Accepted Manuscript

Corrosion protection of carbon steels by electrochemically synthesized V-TiO2/

polypyrrole composite coatings in 0.1�M HCl solution

Zhihao Chen, Wenzhong Yang, Bin Xu, Yun Chen, Mengqi Qian, Xin Su, Zhuohang
Li, Xiaoshuang Yin, Ying Liu
PII: S0925-8388(18)33233-X
DOI: 10.1016/j.jallcom.2018.09.003
Reference: JALCOM 47422

To appear in: Journal of Alloys and Compounds

Received Date: 27 April 2018

Revised Date: 22 August 2018
Accepted Date: 1 September 2018

Please cite this article as: Z. Chen, W. Yang, B. Xu, Y. Chen, M. Qian, X. Su, Z. Li, X. Yin, Y.
Liu, Corrosion protection of carbon steels by electrochemically synthesized V-TiO2/polypyrrole
composite coatings in 0.1�M HCl solution, Journal of Alloys and Compounds (2018), doi: 10.1016/
j.jallcom.2018.09.003.

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 ACCEPTED MANUSCRIPT

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Corrosion protection of carbon steels by electrochemically

synthesized V-TiO2/polypyrrole composite coatings in 0.1 M
HCl solution

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Zhihao Chena, Wenzhong Yanga,*, Bin Xu b,*, Yun Chena,*, Mengqi Qiana, Xin Sua,

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Zhuohang Lia, Xiaoshuang Yina, Ying Liua

a
College of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 210009, China

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b
Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection, Nanjing 210042,
China

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* Corresponding author. Tel.: +86 25 83172359; fax: +86 25 83172359.

E-mail address: yangwznjtech@163.com (W. Z. Yang), xubinnies@163.com (B. Xu)，
ychen@njtech.edu.cn (Y. Chen)

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Abstract

Polypyrrole (PPy) composite coatings had been effectively synthesized in the presence of
TiO2 and V-TiO2 nanoparticles on carbon steel by electrochemical method in aqueous

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oxalic acid solutions. These coatings were characterized by different surface analysis
methods. TEM results confirmed that the size of V-TiO2 nanoparticles (11.91 ± 1.03 nm)

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was smaller than that of TiO2 nanoparticles (17.22 ± 2.84 nm), therefore increasing the
interaction between PPy composite coatings and metal surface. The electrical

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conductivity measurement was carried out to examine the electrical properties of
TiO2/PPy and V-TiO2/PPy composite coatings. Besides, the electrochemical behaviors of

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these coatings were also studied in 0.1 M HCl solution by electrochemical impedance
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spectroscopy and potentiodynamic polarization measurements. Results showed that the
V-TiO2/PPy composite coatings exhibited better anti-corrosion performance than
TiO2/PPy composite coatings. The exceptional anti-corrosion performance of PPy
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composite coatings was associated with the synergistic effect of the increase in physical
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barrier, prevention of charge transport by TiO2 nanoparticles and the complex passive
film on the metal surface.
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Keywords: Corrosion protection; Polypyrrole composite coatings; V-TiO2 nanoparticles;

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EIS; Electrical conductivity

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1. Introduction

Nowadays, despite of a great challenge from advanced alloys such as aluminum and
titanium, the carbon steel (CS) was still considered as the important material in varieties

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of industries due to its excellent mechanical properties, low cost and wide availability [1].
However, the corrosion phenomenon of CS often occurred in harsh environment.

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Unfortunately, corrosion could not be fully avoided, and corrosion control became the
only way by slowing the kinetics and altering the mechanism [2]. Among various

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corrosion inhibition methods, coating protection had become a popular way to produce a
physical barrier that protected against the aggressive environment.

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Conducting polymers (CPs) were a new class of polymeric materials with
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conjugated sequences of double and single bonds, which showed great potential
application because of their high electrical conductivity, easy preparation, mechanical
stability and environmentally friendly [3]. Of the class of CPs materials, PPy was one of
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the most attractive alternatives for corrosion protection when applied as coatings, which
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prevented the contact of substrate with corrosive ions and thus reduced the corrosion rate.
The corrosion protection ability of CPs coatings was dependent on their structure and
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electronic properties [4]. In recent years, the electrosynthesis of PPy coatings had gained
specific interests for researchers due to the easy polymerization process, better control of
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coating thickness and morphology, and cleaner coating when compared with the chemical
oxidation synthesis [5,6].
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Unfortunately, the application of PPy coatings for corrosion protection of metals had
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been limited for long time exposure in the corrosive medium due to the inhomogeneous
surface. In order to overcome this problem, more and more researchers focused on the
PPy composite coatings (CTs). The addition of dopants into PPy coatings was a useful
method because it increased their thermostability, hydrophobicity and anti-corrosion
nature to a greater extent [7]. Moreover, the CPs prepared in the vicinity of nanoparticles
(NPs) had increased surface area, which increased their capability of interaction with the

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released ions in the process of corrosion [8,9]. The added advantage of the NPs was the
synergistic interaction between PPy and fillers in achieving the best possible combination
of properties. In particular, the development of the NPs such as ZrO2 [10], Al2O3 [11],
Fe3O4 [12], SiO2 [13], ZnO [14] and clay [15] in PPy coatings had already been reported

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to improve the corrosion resistance and mechanical properties of coatings. Among these
available NPs, titanium dioxide (TiO2) is one of the best known transition metal oxides

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that could be used as fillers due to its non-toxicity, low cost, high resistance to corrosion
and stable characteristics [16,17]. M. Hosseini et al. [18] synthesized the PPy CTs in the

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presence of TiO2 NPs on Al electrodes. They investigated the anti-corrosion behaviors of
the PPy CTs by using electrochemical impedance spectroscopy (EIS) and

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potentiodynamic polarization (PP) measurements. Results showed that the doping of TiO2
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NPs was proved to be a great improvement in the performance of PPy CTs for corrosion
protection. B.D. Mert [19] investigated the TiO2/PPy CTs used as anode material for
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direct methanol fuel cell. The corrosion resistance of Al/TiO2-PPy was almost 5 times
higher than that of Al after 168 h immersion in 3.5 % NaCl solution.
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In order to further enhance the properties of the TiO2/PPy CTs, some reports
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attempted to modify the TiO2 NPs and then incorporated into PPy coatings. M. Ladan et
al. [20] synthesized PPy CTs in the presence of TiO2 NPs and Co-TiO2 NPs. The EIS
results showed that the log |Z| of Co-TiO2/PPy and TiO2/PPy coated samples reached
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about 8.2 and 6.0 respectively after 30 days of exposure in 3.5% NaCl solution. And the
Co-TiO2/PPy CTs exhibited better performance in corrosion protection of steel surface
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than TiO2/PPy CTs. M.R. Mahmoudian at al. [8] chemically polymerized Sn-TiO2/PPy
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CTs. The electrochemical results showed that the performance of Sn-TiO2/PPy CTs was
better than TiO2/PPy CTs. And the increasing area of the PPy in the presence of Sn-TiO2
NPs could increase its ability to interact with the ions liberated during the corrosion
reaction of steel.

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In present investigation, our efforts are made to fabricate PPy CTs containing TiO2
NPs and V-TiO2 NPs . V is a transition metal with multiple characteristics, and vanadium
compound are a class of promising environmental-friendly corrosion inhibitor for the
paint or pigment systems, which could improve the corrosion resistance [21]. So the idea

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of stable superior anti-corrosive ability was attained by incorporating V into TiO2 lattice.
As far as our knowledge is concerned, no studies have ever been reported on the

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application of V-TiO2/PPy CTs as anti-corrosion coatings. The V-TiO2/PPy CTs were
electrosynthesized by CV method. And then we investigated the influence of doping

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concentration of V in TiO2 lattice on the surface morphology of V-TiO2/PPy CTs. The
weight loss test, EIS and PP measurements were used to evaluate the corrosion behaviors

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of these CTs in 0.1 M HCl solution. In addition, the electrical conductivity measurement
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was performed to examine the electrical properties of TiO2/PPy CTs and V-TiO2/PPy
CTs.
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2. Experimental
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2.1. Materials
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The used CSs contained 0.17 wt % C, 0.20 wt % Si, 0.37 wt % Mn, 0.03 wt % S,
0.01 wt % P and balance Fe. The experimental samples (20×20×1 mm) were polished
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mechanically using 500-2000 grit emery papers successively and then rinsed several
times with ultrapure water and acetone for 10-15 min, finally dried and kept under
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vacuum prior to use.

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2.2. Synthesis of V-TiO2 NPs and TiO2 NPs

The V-TiO2 NPs were prepared by sol-gel methods. Titanium oxysulfate dihydrate
(TiOSO4·2H2O) and ammonium metavanadate (NH4VO3) were the precursors. All the
chemicals were analytical grade. At the beginning, TiOSO4·2H2O solution (0.5 M) was

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prepared with adding ultrapure water into the mixture. Then the pH of the mixture was
adjusted to alkalinity by adding ammonium hydroxide (NH3·H2O). After vigorous stirring
for about 6 h at room temperature, the resultant mixture was kept for 24 h to form a gel.
The as-synthesized gel was placed in a vacuum oven at 60 °C for 6 h. Furthermore, the

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produced powders was calcined at 350 °C for 3 h to form the TiO2 NPs. Then the
synthesized TiO2 NPs (1 g) was mixed with different amount of NH4VO3 and 300 ml

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ultrapure water was added. The obtained mixture with different V contents of 0.05 M, 0.1
M and 0.15 M. The prepared V-TiO2 NPs were called 0.05V-TiO2 NPs, 0.1V-TiO2 NPs

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and 0.15V-TiO2 NPs, respectively.

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2.3. Preparation of TiO2/PPy CTs and V-TiO2/PPy CTs
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TiO2/PPy CTs and V-TiO2/PPy CTs were achieved by CV method. The solutions
contained 0.3 M oxalic acid, 0.1 M Pyrrole (Py) and 1 g L-1 TiO2 NPs or V-TiO2 NPs,
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respectively. Prior to each electrosynthesis, all the solutions were purged with N2 gas for
15 min in order to remove the oxygen in the electrolyte. The cyclic scans were carried out
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with potential range from - 0.5 V to + 0.9 V for 30 scanning circles and the scanning rate
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was 50 mV s-1. After electrosynthesis, TiO2/PPy CTs and V-TiO2/PPy CTs were rinsed
with ultrapure water for several times and then dried at 60 °C in vacuum oven overnight.
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2.4. Coating characterization

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The Fourier Transform Infrared Spectra (FTIR) of TiO2 NPs, V-TiO2 NPs, TiO2/PPy
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CTs and V-TiO2/PPy CTs were recorded with Thermo Scientific Nicolet IS5. The Escalab
250Xi X-ray photoelectron spectroscopy (XPS) was used to determine the chemical
valence of the particular elements in TiO2 NPs. The X-ray diffraction (XRD) was
performed to confirm the phase structure of the TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs
and V-TiO2/PPy CTs by using MiniFlex 600, while the transmission electron microscopy
(TEM) was used to determine the morphologies and size of the TiO2 NPs and V-TiO2 NPs

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by a JEOL JEM-2100F instrument. The morphologies of the TiO2/PPy CTs and

V-TiO2/PPy CTs were observed by a JEOL JEM-6510 scanning electron microscope
instrument (SEM) equipped with NS7 Energy Dispersive X-ray (EDX). The thickness of
these coatings was measured by JC220 Coating Thickness Gauge. The surface wettability

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of TiO2/PPy CTs and V-TiO2/PPy CTs was investigated by DropMeter A-100P contact
angle analyzer. The thermostability of TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs and

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V-TiO2/PPy CTs were performed by TG Q500 thermogravimetric analysis (TGA) with a
heating rate of 10 °C min−1 up to 800 °C. The electrical conductivity of TiO2/PPy CTs

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and V-TiO2/PPy CTs was measured by using the standard method of four points.

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2.5. Immersion tests
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The corrosion behaviors of bare CS and TiO2/PPy and V-TiO2/PPy coated CSs were
investigated through the immersion tests in 0.1 M HCl solution at 298 K. After a
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specified immersion time, the morphologies of these CSs were evaluated by SEM.
Simultaneously, the concentrations of the released Fe2+ ions from CSs were quantified
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through inductively coupled plasma atomic emission spectrometry (ICP-AES) analysis.

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2.6. Electrochemical measurements

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The anti-corrosion property of these coatings was evaluated using EIS and PP
measurements, which were conducted by Gamry Reference 4000 electrochemical
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workstation. A conventional standard three-electrode cell system was utilized for the
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electrochemical tests. A saturated calomel (SCE) was the reference electrode along with a
platinum sheet worked as the counter electrode (CE), and the CS served as the working
electrode (WE). Before EIS experiments, the system was immersed in 0.1 M HCl
solution for 30 min to reach a stable open-circuit potential (OCP) value. Then, the EIS
experiments were analyzed over the frequency range from 100 kHz to 100 mHz at 10 mV

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signal amplitude. For the PP measurements, the Tafel curves were scanned from cathodic
direction to anodic direction (Eocp ± 250 mV) at a scanning rate of 1 mV s-1.

3. Experiments

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3.1. Preparation of TiO2/PPy CTs and V-TiO2/PPy CTs

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The electrosynthesis of TiO2/PPy CTs and V-TiO2/PPy CTs was used CV method as
shown in Fig. 1. The scanning potential was conducted between - 0.5 V and + 0.9 V with

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a scanning rate of 50 mV s-1 for 30 cycles. Fig. 1a was the CV curves of electrosynthesis
of TiO2/PPy CTs. For the first cycle, the anode current peak appeared at - 0.25 V, which

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corresponded to the dissolution of iron. The C2O42− and Fe2+ formed an insoluble
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complex (FeC2O4), which covered the CS surface before the electrosynthesis of the
TiO2/PPy CTs and inhibited the dissolution of iron [5]. The surface of the CS was in a
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passive state after several scanning cycles, which was due to the formation of the
insoluble complex (FeC2O4) covered the CS surface. The oxidation of the Py occurred
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when the potential reached about 0.6 V, then the oxidation current sharply increased at
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0.9 V. Meanwhile, a black PPy coating started to cover the CS surface. With the scanning
cycles increased, the oxidation current exhibited a bit decreased because of the formation
of PPy coatings over the metal surface. During the reverse scanning, the redox peak
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appeared at - 0.25 V, which was attributed to the reduction of PPy and the extraction of
the counter anions [22]. It was worth noting that the oxidation and reduction peaks
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appeared relatively stable, indicating that the TiO2 NPs were successfully incorporated
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into PPy CTs. After a close inspection of the electrode, it was found that a thick black
film appeared on the surface of CS fully after 30 cycles. The thickness of TiO2/PPy CT
was about 2.01 ± 0.24 um.
Besides, the CV curves of these electrosynthesis of V-TiO2/PPy CTs were shown in
Fig. 1 (b-d). The shape of the CV curves was similar to Fig. 1a, the passivation current

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peak of CS, which was at around - 0.23 V in the first cycle, indicating a same
electrosynthesis process as TiO2/PPy CTs. However, the intensity of the passivation
current peak decreased with the increasing amounts of V in TiO2 NPs, indicating that the
dissolution of the iron was greatly depressed. Moreover, it was worth noting that the

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oxidation current density increased with increasing amounts of V in TiO2 NPs. This
phenomenon occurred due to the electrostatic interactions between the oxidized cationic

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PPy structure and TiO2 bearing negative surface charges, which was a result of the
attachment of oxalate ions anions on the surface [23]. After 30 cycles scanning, the black

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film covered the CS surface, and the thicknesses of 0.05V-TiO2/PPy CT, 0.1V-TiO2/PPy
CT and 0.15V-TiO2/PPy CT were calculated to be 2.98 ± 0.14 um, 3.64 ± 0.15 um and

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5.06 ± 0.07 um. The increased thickness of these coatings further enhanced the physical
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barrier effect, which blocked the corrosive ions from CS.

3.2. Material characterization

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3.2.1. FTIR spectra of TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs and V-TiO2/PPy CTs
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Fig. 2 was the FTIR spectra of TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs and
V-TiO2/PPy CTs. For TiO2 NPs, the absorption band at 3140 cm-1 was due to the O-H
stretching vibration, indicating the existence of hydrogen-bonding between OH and TiO2
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surface. The peak at 1630 cm-1 was attributed to the H-O-H bending vibration of water
molecules, as well as Ti-OH. The broad peak between 700 cm-1 and 400 cm-1 was
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assigned to the Ti-O-Ti vibration, which corresponded to the Ti-O bending of the TiO2
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[24-26]. For V-TiO2 NPs, the similar FTIR spectra was observed. However, the intensity
of the peaks decreased because the doping of V in TiO2 NPs reduced the relative content
of titanium. The additional peak located at 1120 cm-1 was likely due to the V-O bending
vibration [27]. Oxygen vacancies were easily formed in the doped TiO2 lattice when Ti4+
was substituted with V5+ to keep charge in balance [16]. For TiO2/PPy CTs and

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V-TiO2/PPy CTs, the band at 3610 cm-1 was due to the N-H stretching vibration and the
1396 cm-1 was attributed to the major breathing vibration of the Py rings. Meanwhile, the
peak around 1200 cm-1 was attributed to the C-N stretching vibration. The band at 1018
cm-1 belonged to the C-H and N-H in-plane deformation vibrations [28]. And the bands

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around 760 cm-1 and 633 cm-1 suggested the presence of TiO2 NPs in PPy CTs.

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3.2.2. XPS of TiO2 NPs and V-TiO2 NPs

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XPS was studied in order to further confirm the chemical composition and states of
the elements of TiO2 NPs and V-TiO2 NPs. The chemical states of Ti 2p and V 2p species
were obtained by analyzing the XPS core levels. As shown in Fig. 3a, the Ti 2p with two

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peaks was obtained corresponding to Ti 2p3/2 (459.2 eV) and Ti 2p1/2 (465.0 eV) species
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[29]. The spin orbit splitting of 5.8 eV indicated that the Ti4+ existed in the V-TiO2 NPs
[30,31]. Besides, as observed in Fig. 3b, the peaks appearing at binding energies of 516.5
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eV and 525.1 eV were ascribed to the V 2p3/2 and V 2p1/2 species. These peaks were
mainly related to the presence of V4+ [32]. And the peak at 517.7 eV was the signal of V5+
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2p3/2 species [33]. Therefore, the fitting data demonstrated that V5+ was the dominant
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composition in V-TiO2 NPs. While, the ionic radii of V5+ (0.54 Å), V4+ (0.58 Å) and Ti4+
(0.61 Å) were close. Therefore V5+ could be easily substituted for the Ti4+ into the TiO2
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crystal lattice, causing the crystal lattice distorted and reducing the crystallite size [34].

3.2.3. XRD of TiO2, V-TiO2, TiO2/PPy and V-TiO2/PPy

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The phase structure of the TiO2 NPs and V-TiO2 NPs was depicted in Fig. 4. From
the XRD diffraction patterns, it could be seen that both TiO2 NPs and V-TiO2 NPs were in
the anatase phase. The different diffraction peaks of TiO2 NPs appeared at 25°, 38°, 48°,
54°, 55° and 63°, which corresponded to the (101), (004), (200), (105), (211) and (204)
crystal planes of the anatase [35]. Also, it was obvious that the XRD pattern of V-TiO2
NPs displayed a similar XRD pattern with that of TiO2 NPs. The pattern did not show any

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obvious peaks of vanadium metal or oxides forms, which implied the incorporation of V
in the lattice of anatase TiO2 was limited and highly dispersed [36]. However, the
intensity of the diffraction (101) peak of V-TiO2 NPs increased compared to TiO2 NPs.
This was a result of the decrease in the crystallite size of V-TiO2 NPs due to the doping of

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V. The crystallite size of TiO2 NPs and V-TiO2 NPs was calculated by the following
Scherrer equation through Eq. (1) [20].

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Kλ
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β cos θ (1)

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where D is the crystallite size of the NPs, K is the shape factor, which is 0.9, λ is the
X-ray wavelength, β is the full-width half maximum of respective diffraction peak (rad),

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θ is the angle of diffraction corresponding to the (101) plane. The calculated average
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crystallite sizes were 18.19 nm, 12.71 nm, 12.53 nm and 12.79 nm for TiO2 NPs,
0.05V-TiO2 NPs, 0.1V-TiO2 NPs and 0.15V-TiO2 NPs, respectively. Therefore, the
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doping of V influenced the crystallite size, but it had no impact on the crystal structure.
Fig. 5 showed the X-ray diffraction spectra of TiO2/PPy CTs and V-TiO2/PPy CTs.
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The peaks appeared at 45° and 65° corresponded to the (200) and (204) crystal planes of
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the TiO2 in PPy CTs [37]. However, the diffraction peaks shifted toward a higher
diffraction angle gradually with the incorporation of V, suggesting V-TiO2 NPs were
successfully doped into PPy CTs without effecting the crystal structure. In our case, the
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successful doping of V was further evidenced by EDX analysis.

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3.2.4. The TEM of TiO2 NPs and V-TiO2 NPs

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To determine the morphology and size of the TiO2 NPs and V-TiO2 NPs, TEM
analysis was performed. The samples were suspended in ethanol separately and sonicated
for 1 h. Fig. 6 was TEM images of TiO2 NPs and V-TiO2 NPs. As seen from the pictures,
the spherical shape aggregate was TiO2 NPs. Darker parts of the images indicated that the
NPs were concentrated. The size distribution of the NPs was determined by measuring

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the diameter of 150 NPs in random. As seen in the Fig. 6 (a-d), the distribution of the
V-TiO2 NPs was more even over the selected surface when compared to the TiO2 NPs.
And the mean size of the TiO2 NPs, 0.05V-TiO2 NPs, 0.1V-TiO2 NPs and 0.15V-TiO2
NPs was calculated to be around 17.22 ± 2.84 nm, 12.40 ± 2.13 nm, 12.02 ± 1.56 nm and

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11.91 ± 1.03 nm, respectively. The results concluded by TEM reached an agreement with
those obtained from XRD analysis. Fig. 7 (a-d) were the size histograms of TiO2 NPs and

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V-TiO2 NPs. The atomic proportion on the surface of the NPs increased when the
dimension of the NPs became smaller. Meanwhile, the highest frequency of these NPs

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diameter achieved at 16 - 18 nm and 12 - 14 nm for TiO2 NPs and V-TiO2 NPs,
respectively. Under these circumstances, the atoms on the surface could influence the

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morphology of the coatings. Taking into a general account, the size of the TiO2 NPs
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decreased evidently by the doping of V in the TiO2 lattice, which contributed to the
formation of the intact and smooth V-TiO2/PPy CTs.
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3.2.5. SEM and EDX analysis of TiO2/PPy CTs and V-TiO2/PPy CTs
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The SEM images of TiO2/PPy CTs and V-TiO2/PPy CTs were displayed in Fig. 8.
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All the PPy CTs had the similar spherical structure like cauliflower. The TiO2/PPy CTs
exhibited a disordered and inhomogeneous surface and the size of these PPy balls was
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generally between 3 µm and 10 µm. However, for the V-TiO2/PPy CTs, it was noteworthy
to realize that the V-TiO2/PPy CTs surface became more compact and smoother as the
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doping ratio of V increased. The distribution of the PPy particles was uniform and the
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size of PPy balls was about 2 µm. It was a result of the strong physicochemical
interaction between V-TiO2 NPs and PPy CTs. Moreover, the good dispersion of V-TiO2
NPs in PPy CTs restrained the growth of PPy structure. Hence, the doping of V-TiO2 NPs
was responsible for the compact and dense V-TiO2/PPy CTs. The 0.15V-TiO2/PPy CTs
exhibited the most uniform and intact coating surface, which ensured a better
hydrophobic coating surface. Therefore, the 0.15V-TiO2/PPy CTs were selected as the

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sample used in the following corrosion tests. In addition, the EDX analysis of
V-TiO2/PPy CTs and V-TiO2/PPy CTs was shown in Fig. 9. The clear signals for carbon,
nitrogen, oxygen, iron, titanium and vanadium were detected in PPy CTs. The N element
was from the amino group in PPy. The Ti element was due to the successful doping of

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TiO2 NPs. The presence of V element confirmed the incorporation of V in TiO2 NPs.

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3.2.6. Static water contact angle measurements

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The contact angle value could be considered as an indicator of the hydrophobicity of
coatings [38]. In our test, static water contact angle measurements were performed before
and after exposure in 0.1 M HCl solution. Fig. 10 depicted the contact angle values of all

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the samples before and after exposure to 0.1 M HCl solution. The bare CS would be
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readily attacked by corrosive ions due to its hydrophilic surface (62°). Consequently, after
12 h immersion in 0.1 M HCl solution, the surface of the bare CS was nearly in a
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complete water-penetrable condition (13°). The hydrophilic surface was transformed to a

hydrophobic surface with higher contact angle values (109° and 116°) when the CS
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covered by TiO2/PPy CT and V-TiO2/PPy CT. The observed high water contact angle
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indicated little water could penetrate through the micro-pores of the coatings [39]. After
12 h immersion, the contact angle value of TiO2/PPy CT decreased to 83°, which
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illustrated that the surface of the coating was in a wet condition. However, the
V-TiO2/PPy CT maintained hydrophobic with a contact angle value of 97°. In conclusion,
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the V-TiO2 NPs were confirmed to be more effective to maintain high resistance during
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prolonged exposure to corrosive environment owing to their hydrophobic surface.

According to the Ogihara et al. report [40], all the hydrophobic surface possessed a low
surface energy. Hence, the V-TiO2/PPy CTs had a low surface energy and water resistance
ability, the corrosive ions hardly penetrated into the coating. Apart from these, all the
contact angle values declined after 12 h immersion, which was due to the variation of the
coating roughness. Corrosion reaction occurred on the coating/electrolyte interface,

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causing the damage of coatings and hence increasing the coatings roughness. It could be
concluded that coatings with lower roughness exhibited higher contact angles. SEM
results were also supported this conclusion, where V-TiO2/PPy CTs exhibited smoother
and more compact surface than that of TiO2/PPy CTs.

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3.2.7. Thermogravimetric analysis

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The thermogravimetric analysis of TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs and

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V-TiO2/PPy CTs was studied up to 800 °C under N2 atmosphere and the resulting
thermograms were shown in Fig. 11. It was demonstrated that the V-TiO2 NPs exhibited
higher thermal stability compared to the pure TiO2 NPs. At the end of analysis (800 °C),

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there were 96.7 % and 86.5 % (w/w) residues of V-TiO2 NPs and TiO2 NPs, respectively.
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Meanwhile, TiO2/PPy CTs and V-TiO2/PPy CTs displayed similar decomposition
behaviors with a slow decomposition trend. As the temperature increasing, the first
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weight loss (180 °C) was related to the evaporation of water, which existed in the
samples. The main weight loss at 250 °C corresponded to the release of C, H and N
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moieties of PPy [41,42]. At 800 °C, the retention percentages of V-TiO2/PPy CTs (62.5 %)
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was higher than that of TiO2/PPy CTs (48.1 %). Liu et al. reported that the major mass
loss for PPy polymer degradation was from 300 °C to 780 °C [43]. Guo et al. studied that
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PPy decomposed properly at 650 °C [44]. Thus, the TiO2/PPy CTs would decompose
properly at about 800 °C, which was related to the decomposition of whole PPy backbone,
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the degradation of main and side PPy chains [45]. In contrast, the V-TiO2/PPy CTs were
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thermally stable when the temperature up to 800 °C, which was due to the stronger
physicochemical interaction between V-TiO2 NPs and PPy chains. In addition, the smaller
size of V-TiO2 NPs acted as a barrier, blocking the degradation of PPy backbone and
hindering the diffusion of degraded PPy from CTs. And the high thermal stability of the
V-TiO2 NPs also restricted the mobility of PPy moieties, which slowed down the thermal

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decomposition [46]. Overall, the incorporation of V in TiO2 NPs greatly enhanced the
thermal stability of TiO2 NPs and TiO2/PPy CTs.

3.3. Electrical conductivity

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In our test, four-point probe was utilized to measure the electrical conductivity of
TiO2/PPy CTs and V-TiO2/PPy CTs. The electrical conductivity of TiO2/PPy CTs and

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V-TiO2/PPy CTs were 0.39 S cm-1 and 0.54 S cm-1, while the pure PPy coating was 0.12
S cm-1. It was reported that the electrical conductivity of PPy CTs depended on the degree

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of doping, particle morphology, intrachain interactions, molecular weight, etc [47]. The
electrical conductivity of TiO2/PPy CTs and V-TiO2/PPy CTs was higher than that of pure

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PPy coating, which was partly caused by the degree of doping. As we known, TiO2 is an
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n-type semiconductor. During the doping process, electrons were pulled out from the PPy
conjugated π-electron cloud to form mobile carriers in the PPy molecular chain, which
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reduced the PPy energy level. As a result, the electron transfer resistance reduced, leading
to an increase in the conductivity of the PPy coating. In addition, the V-TiO2 NPs were
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more easily incorporated into the PPy chain because of the smaller size, which caused a
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more effective doping process. These accounted for the higher electrical conductivity of
V-TiO2/PPy CTs.
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3.4. Immersion tests

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The corrosion behaviors of bare CS, TiO2/PPy and V-TiO2/PPy coated CSs were
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monitored by immersion tests in 0.1 M HCl solution at 298 K. The corrosion

morphologies of bare CS, TiO2/PPy and V-TiO2/PPy coated CSs after 12 h immersion in
0.1 M HCl solution were shown in Fig. 12. The CS surface was badly corroded and
covered by lots of corrosion products. Meanwhile, the surface of TiO2/PPy CT was
localized destroyed with some corrosion pores and cracks on the coating surface. In
contrast, the V-TiO2/PPy CT was still homogeneous and intact, which implied that

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V-TiO2/PPy CTs offered better anti-corrosion performance. For further studies of the
corrosion process, the improved anti-corrosion performance in the case of V-TiO2/PPy
CT was not only due to the high hydrophobic of the coatings, which reduced the
permeation of the aggressive ions into the coatings, but also because of the strong

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adhesion between coatings and CS [48]. The V-TiO2/PPy CTs always adhered to CS
surface and acted as a corrosion resistor during immersion time, which could account for

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the long time corrosion protection performance.
In addition, the dissolution of Fe of CS was evaluated by ICP-AES analysis through

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immersing these samples in 0.1 M HCl solution. Fig. 14 represented the variation of the
released Fe2+ ions as a function of 7 days immersion time of bare CS, TiO2/PPy and

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V-TiO2/PPy coated CSs at 298 K. It was observed that the concentration of the Fe2+ ions
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dissolved in 0.1 M HCl solution was increased with the immersion time. The total
amounts of released Fe2+ ions of bare CS, TiO2/PPy and V-TiO2/PPy coated CSs were
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336 ppm, 208 ppm and 113 ppm, respectively. At the same time, the Fe2+ ions release rate
of V-TiO2/PPy coated CS was relatively lower than that of TiO2/PPy coated CS. Based on
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the corrosion morphologies and ICP-AES experiments, we could find that the
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V-TiO2/PPy CTs exhibited better anti-corrosion performance.

3.5. Electrochemical Measurements

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3.5.1. EIS measurements

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The corrosion behaviors of TiO2/PPy CTs and V-TiO2/PPy CTs at different

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immersion time were expressed by Nyquist plots in 0.1 M HCl solution. Open circuit
potential (OCP) was first performed for 30 min to ensure a steady-state system, then the
EIS measurements were carried out. Fig. 14 depicted the Nyquist plots of bare CS,
TiO2/PPy and V-TiO2/PPy coated CSs in 0.1 M HCl solution after different immersion
time. As illustrated in Fig. 14a, the Nyquist plots of bare CS showed only one capacitive

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loop and the diameter decreased with the immersion time. Meanwhile, the TiO2/PPy and
V-TiO2/PPy coated CSs (Fig. 14b and c) were consisted of two depressed capacitive
loops, while one loop was not obvious. The two time constants corresponded to two
different electrochemical processes, where the high frequency region reflected the

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response of the coating/electrolyte and the low frequency part corresponded to the
electrochemical reaction of the metal/coating interface, respectively [49]. The diameter of

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capacitive loop expanded with the immersion time, which could be interpreted as a result
of the good barrier effect of PPy CTs [50]. The TiO2 and V-TiO2 NPs in PPy CTs acted as

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a corrosion resistor to prevent the penetration of corrosive electrolyte.
The curves were fitted with simple Randles circuit (Fig. 15a) for bare CS and the

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circuit shown in Fig. 15b for coated CSs, where Rs represented the solution resistance,
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Rpore corresponded to the pore resistance, Rct was the charge transfer resistance, Cdl
represented the double layer capacitance, and Cc indicated the coating capacitance. To
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attain more accurate fitting results, a constant phase element (CPE) was introduced to
describe the non-ideal capacitive response of the corrosion system. The CPE impedance
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was given by Eq. (2).

Z CPE = Y0 −1 ( jω ) − n
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(2)
where Y0 is a proportional factor, ϳ is the imaginary number, ω is the angle frequency,
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n has the meaning of a phase shift, which is strongly influenced by the surface roughness.
For n=1, it indicates that the surface is perfect and the CPE represents an ideal capacitor.
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For n=0, an ideal resistor. The coating capacitance (Cc) was calculated by Eq. (3).

C c = Y0 (ω ') n −1
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(3)
where ω’ is the angular frequency at which Z imaginary is maximum. The
electrochemical parameters fitted by equivalent circuit models were shown in Table 1.
The polarization resistance (Rp) was the sum of Rpore and Rct value, which reflected the
corrosion resistance of these coatings.

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The protection ability of TiO2/PPy CTs and V-TiO2/PPy CTs could be understood
from the Rpore and Cc and Rct value. The Rpore was related to the penetration of the ionic
transfer into the micro-pores of the coating [51]. The increased Rpore value indicated that
the pores were blocked by the corrosion products, which made the penetration of

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corrosive medium difficult. It was worth noting that the Rpore value of TiO2/PPy CTs
increased with the prolonged immersion time and achieved its maximum value at 48 h.

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However, the protection performance was usually compromised with the lapse of time.
The Rpore value of TiO2/PPy CTs began to decrease after 48 h immersion, which was

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caused by the penetration of the corrosive ions into the coatings and the passive films
formed by Fe2+ and C2O42- started to dissolve. Hence, defects and pores developed over

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time, which acted as channels for the penetration of the corrosive ions. In this case,
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corrosion process occurred at coating/metal interface accompanied by the destruction of
coatings. In contrast, the Rpore value of V-TiO2/PPy CTs increased with the immersion
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time, indicating that V-TiO2/PPy CTs could maintain a long time protection ability.
The variation of Cc value was an alternative approach to recognize the behaviors of
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the coating, which was used to characterize the water absorption ability of the coating
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[52]. The higher Cc value of coatings, the more affinity towards electrolyte uptake [46].
As seen from Table 1, the values of both TiO2/PPy and V-TiO2/PPy CTs increased with
the immersion time, which was an indication of the increase in the uptake of electrolyte.
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Moreover, it was noticed that the value of V-TiO2/PPy CTs was smaller than that of
TiO2/PPy CTs, indicating a smoother and more intact surface of V-TiO2/PPy CTs. This
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conclusion could be supported by SEM. After a long time observation, V-TiO2/PPy CTs
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were confirmed to offer better protection ability than TiO2/PPy CTs.

The charge transfer was also necessary for the formation of rust and dissolution. So,
one of the ways to reduce the corrosion was the prevention of charge transfer. An
estimation of the change in coating deterioration was obtained by considering the
variation of Rct value, which was a symbol of the electron transfer across the metal

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surface. Higher values of Rct indicated lower corrosion rate and better protection ability
[53]. From Table 1, the Rct value of V-TiO2/PPy CTs was always larger than that of
TiO2/PPy CTs, indicating the degree of the electron transfer rate between metal and
coating was lower. This phenomenon illustrated that the V-TiO2/PPy CTs had a better

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anti-corrosion performance by preventing the charge transfer process. It was understood
that the PPy was a p-type semiconductor presented a large barrier for electron transport

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while TiO2 was an n-type semiconductor, which gave hindrance to the hole transport
across the interface. Intimate contact of CPs with TiO2 NPs leaded to the formation of p-n

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junction. The p-n junction could act as a potential barrier for charge transport, which
allowed the electrons transported in only one direction [54]. Also, the charge transport

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from PPy to TiO2 and vise versa was not easy due to the difference in the position of their
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valence bands and the energy gaps [55]. Hence, with the decrease of charge transfer,
corrosion process was prevented, leading to the decrease in the corrosion performance.
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During the corrosion process, TiO2/PPy and V-TiO2/PPy coated CSs could happened
by the following Reactions (4) - (5).
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a. Anode: the dissolution of the iron

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Fe − 2e− → Fe2+ (4)

b. Cathode: the reduction of PPy CTs caused the release of counter anions (i.e. C2O42-)
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[PPy y+ (C2O4 2- )y]n + nye− → (PPy)n + nyC2O4 2- (5)

As the PPy coating gradually reduced, the doped C2O42− would release and interact
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with Fe2+ through the Reaction (6) to form an insoluble complex (FeC2O4) films. The
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formed complex films were deposited on CS surface and favored maintenance of the
passive FeC2O4·2H2O layer continuously.

C2O4 2- + Fe 2+ + 2H2O → FeC2O4 ⋅ 2H2O (6)

Thus, the value of Rp increased with immersion time, which was related to the
synergistic effects of the reduction of the PPy CTs and the self-healing ability of passive

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layers by the continuous released C2O42− anions. Moreover, the formed passive film and
the doped V-TiO2 and TiO2 NPs could seal off the holes in PPy CTs and block the
permeation channels of the corrosive medium. As a result, the corrosive ions would be
prevented from contacting with CS surface and the corrosion would be inhibited. These

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could explain the mechanism of the self-healing of the PPy CTs.

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3.5.2. PP measurements

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PP measurements were carried out in order to get more information regarding the
corrosion protection performance of TiO2/PPy CTs and V-TiO2/PPy CTs in 0.1 M HCl
solution. Fig. 16 presented the PP curves of these CTs after 72 h of immersion in 0.1 M

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HCl solution. Both cathodic and anodic reactions of corrosion process were significantly
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suppressed after incorporation of TiO2/PPy CTs or V-TiO2/PPy CTs. It was due to the
barrier effect of these intact coatings which effectively blocked corrosive medium from
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entering into the substrate surface. The electrochemical parameters obtained from PP
curves were displayed in Table 2. The protective efficiency (η) values were obtained
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according to Eq. (7).

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Icorr - Icorr(c)
η= ×100 %
Icorr (7)
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where Icorr and Icorr(c) are the corrosion current density values in the absence and
presence of the PPy CTs.
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From Table 2, it found that the corrosion potential (Ecorr) of all the coated CSs
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shifted to more positive value. In general, the Ecorr mainly represented the tendency of
corrosion reaction, where a high Ecorr value reflected a good corrosion resistance of the
coatings [56]. In fact, the derived corrosion current density was the most important
parameter to evaluate the corrosion protection performance. The smaller Icorr was, the
better corrosion protection performance. For the bare CS, it exhibited the highest
corrosion current density (510.0 µA cm-2) after 72 h immersion. And the TiO2/PPy and

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V-TiO2/PPy coated CSs exhibited much lower corrosion current densities (84.5 µA cm-2
and 41.5 µA cm-2), which meant the dissolution of CS was delayed by incorporating of
coatings. The observed η values of TiO2/PPy CTs and V-TiO2/PPy CTs were 83.43 % and
91.86 %, respectively. Hence, the result evidently showed that the V-TiO2/PPy

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hdramatically improved the anti-corrosion property.
The V-TiO2/PPy CTs offered superior protection of the CS than the TiO2/PPy CTs,

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which was due to barrier effects preventing corrosion ions from reaching the surface of
CS in the formation of a passive layer [57]. Q. Sun [58] had also reported that the effect

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of nano-size additives used to improve the barrier effects of polymers. Furthermore, the
smaller size of NPs, the higher block properties of the coating could be attained. Our

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experiments suggested that the crystalline size of V-TiO2 NPs was smaller than that of
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TiO2 NPs, hence the performance of V-TiO2/PPy CTs had more effective corrosion
control than TiO2/PPy CTs. With the decrease in V-TiO2 NPs size, the area of interaction
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between PPy and the surface of CS increased. In addition, electroactive polymer such as
PPy added to the electric field formation at CS surface, thereby decreasing the electrons
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flowed from the steel to the oxidant. Electroactive polymer coatings compelled the
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formation of protective passive layers of metal oxides on CS surface and this could
prevent the corrosion process [55]. Based on these conclusions, we could suggest that one
of the metal oxides produced during the corrosion of the V-TiO2/PPy CTs was V2O5. The
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XPS tests had showed that the V5+ was the dominant composition in V-TiO2 NPs. Thus,
the formation of V2O5 on the steel surface could be due to the penetration of the
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electrolyte during the corrosion reaction. The increased surface area of the TiO2/PPy CTs
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with V doping could reduce the charge transfer across the electrolyte/steel interface and
effectively isolate the coating surface from aggressive environment. Thus, the
V-TiO2/PPy CTs displayed better anti-corrosion performance.

4. Conclusion

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The TiO2/PPy CTs and V-TiO2/PPy CTs on CS were electrosynthesized by CV

method in aqueous oxalic acid solutions. TEM results confirmed the size of V-TiO2 NPs
was smaller smaller than that of TiO2 NPs. The surface of the V-TiO2/PPy CTs was more
intact and smoother with the increase in doping amount of V in TiO2 lattice, which was

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also supported by SEM. Meanwhile, the electrical conductivity of TiO2/PPy CTs was also
improved. Moreover, electrochemical experiments confirmed that the V-TiO2/PPy CTs

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displayed better corrosion protection performance than TiO2/PPy CTs. The immersion
tests also indirectly proved this conclusion. The excellent corrosion protection was due to

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the synergistic effects of the increase in barrier effect, prevention of p-n junction for
charge transport by the TiO2 NPs as well as the formation of the passive film.

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Acknowledgement

The authors thank the National Science & Technology Pillar Program during the
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Twelfth Five-year Plan Period for Seawater Desalination Technology (2015BAB08B00),

the Natural Science Foundation for Young Scholars of Jiangsu Province, China
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(BK20160983), the National Key R&D Plan (2017YFC0404100), the National Natural
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Science Foundation of China (21605084), the Jiangsu Province Natural Science

Foundation for Young Scholars of China (BK20160983 and BK20170111) and Special
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basic research service for the Central Level Public Welfare Research Institute
(GYZX170302).
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Figure captions

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Fig. 1 Cyclic voltammograms of (a) TiO2/PPy CTs, (b) 0.05V-TiO2/PPy CTs, (c)

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0.1V-TiO2/PPy CTs and (d) 0.15V-TiO2/PPy CTs in oxalic acid solution.
Fig. 2 FTIR spectra of TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs and V-TiO2/PPy CTs.

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Fig. 3 Deconvoluted XPS spectra of (a) Ti 2p and (b) V 2p for V-TiO2 NPs.
Fig. 4 XRD spectra of TiO2 NPs, 0.05V-TiO2 NPs, 0.1V-TiO2 NPs and 0.15V-TiO2 NPs.

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Fig. 5 XRD spectra of TiO2/PPy and V-TiO2/PPy CTs.
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Fig. 6 TEM images of (a) TiO2 NPs, (b) 0.05V-TiO2 NPs, (c) 0.1V-TiO2 NPs and (d)
0.15V-TiO2 NPs.
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Fig. 7 The size histograms of (a) TiO2 NPs, (b) 0.05V-TiO2 NPs, (c) 0.1V-TiO2 NPs and
(d) 0.15V-TiO2 NPs.
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Fig. 8 SEM micrographs of (a) TiO2/PPy CTs, (b) 0.05V-TiO2/PPy CTs, (c)
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0.0V-TiO2/PPy CTs and (d) 0.15V-TiO2/PPy CTs.

Fig. 9 The EDX analysis of (a) TiO2/PPy CTs and (b) V-TiO2/PPy CTs.
Fig. 10 Static contact angle images for the bare CS, TiO2/PPy and V-TiO2/PPy coated
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CSs before and after 12 h of immersion in 0.1 M HCl solution.

Fig. 11 TGA curves of TiO2 NPs, V-TiO2 NPs, TiO2/PPy CTs and V-TiO2/PPy CTs.
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Fig. 12 SEM micrographs of (a) bare CS, (b) TiO2/PPy CT and (c) V-TiO2/PPy CT after
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12 h of immersion in 0.1 M HCl solution.

Fig. 13 The concentration of released Fe2+ ions from bare CS, TiO2/PPy and V-TiO2/PPy
coated CSs after 7 days of immersion in 0.1 M HCl solution.
Fig. 14 The Nyquist plots of (a) bare CS, (b) TiO2/PPy and (c) V-TiO2/PPy coated CSs
after different immersion time in 0.1 M HCl solution.

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Fig. 15 Equivalent circuit for fitting the impedance diagram: (a) bare CS, (b) TiO2/PPy
and V-TiO2/PPy coated CSs.
Fig. 16 PP curves of bare CS, TiO2/PPy and V-TiO2/PPy coated CSs in 0.1 M HCl
solution.

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Table 1 EIS parameters fitted by the equivalent circuit proposed in Fig. 15.

Rpore (Ω
Electrodes Time (h) Cc (F cm-2) Rct (Ω cm2) Rp (Ω cm2)
2
cm )
1 - 3.71×10-4 87.59 -

24 - 3.92×10-4 64.01 -
CS

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48 - 6.93×10-4 31.13 -
72 - 7.67×10-4 15.28 -

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1 20.01 2.10×10-4 138.81 158.82
24 28.99 2.58×10-4 217.19 246.18

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TiO2/PPy
48 46.74 4.65×10-4 357.76 404.50
72 39.56 5.37×10-4 288.93 328.49
1 28.01
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24 39.51 1.59×10-4 354.94 394.45
V-TiO2/PPy
48 42.59 1.84×10-4 502.62 545.21
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72 53.64 2.13×10-4 540.43 594.07

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Table 2 PP parameters of bare CS, TiO2/PPy and V-TiO2/PPy coated CSs in 0.1 M
HCl solution.

bc（mV
Electrodes Ecorr (V) b（ -1
a mV dec ) Icorr (µA cm-2) η (%)
-1
dec )

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CS -0.483±0.005 165.9±2.4 551.8±5.5 510.0±4.3 -
TiO2/PPy -0.441±0.008 114.7±5.1 345.3±4.2 84.5±6.2 83.43

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V-TiO2/PPy -0.381±0.004 78.8±2.2 121.6±3.6 41.5±5.8 91.86

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Highlights:

The doping of V-TiO2 nanoparticles decreases the size of the PPy particles.

The doping of V-TiO2 nanoparticles improves the physical properties of PPy
coating.

The doping of V-TiO2 nanoparticles enhances the corrosion protection of PPy

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coating.

V-TiO2/PPy coatings reduce the charge transfer across the electrolyte/CS

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interface.

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