transitions, respectively, which demonstrated the formation of con- polaron band transition of nanofiber [41]. The morphology of fracture
ductive state [23]. surface of as-prepared coatings was investigated by SEM. As shown in
Fig. 6a, for pure epoxy coating, the fractured surface was uneven with
3.2. Electroactivity and conductivity of TANF obvious holes (red dotted circle). However, the surface of epoxy/TANF
coating became smooth, because the nanofibers have filled the defects
CV curve was obtained in 0.1 M H2SO4 solution with a sweep speed in the matrix (Fig. 6b and c). In addition, we found that the coating with
of 50 mV s−1 in a three-electrode electrochemical cell (Fig. 4). It was 1.0 wt% TANF packing exhibited more wrinkles because the more TANI
observed two strong redox processes in CV curve, which proved that nanofibers were agglomerated in the coating matrix (Fig. 6b and c).
this TANF sample possessed a high capacitive performance [37–39].
The oxidation peak at 0.453 V corresponded to the leucoemeraldine 3.4. Anticorrosive performance
base (LEB)/emeraldine base (EB) transition, furthermore, oxidation
peak at 0.734 V showed the transition transform the emeraldine base 3.4.1. Electrochemical impedance spectra
(EB) and the pernigraniline base (PNB). The Nyquist and Bode patterns of the different samples during the
The conductivity of the doped TANF was measured by four-point immersion of 37 d were presented in Fig. 7. With regard to pure wa-
probe technique (CRESBOX). To study the conductivity of TANF, its terborne epoxy coating (Fig. 7a), its Nyquist pattern showed the
powder was pressed into a piece with the diameter of approximately shrinking capacitive loop during the entire immersion, indicating the
13 mm (Fig. A. 3). Previous works on the electric capability of HCl- declined corrosion resistance for mild steel. TANF0.5% composite
doped TANI nano-product measured on pressed piece yielded con- coating displayed the same shrinking trend for capacitive arcs in high
ductivity with the range of 10−5 to 10 mS cm−1 [28,40], while the frequency region during the initial 10 d. Unlike the pure epoxy, after 20
conductivity of our nanofibers was 105 mS cm−1. The high con- d, its radii of capacitive arc at low frequency region was gradually
ductivity of product indicated the superiority of self-assembled nano- expanded, even beyond that of second day (Fig. 7c). As shown in
fibers with nanostructures, which proved its application prospect as Fig. 7e, the Nyquist plots for TANF1.0% coating showed the same trend
coating additive. like TANF0.5% coating until the immersion lasted 24 d.
For the Bode patterns, the impedance value at the lowest frequency
3.3. Characterization of waterborne epoxy/TANF coatings (f = 0.01 Hz) has been used as a semi-quantitative standard of coating’s
shielding performance [42,43]. The measured value of |Z|0.01Hz for
The epoxy/TANF composite coatings were obtained by curing re- TANF0.5% coating, in the early immersion stage, was up to 1.35 × 108 Ω
action of waterborne hardener and epoxy resin (E51) containing 0.5 cm2, higher than those of pure epoxy and TANF1.0% (both are closed to
and 1.0 wt% TANF packing. As shown in Fig. 5, UV–vis patterns of 5 × 107 Ω cm2) by more than half an order of magnitude. In detail for
different composite epoxy coatings were obtained from the transparent Fig. 6d, the Bode plots of TANF0.5% coating exhibited a more highly
coating. There was no absorption peak in the metrical region between impedance value in the initial test and maintained at 7.72 × 106 Ω cm2
340 and 800 nm for waterborne epoxy coating, while all the TANF through 37 d of immersion, higher than that of pure epoxy (7.48 × 105
containing coatings showed strong peaks at around 347 nm and weak Ω cm2) by 1 order of magnitude. Therefore, it could be safely concluded

141
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

Fig. 7. Nyquist and Bode patterns of different coating samples: (a/b) pure epoxy, (c/d) epoxy/TANF0.5% and (e/f) epoxy/TANF1.0% coatings.

that both higher impedance duration and the final impedance of 3.4.2. The analysis of electrical equivalent circuits and corrosion
TANF0.5% coating were better than TANF1.0%, let alone the pure epoxy parameters
coating. Furthermore, the EIS results were fitted by ZSimDemo software
using the equivalent electric circuits, as shown in Fig. 8a and b. In terms

142
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

Fig. 8. (a), (b) Equivalent circuits and (c) Rpore, (d) Cc, (e) Rct, (f) Cdl values with test in 3.5 wt% NaCl solution.

of corrosion parameters, the Rs, Rpore, Rct and Zw represented the so- constant elements, represented the coating capacitance and steel/so-
lution resistance, pore resistance, charge transfer resistance on the steel lution (double-layer) capacitance. Frequently, “Q” was used to equalize
substrate and Warburg impedance, respectively. Warburg element (Zw) for the capacitance deviation and “n”, as an exponent, embodied the
showed the diffusion of electrolyte in the film, leading to an increase in deviation level from ideal dielectric behavior. Generally, ideal capaci-
the cathodic reaction. For capacitance, Qc and Qdl, the important tance was regarded as “Q = C” (n = 1) [44–46]. Circuit (a) was suited

143
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

Fig. 9. (a) Polarization curve pattern and (b) calculated parameter results of bare steel; pure epoxy; epoxy/TANF0.5%; epoxy/TANF1.0% coatings on the Q235 steel
electrodes immersed in 3.5% NaCl solution for 37 d.

Fig. 10. SVET 3D current density distribution maps of Q235 steel coated with an waterborne epoxy coating immersed in 3.5 wt% NaCl solution: pure epoxy for 2 h (a)
and 24 h (b); epoxy/TANF0.5% coating for 2 h (c) and 24 h (d); epoxy/TANF1.0% coating for 2 h (e), 24 h (f).

for pure epoxy coating and circuit (b) was fitted with the corrosion coating reached the minimum value of Rpore (1.94 × 105 Ω cm2) and
behaviors of epoxy/TANF composite coating. maximum value of Cc (4.14 × 10−10 F cm−2) at 10 d of immersion. On
As shown in Fig. 8c–f, these line charts exhibited the time-depen- the other hand, in Fig. 8e and f, the waterborne TANF coatings had
dent of Rpore, Cc, Rct and Cdl immersed in 3.5 wt% NaCl solution. Fitting higher Rct and lower Cdl than those of epoxy composite coating. For
degree (χ2 data) for equivalent circuits was showed in Table A. 4. 0.5 wt% and 1.0 wt% of epoxy/TANF composite coatings, they had a
Generally, a higher Rpore and lower Cc illustrated the less H2O and O2 tiny drop in Rct with the immersion. Moreover, Cdl of TANF0.5% coating
penetration into the coatings [47]. First of all, Rpore of coating dropped was less than that of TANF1.0% sample. The above result showed that
by degrees until the electrolyte reached saturation in the film, resulting epoxy/TANF0.5% composite coating was enough to passivate the mild
in the loss of the coating's ability to act as a physical barrier. Further- steel surface.
more, with the continual immersion, the enriched water brought about
the increase of Cc value due to higher local dielectric constant. In terms
of pure epoxy coating, Rpore decreased from the initial 2.00 × 106 to 3.4.3. Polarization curves test
4.45 × 104 Ω cm2 after 37 d of immersion. On the contrary, the value of The polarization curves, electrochemical parameters of pure epoxy
Cc increased gradually from 6.44 × 10−11 to 1.83 × 10−9 F cm−2 coating and epoxy/TANF composite coatings after the immersion of 37
(Fig. 8c and d). It was noteworthy that Rpore value fluctuated very little d were exhibited in Fig. 9. Generally, a higher Ecorr and lower icorr
at around the 10 d of immersion owing to the build-up of corrosive implied better corrosive protection effect. It was observed that bare
products in the coating defects. By comparison, the epoxy/TANF com- steel had the lowest Ecorr (−0.782 V) and the highest icorr
posite coatings displayed higher Rpore and lower Cc. In addition, Rpore of (4.427 × 10−7 A cm−2). By comparison, these values of pure epoxy
epoxy/TANF composite coatings showed a declining trend and then coating (Ecorr= -0.748 V, icorr = 1.135 × 10−7 A cm−2) were improved
increased slowly, contrary to its Cc. For example, epoxy/TANF0.5% in corrosion performance after 37 d immersion. The Ecorr of the com-
posite coatings transformed to superior value with increasing of TANF

144
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

3.5. Scanning vibrating electrode technique analysis

For investigating the corrosive activity at the coating artificial

scratch, SVET was used to monitor the localized corrosion of the bare or
coated metal substrate [48,49]. The electric potential signals at the
scratch were detected from platinum probe and electric potential data
was transformed into the local current density via Ohm law [50].
Fig. 10 showed the current density maps of pure epoxy, TANF0.5% and
TANF1.0% coatings immersed in 3.5 wt% NaCl solution at different in-
tervals. For pure waterborne epoxy coating (Fig. 10a and b), the arti-
ficial defect remained active and the highest anodic current density in
the test region was increased from 0.09 μA cm−2 (2 h) to 0.28 μA cm−2
(24 h), implying anodic corrosion occurred in the mild steel nearby
scratch with the permeation of NaCl solution [51]. By contrast, the
epoxy/TANF coatings exhibited lower corrosion activity after 24 h of
immersion. In detail, for TANF0.5% and TANF1.0% epoxy coating, anodic
current density had dropped from 0.28 μA cm−2 to 0.20 μA cm−2
(Fig. 10b and f). What’s more, it can be observed that anodic corrosion
activity for scan region of TANF0.5% coating was slightly lower than that
Fig. 11. XRD patterns of corrosion zones on the mild steel substrate surface of TANF1.0% after 24 h of exposure. This demonstrated that TANF
beneath epoxy and epoxy/TANF0.5% coatings after immersion in 3.5 wt% NaCl packing possessed the suppression action for anodic reaction and
for 37 d. slowed down the dissolution of mild steel [13,52,53].

content, which was −0.605 V for 0.5 wt% TANF coating and −0.645 V
for 1.0 wt% TANF containing coating. On the contrary, the icorr in- 3.6. Characterization of rust layers on the Q235 steel
creased from 4.717 × 10−9 to 9.348 × 10−9 A cm−2. Obviously,
0.5 wt% TANF waterborne coatings exhibited the lowest corrosion In further study, XRD was used to investigate the corrosion products
current density, thus it can be concluded that it possessed the best beneath the coatings. As we can see in Fig. 11, the metal oxide showed
corrosion performance. the weak diffraction peaks, relative to the peaks of metal substrate
surface. Compared to pure epoxy sample, the metal surface beneath
epoxy/TANF composite coating showed the new peaks associated with
Fe2O3, Fe2(OH)3Cl and Fe3O4 after 37 d of immersion in 3.5 wt% NaCl
solution. The identified Fe3O4 product was closed to the steel substrate

Fig. 12. SEM images of corrosion products for rust regions on the steel substrate coated by (a1, a2) pure epoxy and (b1, b2) epoxy/TANF0.5% coating after 37 d of
immersion.

145
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

and this oxide film prevented the oxygen from invading into inter- protection of magnesium alloys by organic coatings, Prog. Org. Coat. 73 (2012)
mediate layer [54] and the enriched chloridion through the coatings 129–141.
[10] V. Guillaumin, D. Landolt, Effect of dispersion agent on the degradation of a water
was united with metal oxide to form Fe2(OH)3Cl as long as the Fe3O4 borne paint on steel studied by scanning acoustic microscopy and impedance,
content was relatively higher [55]. From the above results, it could be Corros. Sci. 44 (2002) 179–189.
safely concluded the enhanced corrosive resistance properties was as- [11] C. Heitner-Wirguin, D. Friedman, Development of waterborne inorganic zinc sili-
cate anticorrosion coatings, Corros. Sci. Prot. Technol. 18 (2006) 41–45.
cribed to formation of a passive oxide layer via addition of conducting [12] M. Liu, X. Mao, H. Zhu, A. Lin, D. Wang, Water and corrosion resistance of epox-
TANF in the epoxy coating matrix. y–acrylic–amine waterborne coatings: effects of resin molecular weight, polar group
Furthermore, it was showed in Fig. 12 that the morphology images and hydrophobic segment, Corros. Sci. 75 (2013) 106–113.
[13] S. Qiu, W. Li, W. Zheng, H. Zhao, L. Wang, Synergistic effect of polypyrrole-inter-
of rust products beneath pure epoxy or epoxy/TANF composite coatings calated graphene for enhanced corrosion protection of aqueous coating in 3.5%
for comparison. In Fig. 12a1 and a2, there were lots of scattered frag- NaCl solution, ACS Appl. Mater. Interfaces 9 (2017) 34294–34304.
ments and irregular projections in the NaCl solution immersion. How- [14] L. Gu, X. Zhao, X. Tong, J. Ma, B. Chen, S. Liu, H. Zhao, H. Yu, J. Chen,
Electrochemical science facile preparation of polyaniline nanoparticles and their
ever, for 0.5 wt% of epoxy/TANF coating (Fig. 12b1 and b2), there were
dispersion for waterborne anticorrosion coatings, Int. J. Electrochem. Sci. 11 (2016)
only minor granular substance with the structure of “nuts” or “bread 1621–1631.
crumbs” and scarcely any traces on the surface. [15] D.W. DeBerry, Modification of the electrochemical and corrosion behavior of
stainless steels with an electroactive coating, J. Electrochem. Soc. 132 (1985)
1022–1026.
4. Conclusions [16] S. Qiu, C. Chen, W. Zheng, W. Li, H. Zhao, L. Wang, Long-term corrosion protection
of mild steel by epoxy coating containing self-doped polyaniline nanofiber, Syn.
In this paper, we have synthesized self-assembled tetraaniline na- Met. 229 (2017) 39–46.
[17] M.G. Hosseini, M. Sabouri, T. Shahrabi, Corrosion protection of mild steel by
nofiber (TANF) with high length-to-diameter ratio in acidic solution. polypyrrole phosphate composite coating, Prog. Org. Coat. 60 (2007) 178–185.
The as-prepared nanofibers had excellent processability, relative high [18] G. Kousik, S. Pitchumani, N.G. Renganathan, Electrochemical characterization of
conductivity and reversible redox behavior, making it suitable as an polythiophene-coated steel, Prog. Org. Coat. 43 (2001) 286–291.
[19] C. Ocampo, E. Armelin, F. Liesa, C. Alemán, X. Ramis, J.I. Iribarren, Application of a
efficient anticorrosive pigment for waterborne epoxy coating. Only polythiophene derivative as anticorrosive additive for paints, Prog. Org. Coat. 53
addition of 0.5 wt% TANF notably enhanced the corrosion resistance of (2005) 217–224.
waterborne coating as proven by Tafel curves and EIS. Further in- [20] F. Yang, T. Liu, J. Li, S. Qiu, H. Zhao, Anticorrosive behavior of a zinc-rich epoxy
coating containing sulfonated polyaniline in 3.5% NaCl solution, RSC Adv. 8 (2018)
vestigation of rust products underneath of the coating via XRD and 13237–13247.
SEM, it was concluded that the addition of TANI nanofibers facilitated [21] J. He, V.J. Gelling, D.E. Tallman, G.P. Bierwagen, G.G. Wallace,
the formation of a relatively stable passive layer composed of Fe2O3 and Conducting Polymers, I.I.I. Corrosion, A scanning vibrating electrode study of poly
(3-octyl pyrrole) on steel and aluminum, J. Electrochem. Soc. 147 (2000)
Fe3O4. This tetraaniline-based nanofiber prepared by facile and en-
3667–3672.
vironmental-friendly self-assembly approach can potentially be applied [22] B.O. Alexander, G. Wu, J.S. Haataja, B. Felicitas, F. Natalie, A.M. Seddon,
for other applications such as anti-electrostatic coating, electro- R.L. Harniman, R.M. Richardson, I. Olli, Z. Xi, Self-assembly of a functional oligo
magnetic interference (EMI) coating. (Aniline)-based amphiphile into helical conductive nanowires, J. Am. Chem. Soc.
137 (2015) 14288–14294.
[23] Y. W., H.D. T., L. L., X. D., R.B. Kaner, Nanoscale morphology, dimensional control,
Conflicts of interest and electrical properties of oligoanilines, J. Am. Chem. Soc. 132 (2010) 10365-
10373.
[24] S.H. Qiu, C. Chen, M.J. Cui, W. Li, H.C. Zhao, L.P. Wang, Corrosion protection
All of authors declare no competing financial interest. performance of waterborne epoxy coatings containing self-doped polyaniline na-
nofiber, Appl. Surf. Sci. 407 (2017) 213–222.
Acknowledgements [25] L. Zang, Y. Che, J.S. Moore, ChemInform abstract: one‐dimensional self‐assembly of
planar π‐conjugated molecules: adaptable building blocks for organic nanodevices,
Acc. Chem. Res. 40 (2009) 1596–1608.
This work was supported by funds from “One Hundred Talented [26] C.O. Baker, X. Huang, W. Nelson, R.B. Kaner, Polyaniline nanofibers: broadening
People” of the Chinese Academy of Sciences (No. Y60707WR04), and applications for conducting polymers, Chem. Soc. Rev. 46 (2017) 1510–1525.
[27] T.K. Rout, G. Jha, A.K. Singh, N. Bandyopadhyay, O.N. Mohanty, Development of
Natural Science Foundation of Zhejiang Province (No. Y16B040008).
conducting polyaniline coating: a novel approach to superior corrosion resistance,
Surf. Coat. Technol. 167 (1) (2003) 16–24.
Appendix A. Supplementary data [28] S.P. Surwade, S.R. Agnihotra, V. Dua, N. Manohar, S. Jain, S. Ammu, S.K. Manohar,
Catalyst-free synthesis of oligoanilines and polyaniline nanofibers using H2O2, J.
Am. Chem. Soc. 131 (2009) 12528–12529.
Supplementary material related to this article can be found, in the [29] L. Jiang, X. Wang, L. Chi, Nanoscaled surface patterning of conducting polymers,
online version, at doi:https://doi.org/10.1016/j.porgcoat.2018.11.033. Small 7 (2011) 1309–1321.
[30] W. Lv, J.T. Feng, W. Yan, C.F.J. Faul, Self-assembly and pH response of electro-
active liquid core-tetra(aniline) shell microcapsules, J. Mater. Chem. B Mater. Biol.
References Med. 2 (2014) 4720–4725.
[31] M. Ziabari, V. Mottaghitalab, S.T. McGovern, A.K. Haghi, A new image analysis
[1] V. Upadhyay, D. Battocchi, Localized electrochemical characterization of organic based method for measuring electrospun nanofiber diameter, Nanosc. Res. Lett. 2
coatings: a brief review, Prog. Org. Coat. 99 (2016) 365–377. (2007) 597–600.
[2] J.T. Zhang, H.U. Ji-Ming, J.Q. Zhang, A Review on modern study methods of or- [32] L. Gu, S.A. Liu, H.C. Zhao, H.B. Yu, Anticorrosive oligoaniline-containing electro-
ganic coatings, Mater. Sci. Eng. 21 (2003) 763–768. active siliceous hybrid materials, RSC Adv. 5 (2015) 56011–56019.
[3] K.S. Kim, N. Gunari, D. MacNeil, J. Finlay, M. Callow, J. Callow, G.C. Walker, [33] H. Kim, J.W. Park, Self-assembly of rod-coils consisting of tetraaniline and alkyl
Aqueous-based fabrication of low-VOC Nanostructured block copolymer films as chains in different oxidation states, J. Mater. Chem. 20 (2010) 1186–1191.
potential marine antifouling coatings, ACS Appl. Mater. Interfaces 8 (2016) [34] W. Lyu, J.T. Feng, W. Yan, C.F.J. Faul, Self-assembly of tetra(aniline) nanowires in
20342–20351. acidic aqueous media with ultrasonic irradiation, J. Mater. Chem. C Mater. Opt.
[4] O. Herbarth, S. Matysik, Decreasing concentrations of volatile organic compounds Electron. Devices 3 (2015) 11945–11952.
(VOC) emitted following home renovations, Indoor Air 20 (2010) 141–146. [35] P. Colomban, A. Gruger, A. Novak, A. Régis, Infrared and Raman study of poly-
[5] M.D. Meijer, Review on the durability of exterior wood coatings with reduced VOC- aniline Part I. Hydrogen bonding and electronic mobility in emeraldine salts, J. Mol.
content, Prog. Org. Coat. 43 (2001) 217–225. Struct. 317 (1994) 261–271.
[6] M. Hernández, J. Genescá, J. Uruchurtu, A. Barba, Correlation between electro- [36] Q. Tang, J. Wu, X. Sun, Q. Li, J. Lin, Shape and size control of oriented polyaniline
chemical impedance and noise measurements of waterborne coatings, Corros. Sci. microstructure by a self-assembly method, Langmuir 25 (2009) 5253–5257.
51 (2009) 499–510. [37] D. Chao, S. Wang, R. Yang, E.B. Berda, C. Wang, Synthesis and properties of mul-
[7] J.V. Barbosa, E. Veludo, J. Moniz, A. Mendes, F.D. Magalhães, M.M.S.M. Bastos, tifunctional poly(amic acid) with oligoaniline and fluorene groups, Colloid Polym.
Low VOC self-crosslinking waterborne acrylic coatings incorporating fatty acid Sci. 291 (2013) 2631–2637.
derivatives, Prog. Org. Coat. 76 (2013) 1691–1696. [38] W. Lv, J. Feng, W. Yan, C.F.J. Faul, Self-assembly and pH response of electroactive
[8] F. Chen, P. Liu, Conducting polyaniline nanoparticles and their dispersion for wa- liquid core–tetra(aniline) shell microcapsules, J. Mater. Chem. B Mater. Biol. Med. 2
terborne corrosion protection coatings, ACS Appl. Mater. Interfaces 3 (2011) (2014) 4720–4725.
2694–2702. [39] S. Wang, D. Chao, E.B. Berda, X. Jia, R. Yang, X. Wang, T.T. Jiang, C. Wang,
[9] R.G. Hu, S. Zhang, J.F. Bu, C.J. Lin, G.L. Song, Recent progress in corrosion Fabrication of electroactive oligoaniline functionalized poly(amic acid) nanofibers

146
T. Liu et al. Progress in Organic Coatings 128 (2019) 137–147

for application as an ammonia sensor, RSC Adv. 3 (2013) 4059–4065. Coat. 76 (2013) 804–811.
[40] I. Kulszewicz-Bajer, I. Rozalska, M. Kurylek, 1 Linear, 4-coupled oligoanilines of [48] T.C. Huang, T.C. Yeh, H.Y. Huang, W.F. Ji, T.C. Lin, C.A. Chen, T.I. Yang, J.M. Yeh,
defined length: Preparation and spectroscopic properties, New J. Chem. 28 (2004) Electrochemical investigations of the anticorrosive and electrochromic properties of
1235–1243. electroactive polyamide, Electrochim. Acta 63 (2012) 185–191.
[41] A. Airoudj, D. Debarnot, B. Beche, F. Poncin-Epaillard, Development of an optical [49] J.M. Falcón, F.F. Batista, I.V. Aoki, Encapsulation of dodecylamine corrosion in-
ammonia sensor based on polyaniline/epoxy resin (SU-8) composite, Talanta 77 hibitor on silica nanoparticles, Electrochim. Acta 124 (2014) 109–118.
(2009) 1590–1596. [50] C. Liu, S. Qiu, P. Du, H. Zhao, L. Wang, An ionic liquid-graphene oxide hybrid
[42] B.R. Hinderliter, S.G. Croll, D.E. Tallman, Q. Su, G.P. Bierwagen, Interpretation of nanomaterial: synthesis and anticorrosive applications, Nanoscale 10 (2018)
EIS data from accelerated exposure of coated metals based on modeling of coating 8115–8124.
physical properties, Electrochim. Acta 51 (2006) 4505–4515. [51] T. Siva, S. Sathiyanarayanan, Self healing coatings containing dual active agent
[43] N. Sarkar, G. Sahoo, R. Das, G. Prusty, D. Sahu, S.K. Swain, Anticorrosion perfor- loaded urea formaldehyde (UF) microcapsules, Prog. Org. Coat. 82 (2015) 57–67.
mance of three-dimensional hierarchical PANI@BN nanohybrids, Ind. Eng. Chem. [52] Y. González-García, J.M.C. Mol, T. Muselle, I. De Graeve, G. Van Assche,
Res. 55 (2016). G. Scheltjens, B. Van Mele, H. Terryn, A combined mechanical, microscopic and
[44] G.J. Brug, A.L.G. Vandeneeden, M. Sluytersrehbach, J.H. Sluyters, The analysis of local electrochemical evaluation of self-healing properties of shape-memory poly-
electrode impedances complicated by the presence of a constant phase element, urethane coatings, Electrochim. Acta 56 (2011) 9619–9626.
Corros. Sci. 176 (1984) 275–295. [53] A. Lutz, O. van den Berg, J. Van Damme, K. Verheyen, E. Bauters, I. De Graeve,
[45] E. Cano, D. Lafuente, D.M. Bastidas, Use of EIS for the evaluation of the protective F.E. Du Prez, H. Terryn, A shape-recovery polymer coating for the corrosion pro-
properties of coatings for metallic cultural heritage: a review, J. Solid State tection of metallic surfaces, ACS Appl. Mater. Interfaces 7 (2015) 175–183.
Electrochem. 14 (2009) 381–391. [54] D. de la Fuente, I. Díaz, J. Alcántara, B. Chico, J. Simancas, I. Llorente, A. García-
[46] J. Mondal, A. Marques, L. Aarik, J. Kozlova, A. Simões, V. Sammelselg, Delgado, J.A. Jiménez, P. Adeva, M. Morcillo, Corrosion mechanisms of mild steel
Development of a thin ceramic-graphene nanolaminate coating for corrosion pro- in chloride-rich atmospheres, Mater. and Corros. 67 (2016) 227–238.
tection of stainless steel, Corros. Sci. 105 (2016) 161–169. [55] J. Alcántara, B. Chico, I. Díaz, D. de la Fuente, M. Morcillo, Airborne chloride de-
[47] Y. Zhang, Y. Shao, T. Zhang, G. Meng, F. Wang, High corrosion protection of a posit and its effect on marine atmospheric corrosion of mild steel, Corros. Sci. 97
polyaniline/organophilic montmorillonite coating for magnesium alloys, Prog. Org. (2015) 74–88.

147