Colloids and Surfaces A 537 (2018) 334–342

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Colloids and Surfaces A

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

Research Paper

Water-based rust converter and its polymer composites for surface MARK
anticorrosion
⁎
Jianfeng Lia, Shengsong Gea, , Junxiang Wanga, Huayun Dub,c, Kenan Songd, Zhiying Feia,
⁎ ⁎
Qian Shaoa, , Zhanhu Guob,
a
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, China
b
Integrated Composites Laboratory (ICL), Chemical and Biomolecular Engineering Department, University of Tennessee, Knoxville, TN 37996, USA
c
College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
d
Department of Materials Science and Engineering, Massachusetts Institute of Technology, 77 Mass AV., Cambridge, MA, 02139, USA

G RA P H I C A L AB S T R A C T

The plate, treated with RC-GAE, has a dense black protective chelate film with a better anticorrosion performance than the untreated.

A R T I C L E I N F O A B S T R A C T

Keywords: A novel water-based rust converter 2-hydroxypropyl 3, 4, 5-trihydroxybenzoate (named as RC-GAE) was pre-
Adhesion pared by using an esterification reaction between 1, 2-propylene glycol (PG) and gallic acid (GA). The effects of
Anticorrosion PG and GA mass ratio in the RC-GAEs on the anticorrosion were investigated by the Tafel polarization with the
Coatings rusty plate samples coated with RC-GAEs in a 3.5 wt% NaCl solution. The rust was converted to a compact black
Gallic acid
protective rust-conversion film with this rust converter. The metallographic microstructure, morphology, and
Water-based rust converter
crystalline phase of the rust-conversion films were conducted systematically by optical microscopy, X-ray dif-
fraction, and scanning electron microscopy with energy-dispersive spectrometry. The corroded plate with un-
even and rough brown surface became smoother and darker after treated with converter. X-ray photoelectron
spectroscopy indicated that the RC-GAE reacted with Fe2+/Fe3+ and formed a compact Fe2+/Fe3+ chelate film
that played the role of anticorrosion. Additionally, new water-based anticorrosion coating was prepared by

⁎
Corresponding authors.
E-mail addresses: geshengsong@126.com (S. Ge), shaoqian01@126.com (Q. Shao), zguo10@utk.edu (Z. Guo).

http://dx.doi.org/10.1016/j.colsurfa.2017.10.041
Received 5 June 2017; Received in revised form 16 October 2017; Accepted 18 October 2017
Available online 18 October 2017
0927-7757/ © 2017 Elsevier B.V. All rights reserved.
J. Li et al.
applying a mixture of RC-GAE and other additives to form polymer composites on the rusty steel plates. Both
adhesion test and neutral salt spray test indicated that the anticorrosion coating presented a good corrosion
resistance and a remarkably strong film adhesion of the new water-based anticorrosion polymer composites
coating.
1. Introduction
Corrosion protection and prevention are remarkably important,
since considerable parts of the gross national products are consumed
annually for corrosion and corrosion prevention [1–3]. Among the
frequently reported protection methods such as organic or inorganic
coating [4,5], electrochemical protection [6] and corrosion inhibition
[7–10] used to prevent metal corrosion, the most effective and eco-
nomic corrosion prevention technique is the application of coating,
particularly organic coatings. Ideally, organic coatings would provide
long-lasting corrosion protection [11–13]. However, most organic
coatings used previously in anticorrosion systems are solvent-based
coatings, which contain large amount of organic solvent. With the in-
crease of environmental awareness, zero-volatile organic compounds
(VOC) or low-VOC water-based anticorrosion coatings are demanded to
save natural resources and protect the environments. High-molecular
weight organic corrosion inhibitors (such as a castor oil derivative) [14]
and barrier anticorrosive pigments (such as calcium metasilicate) [15]
and convertible anticorrosive pigments (such as zinc chromate) [16]
are active protective elements in paint formulations [17]. The primary
paints that protect the steel structures from corrosion normally contain
corrosion-inhibiting pigments, which are mostly lead oxide (red lead)
or chromate [18,19]. These compounds are hazardous to the environ-
ments because of their toxicity, and must be substituted by environ-
ment-friendly corrosion inhibitors.
Although tannic acid and their derivatives such as gallic acid (GA, 3,
4, 5-trihydroxy benzoic acid) have been studied as non-toxic and non-
polluting multipurpose rust converters [20–24], its weak rust-conver-
sion capacity, poor water resistance and low solubility limit their ap-
plications [25,26]. Modifications need be taken for its potential uses for
rust conversion. The reported improvement approaches [26–28] in-
volved mixing with other organic or inorganic acids such as phosphoric
acid and oxalic acid, which can improve the conversion capacity of rust
converter. Most studies regarding water-based anticorrosion coating are
based on a mixture of tannic acid and phosphoric acid because of their
convenient applications and simple operation [29,30]. However, excess
acids can introduce a large number of active groups and consequently
cause instability and water resistance of the coating. GA is a natural
plant polyphenol that is widely distributed in fruits and plants [31,32].
GA and its derivatives possessing antioxidative, antineoplastic proper-
ties and synergistic inhibition effects [33–35] are widely used in
biology, pharmacy and chemistry. The structure of GA causes strong
chelating capability with metal ions through hydroxyl groups [36,37].
Although a GA ester with excellent water solubility and the existence of
hydroxyl groups could have great chelating capability with rust, the
synthesis of GA ester as a rust converter for residual rust coating
treatments has not been reported yet.
Herein, a novel water-based rust converter 2-hydroxypropyl 3, 4, 5-
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Colloids and Surfaces A 537 (2018) 334–342
trihydroxybenzoate (named as RC-GAE in this paper) based on GA was
synthesized. The rust conversion behaviors were examined on the rusty
samples by preparing an anticorrosion painting with the as-prepared
RC-GAE. The success of RC-GAE synthesis was confirmed by Fourier
transform infrared spectroscopy (FT-IR). The rust conversion capability
of the as-prepared RC-GAE and the corrosion resistance behaviors of the
anticorrosion polymer composite coatings were studied by scanning
electron microscopy (SEM), X-ray diffraction (XRD), polarization curve,
and neutral salt spray test. The anticorrosion mechanism of the as-
prepared RC-GAE was explained by considering the formed iron che-
lation film on the surface of the plate. The adhesion test and the salt
spray corrosion resistance test were used to evaluate the barrier prop-
erties and protective capacity of the RC-GAE coating, and to reveal the
penetration of aggressive species during the corrosion test over a long
time.
2. Materials and methods
2.1. Materials
GA (powder, Analytical Reagent) was purchased from Tianjin
Daguche Chemical Co. Ltd., Tianjin, China. 1, 2–Propylene glycol (PG,
Analytical Reagent), p-toluene sulfonic acid (p-TSA, Analytical
Reagent), sodium chloride (NaCl, Analytical Reagent), ethanol
(Analytical Reagent), and 2-Butoxy ethanol (Analytical Reagent) were
purchased from Tianjin Bodi Chemical Co. Ltd., Tianjin, China. Vinyl
acrylic water-based resin (Haloflex 202) was obtained from DSM Co.
Ltd., Shanghai, China. Texanol with the effective chemical composition
of 2,2,4-Trimethyl-1,3-pentanediolmono (2-methylpropanoate) was
purchased from EASTMAN Chemical Company, Shanghai, China.
Aluminum tripolyphosphate (AlH2P3O10, 45 μm), sericite (45 μm),
talcum powder (45 μm), barium sulfate (45 μm), and nanosilica fillers
(30 nm) were purchased from Guangzhou Yifeng chemical Co. Ltd.,
Guangdong, China. All the other chemicals were of industrial grade and
used as received without any further purification. Distilled water was
used throughout the experiment.
2.2. Preparation of the water-based rust converter
The synthesis of the as-prepared RC-GAE is illustrated in Scheme 1.
GA reacted with PG through an esterification method with p-TSA as
catalyst.
In a typical synthesis, PG (30.6 g) and GA (10.2 g) were added into a
four-necked flask with a condenser and thermometer. The mixture was
stirred at 70 °C in a temperature-controlled water bath. Approximately,
1.02 g p-TSA was added into the flask, and GA was all dissolved. The
suspension was stirred at 70 °C for 1 h and heated to 105 °C. After 3 h
continuous agitation and reaction, the four-necked bottle was naturally
Scheme 1. Synthesis of RC-GAE from the reaction
between GA and PG.
J. Li et al.
cooled down to room temperature. The obtained product was a pale
yellow liquid. PG was used as a film-coalescing aid in the anticorrosion
painting; thus, it did not need be separated from the as-prepared rust
converter.
The mass ratio of PG to GA was important for the performance of
the novel water-based rust converter. GA could not react completely
when PG was not more than GA; otherwise, the anticorrosion perfor-
mance of the rust converter was not high when PG was more than GA.
Therefore, RC-GAEs were prepared with different mass ratios of PG and
GA to evaluate the influence of mass ratio on the anticorrosion per-
formance of RC-GAE. These samples were marked as RC-GAEs (m:n) to
designate the samples prepared with the mass ratio (m:n) of PG and GA.
2.3. Preparation of samples
The cold rolled plates (The compositions of the cold rolled steel
plates are listed as follows (%): C: ≤0.10, Si: ≤0.05, Mn: ≤0.50, P:
≤0.035, S: ≤0.025, Fe: Residual dose.) of 6 cm × 12 cm × 0.05 cm
were degreased with alkaline degreasing agent. The degreasing agent
was made in our lab. To be more specific, its main compositions are
listed as follows (for example to make one g degreasing agent):
Na4P2O7∙10H2O: 0.03 g, Na2CO3: 0.12 g, NaOH: 0.05 g, NaCl: 0.01 g,
sodium gluconate: 0.04 g, triethanolamine: 0.08 g, sodium carbox-
ymethylcellulose: 0.002 g, polyoxyethylene nonylphenol ether (NP-10):
0.02 g, and distilled water: residual dose. The plates were then rinsed
with distilled water, and then exposed to air for three months to rust.
The pre-rusted plates were only roughly cleaned to remove the floating
rust and dust on their surface using a metallic brush and rinsed with
ethanol before the test. The pre-treatment of the rusted plates could
make a good effort to improve the adhesion performance of the coating
film. Then the plate was coated with the rust converter synthesized in
Section 2.2 using a banister hairbrush when the ethanol was evapo-
rated. The coated samples were allowed to be dried for 48 h at room
temperature.
A new water-based anticorrosion coating based on RC-GAE was
prepared. The composition of the anticorrosion coating is shown in
Table 1. Briefly, distilled water, dispersant and appropriate amount of
defoamer and Texanol with the amount described in Table 1 were
added into a beaker with a mixer. Then, aluminum tripolyphosphate
(AlH2P3O10), sericite, talcum powder, barium sulfate, and nanosilica
fillers were added into the beaker sequentially to make the rust con-
verter paint. The suspension was stirred for 15 min. Afterward, the RC-
GAE prepared in Section 2.2, Haloflex 202, 2-Butoxy ethanol and ap-
propriate amount of defoamer, Texanol and thickener were added into
the suspension with stirring for 30 min.
The new water-based anticorrosion coating containing RC-GAE and
other additives was painted on the prepared corroded plates to form
polymer composites on the rusty steel plates. Before the coating film
performance test, the samples were dried for 120 h at room tempera-
ture.
2.4. Characterization
FT-IR spectra of the samples were recorded on a NICOLTE 380 FT-IR
spectrometer ((Thermo, USA)) using the KBr method. The crystal-
lographic information of the samples was analyzed by XRD (Rigaku
Ultima IV) equipped with graphite monochromatized Cu Kα radiation
(λ = 0.15418 nm), with a scanning rate of 4°/min in 2θ range of
10°–80°. X-ray photoelectron spectroscopy (XPS) analyses were de-
termined with an X-ray spectrometer K-Alpha (Thermo Scientific, USA),
using Mg Kα X-ray radiation (1486.6 eV).
The morphology and microstructure of the samples were observed
by a field-emission scanning electron microscope (SEM, SU-70, Hitachi,
Japan) equipped with energy dispersive spectrometer (EDS) at an ac-
celerating voltage of 30 kV.
Metallographic test of sample profiles was done on a microscope
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Colloids and Surfaces A 537 (2018) 334–342
(DVM2500, Leica, Germany). The samples were prepared by en-
capsulating the sample prepared in Section 2.2 in black phenolic resin,
sanding on #400, #500, #600, #800, #1000 and #1200 sandpaper,
polishing with alumina suspensions of particle sizes between 1.0 μm
and 0.3 μm and etching with nital solution.
2.5. Tafel polarization measurements
The Tafel polarization measurements were carried out on a
LK2005A electrochemical workstation (Lanlike, Tianjin, China) in a
3.5 wt% NaCl solution, with a saturated calomel electrode (SCE) as
reference and platinum electrode as counter electrode. The sample
plates prepared in section 2.3 were cut to fixed size
(1.2 cm × 1.2 cm × 0.05 cm), and then coated with wax and made
sure the surface area of the plate to be 1 cm2. Then it can be used as the
working electrode for the Tafel studies. The open circuit potential
(OCP) of plate samples coated with the as-prepared rust converter was
measured before the Tafel polarization measurements to confirm the
range of the sweeping potential. The Tafel polarization measurements
were performed by sweeping the potential between −0.25 and 0.25 V
from OCP at a scan rate of 0.0005 V/s. The specimen was stabilized in
the electrolyte for 30 min before the experiment. The same amount of
RC-GAEs (m:n) was used to treat the unrusted plate samples. All the
measurements were repeated at least three times to ensure good re-
producibility of the results.
2.6. Polymer composite coating film performance test
2.6.1. Film adhesion experiment
The adhesion test was conducted to evaluate the adhesion of the
anticorrosion coating in the plate samples according to the ASTM
D3359 standard. Briefly, a lattice pattern with six cuts in each direction
was made in the film to the substrate, the pressure-sensitive tape was
applied over the lattice and then removed, and the adhesion was
evaluated by comparison with the descriptions and illustrations There
are six levels in total, 0B, 1B, 2B, 3B, 4B and 5B, in which 0B is the
worst while 5B is the best. The level of the adhesion in accordance with
the following scale is illustrated as following. For level of “5B”, the
edges of the cuts are completely smooth, none of the squares of the
lattice is detached. For level of “4B”, small flakes of the coating are
detached at intersections, less than 5% of the area is affected. For level
of “3B”, small flakes of the coating are detached along edges and at
intersections of cuts; the area affected is 5–15% of the lattice. For level
of “2B”, the coating has flaked along the edges and on parts of the
squares, the area affected is 15–35% of the lattice. For level of “1B”, the
coating has flaked along the edges of cuts in large ribbons and whole
squares have detached, the area affected is 35–65% of the lattice. For
Table 1
The composition of the prepared water-based anticorrosion
coatings.
Material Mass (g)
distilled water 22
sericite 8
AlH2P3O10 8
talcum powder 4
barium sulfate 4
nanosilica filler 1.5
Texanol 0.8
RC-GAE 4
Haloflex 202 45
2-Butoxy ethanol 2.0
Defoamer 0.5
Thickener 0.1
Dispersant 0.1
Total 100
J. Li et al.
level of “0B”, flaking and detachment are worse than Grade 1.
2.6.2. Salt spray corrosion resistance test
Neutral salt spray test was used to evaluate the corrosion resistance
of the anticorrosion coating according to the ASTM B117 standard. The
tested samples were placed in a salt spray corrosion test chamber
(1100 × 780 × 1150 mm) at an angle of 45°. The instrument used for
the neutral salt spray test was a FQY015 pneumatic salt spray corrosion
test chamber (Shanghai Experimental Instrument Co. Ltd., China)
containing sodium chloride (5 ± 0.5) wt% with a pH value range of
6.5–7.2 and temperature of 47 ± 0.5 °C. The degree of protection
rating (Rp), which is defined by the area of defects (A(%)) in polymer
composite coating film, is used to represent the ability of the coating to
protect the base metal from corrosion according to ISO 10289–1999.
The coating film was checked with an optical microscope to evaluate
the area of the substrate that could exhibit localized attacks. There are
ten levels in total, 10, 9, 8, 7, 6, 5, 4, 3, 2 and 1, in which 1 is the worst
while 10 is the best (No defects: 10, 0 < A ≤ 0.1: 9, 0.1 < A ≤ 0.25:
8, 0.25 < A ≤ 0.5: 7, 0.5 < A ≤ 1.0: 6, 1.0 < A ≤ 2.5: 5,
2.5 < A ≤ 5.0: 4, 5.0 < A ≤ 10: 3, 10 < A ≤ 25: 2, 25 < A ≤ 50:
1, 50 < A: 0). Moreover, the time of the salt spray corrosion resistance
test is important to evaluate the performances of the anticorrosion
composite coating film, so the protection rating of the coating after salt
spray corrosion resistance test of X h were marked as Rp/X h, for ex-
ample, Rp/240 h means the protection rating of the coating after salt
spray corrosion resistance test of 240 h.
3. Results and discussion
Fig. 1 shows the Tafel curves of plate samples coated with the as-
prepared RC-GAEs (m:n). And the potentiodynamic polarization results
obtained by the Tafel extrapolation method [38–40] are summarized in
Table 2. The corrosion potential (Ecorr) of the samples coated with the
rust converter (Fig. 1c–i) remained positive with respect to the rusted
plate (−1.157 V, Fig. 1a) and the unrusted plate (−1.060 V, Fig. 1b).
Herein, the rusted plate is more susceptible to corrosion than the un-
rusted plate and the samples coated with the rust converter, it will be
easier to be corroded. Moreover, all of the plate samples coated with
RC-GAEs (m:n) provide a certain degree of galvanic or passivate pro-
tection to the steel substrate. Therefore, the plate sample, when coated
with RC-GAEs (m:n), is significantly less susceptible to corrosion and
shows a better corrosion performance than the case when it is not
treated with RC-GAEs (m:n) [41,42].
All of the plate samples coated with RC-GAEs (m:n) showed lower
corrosion current density than that of the rusted plate
(1.157 × 10−3 A cm−2) and the unrusted plate (1.827 × 10−4 A cm−2)
This is attributed to the reaction between rust and RC-GAE that enhances
both the kinetics of passivation and the stability of the protective passive
film formed. Moreover, the sample coated with RC-GAE (3:1) (Fig. 1e)
showed the lowest corrosion current density (7.194 × 10−7 A cm−2).
This is in turn due to the higher relative content of RC-GAE in RC-GAE
(3:1) with respect to others that speed up the formation of a stable and
protective passive film. This indicates that the rusty plate sample, when
coated with RC-GAE (3:1), has a significantly higher corrosion resistance
than the case when it is coated with other RC-GAEs (m:n). In addition, its
corrosion potential positively shifted to a higher value (−0.892 V) than
that of other coated samples (−0.937 V for RC-GAE (1:1), −0.958 V for
RC-GAE (7:1), etc). As the more negative corrosion potential and the larger
corrosion current usually correspond to faster corrosion rates while the
more positive corrosion potential and the smaller corrosion current density
(icorr) mean a slower corrosion process, thus the plate sample, when coated
with RC-GAE (3:1), is significantly less susceptible to corrosion than the
case when it is coated with other RC-GAEs (m:n). Furthermore, the pro-
tection efficiency was increased from RC-GAE (1:1) to RC-GAE (3:1)
(Fig. 1c–e) and decreased from RC-GAE (4:1) to RC-GAE (7:1) (Fig. 1f–i),
which might be due to the fact that GA cannot react completely when the
337
Colloids and Surfaces A 537 (2018) 334–342
relative content of PG was not more than that of GA (RC-GAE (1:1) and
RC-GAE (2:1)), therefore, the rust had not been transformed by RC-GAEs
completely. Otherwise, when the amount of PG was higher than that of
GA, the relative content of the GA esters was small in the same dosage, the
GA esters were not sufficient to convert all rust into iron chelate (for ex-
ample, RC-GAE (4:1), RC-GAE (5:1), RC-GAE (6:1), and RC-GAE (7:1)),
and the rust had not been transformed by RC-GAEs completely. As the as-
prepared RC-GAE (3:1) showed the more positive corrosion potential and
the smaller corrosion current (−0.892 V in the Ecorr and
7.194 × 10−7 A cm−2 in the icorr) and possessed an excellent antic-
orrosion property, thus the optimal mass ratio of PG and GA for the
coating was 3:1.
Fig. 2 shows the typical FT-IR spectra of PG (Fig. 2a), GA (Fig. 2b)
and RC-GAE (Fig. 2c). The strong broad peak in all FT-IR spectra at
around 3300 cm−1 is due to the eOeH stretching vibration. The ab-
sorptions around 1230 and 2975 cm−1 are the eCeH bending and
stretching vibrations, respectively (Fig. 2a and c). The observed various
peaks between 771 and 744 cm−1 correspond to the substituted ben-
zene rings in RC-GAE [43]. The observed peaks at 1714 and 1230 cm−1
are owing to the formation of −COO− in RC-GAE, and the peak at
1340 cm−1 corresponds to the eOeH in-plane bending vibration of the
benzene ring in RC-GAE. The stretching vibration peaks of eOeH at
3334, 1136 and 1039 cm−1 are enhanced significantly, this is due to
the appearance of polyhydric phenol in RC-GAE. The stretching vibra-
tion peak at 1652 cm−1 is disappeared, this is caused by the dis-
appearance of aliphatic polyols structure in PG. For Fig. 2b and Fig. 2c,
the characteristic peaks at 1714 and 1230 cm−1 arise from the eCOOe
stretching vibration [28,44], the peaks at 1451, 1539 and 1613 cm−1
are due to the eC]Ce bending and stretching vibrations of the ben-
zene ring [44]. Moreover, when compared with Fig. 2b, the position
and intensity of absorption peaks in Fig. 2c have changed obviously.
The eCeH stretching vibration peaks at 2973 and 2933 cm−1 are sig-
nificantly enhanced, the stretching vibration peaks of eOeH peaks at
around 3300, 1136 and 1039 cm−1 are owing to the reaction between
GA and PG, which results in the appearance of eCeH and eOeH of
fatty alcohol in RC-GAE. Therefore, the FT-IR analyses indicate the
successful synthesis of RC-GAE.
Fig. 3 shows the typical FT-IR spectra of rust (Fig. 3a), rust treated
with rust converter (Fig. 3b), and rust converter (Fig. 3c). The char-
acteristic peaks at 1022 and 598 cm−1 in Fig. 3a are the absorptions of
γ-FeOOH and Fe3O4 [23]. The peaks at 3440 and 1642 cm−1 are the
eOeH stretching vibration of the rust. The absorption peaks at 1642,
1022 and 598 cm−1 are disappeared, the absorption peaks at
1382 cm−1 are enhanced, the absorption peaks at 3440 and 1642 cm−1
are significantly reduced, which are correspond to the decrease of
eOeH in the rust (γ-FeOOH, α-FeOOH). The observed absorption peaks
Fig. 1. Tafel polarization curves of (a) rusted plate, (b) unrusted plate and samples coated
with (c) RC-GAE (1:1), (d) RC-GAE (2:1), (e) RC-GAE (3:1), (f) RC-GAE (4:1), (g) RC-GAE
(5:1), (h) RC-GAE (6:1), and (i) RC-GAE (7:1) in 3.5 wt% NaCl solution.
J. Li et al. Colloids and Surfaces A 537 (2018) 334–342

Table 2 rust had reacted with rust converter.

Corrosion parameters calculated from Tafel plots of (a) rusted plate, (b) unrusted plate The rusted steel plate surface (Fig. 4a) would be transformed into
and samples coated with (c) RC-GAE (1:1), (d) RC-GAE (2:1), (e) RC-GAE (3:1), (f) RC-
black (Fig. 4b) after applying the RC-GAE coating for about 15 min.
GAE (4:1), (g) RC-GAE (5:1), (h) RC-GAE (6:1), and (i) RC-GAE (7:1).in 3.5 wt% NaCl
solution. This is due to the reaction between the rust and rust converter and the
formation of the iron chelate (the color of the iron chelate of gallic acid
Sample Ecorr (V vs SCE) icorr (A cm−2) βa (V/dec) βc (V/dec) and it derivative [22]). From Fig. 4b, we can see that a dense shiny
−3
black iron chelate protective film was obtained when the rust converter
a −1.170 1.157 × 10 0.012 0.013
b −1.060 1.827 × 10−4 0.019 0.099 reacted with rust.
c −0.937 1.195 × 10−5 0.013 0.024 Fig. 5 shows the metallographic microstructure of sample profiles
d −0.924 2.637 × 10−6 0.008 0.013 before and after the treatment with the rust converter. The average
e −0.892 7.194 × 10−7 0.014 0.022 thickness of rust was about 3.5 μm for all the samples. This is due to the
f −0.910 8.371 × 10−6 0.041 0.044
rust on the surface of the sample plates is a short-term product, so it is
g −0.935 5.482 × 10−5 0.009 0.047
h −0.941 4.205 × 10−5 0.012 0.029 uniform and there are no long-term products from seriously localized
i −0.958 6.213 × 10−6 0.040 0.019 attack and pitting corrosion on the surface of the sample plates. As
shown in metallographic microstructure of untreated rusted plate
(Fig. 5a), there is an obvious dividing line between the rusted layer and
the steel substrate, which is not seen in the metallographic micro-
structure of treated rusted plate (Fig. 5b). Furthermore, the rust con-
verter seeped onto the substrate and reacted with the substrate
(Fig. 5b), in this case, the converted rust layer will have better bonding
force with the steel substrate, so the rust converted layer will have a
good adhesion performance. Moreover, the rust layer on the steel
substrate is thin, thus the dense covered protective film is also thin
compared with the steel substrate. As the dense protective film has
excellent barrier and corrosion resistant properties, it will avoid the
materials from further corrosion and decrease in mass and thus makes
no damage to the metal pieces, so the mechanical or physical properties
of the metal pieces are well improved than the loose rust on the rusted
metal pieces.
Fig. 6 shows SEM and EDS images of the rusty plate samples before
and after the treatment with the rust converter. Fig. 6a shows the
surface with fine grain morphology of rusts. The structures were also
highly porous and rough, and they presented cavities of different sizes.
Both lamellar regions and cactus-shaped particle regions can be ob-
Fig. 2. FT-IR spectra of (a) PG, (b) GA and (c) RC-GAE.
served in Fig. 6a. The morphologies are indicative of the presence of γ-
FeOOH (lamellar regions) and traces amount of α-FeOOH (cactus-
shaped particle regions) [45], which can also be confirmed by the XRD
test results. The crystalline morphology on the sample surface dis-
appeared, and an amorphous compact and cracked layer was formed
after the treatment with the rust converter (Fig. 6c and inset). These
changes indicated that the rusted phases were transformed by the rust
converter. Fig. 6b and d show the EDS spectra of the plate samples
before and after the treatment with the rust converter. The EDS spectra
indicate that the rusty plate samples before and after the treatment with
the rust converter are all composed of Fe, C and O elements, and the
composition percentages of Fe and C of the plate sample after the
treatment both increase, while the composition percentage of O de-
creases compared with the rusty plate sample after the treatment. The
results indicate that the rust is converted by the rust converter [44].
Fig. 7 shows a typical XRD pattern of the plate samples before and
after the treatment with the rust converter. Only Fe (JCPDS 06-0696)
and a small amount of γ-FeOOH (JCPDS 18-0639) can be identified on
the plate samples (Fig. 7a). No Fe2O3 peaks were observed, which might
be caused by the thin thickness of rust layer, as well as low content,
Fig. 3. FT-IR spectra of (a) Rust, (b) Rust treated with rust converter, (c) Rust converter.
poor crystallinity, and amorphous characteristics of Fe2O3. Therefore,
the rust powders obtained from the plate sample were also tested to
at 1578, 1210 and 602 cm−1 are due to the new bond formation of compare with other samples. The XRD pattern of the corrosion products
OeFeeO and the CeOeFe in the Fe2+/Fe3+ chelate in the reaction treated with RC-GAE revealed that the intensities of Fe2O3 (JCPDS 25-
between rust and rust converter. Moreover, when compared with 1402) and γ-FeOOH (JCPDS 18-0639) peaks diminished significantly or
Fig. 3c, the position and intensity of many absorption peaks in Fig. 3b disappeared (Fig. 7c), as easily observed in Fig. 7b. Only crystallized Fe
have changed obviously. The stretching vibration absorption peaks of peaks were observed, indicating that the rust reacted with the rust
AreOeH at 3362, 1136 and 1034 cm−1 are significantly reduced owing converter, the crystal shape of the rusted surface changed obviously,
to the decrease of eOeH in RC-GAE. There are new absorption peaks at the content of active rust on the rusty surface was considerably reduced,
1578, 1081 and 602 cm−1 observed, this is due to the new bond for- and the corrosion products treated with RC-GAE were mainly amor-
mation of OeFeeO and the CeOeFe in the Fe2+/Fe3+ chelate in the phous iron chelate [46].
reaction between rust and rust converter. All these indicated that the Fig. 8a shows the general XPS spectra of the rusty plate samples

338
J. Li et al.
before and after the treatment with the as-prepared RC-GAE, and the
results are shown in Table 3. The electron binding energy of O de-
creased from 531.58 to 530.88 eV after the treatment with the as-pre-
pared RC-GAE (Fig. 8c), suggesting the formation of the FeeOeC bond.
In the XPS high-resolution spectrum for the Fe2p transition (Fig. 8b),
the energies of 712.14 and 722.80 eV, corresponding to Fe2p3/2 and
Fe2p1/2 levels, transformed to 711.25 and 722.23 eV after the
Fig. 6. SEM and EDS images of the plate samples before (a, b) and after (c, d) the treatment with the RC-GAE rust converter.
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Colloids and Surfaces A 537 (2018) 334–342
Fig. 4. Optical images of the rusty steel sample be-
fore (a) and after (b) the treatment with the RC-GAE
rust converter. The brown rust in the sample plate is
converted into a dense black protective iron chelate
film after the treatment of RC-GAE.
Fig. 5. Metallographic microstructures of sample
profile (a) before and (b) after the treatment with the
RC-GAE rust converter (BPR: Black phenolic resin,
CRP: Cold rolled plates).
treatment with the rust converter, respectively. Gallic acid and their
derivatives are believed to possess reductive and antioxidative prop-
erties, and most of gallic acid esters are often used as antioxidants [33].
Moreover, the pH value strongly influences the property of gallic acid
and their derivatives, when the pH value is low, the reductive proper-
ties of gallic acid and their derivatives became stronger [22,24]. Herein,
part of Fe3+ transformed into Fe2+ by RC-GAE in acidic conditions,
J. Li et al. Colloids and Surfaces A 537 (2018) 334–342

Table 3
Element composition and electron binding energy of the rust before and after the treat-
ment with the rust converter.

Element Condition Content (Mass Binding energy (eV)

fraction%)

Fe2p Before treatment 50.06 712.14 (Fe2p3/2) 722.80

(Fe2p1/2)
After treatment 78.11 711.25 (Fe2p3/2) 722.23
(Fe2p1/2)
O1s Before treatment 44.37 531.58
After treatment 4.68 530.88
C1s Before treatment 5.57 285.44
After treatment 17.21 285.71

Lots of the traditional rust converters are well-known to have excess

Fig. 7. XRD patterns of the samples before and after treatment with the rust converter.
which was in agreement with other reports [22,24], and Fe2+ reacted
easier than the Fe3+ during the reaction between the rust and the as-
prepared RC-GAE. Additionally, the Fe3+ content decreased, which was
well consistent with the XRD pattern. In this case, we concluded that
the conversion mechanism of rust was that the ortho-phenolic hydroxyl
groups of the rust converter molecules reacted with Fe2+/Fe3+ and
formed a Fe2+/Fe3+ chelate (Scheme 2). The Fe2+ chelate is more
stable than Fe3+ chelate within a short period of time in an acidic
condition, which is in agreement with other reports [47].
Haloflex 202, a kind of acidic vinyl acrylic water-based resin, has
excellent barrier and adhesion properties and often used as the film
forming material in the anticorrosion primer coating. Furthermore, the
water-based rust converter is also acidic, a kind of acidic resin has to be
selected as the film forming material to ensure the stability of polymer
composite coating. When used as a rust converting agent, Haloflex 202
does not show a better performance and cannot convert the rust into the
inert material. The rust also exists in the substrate plate under the
coating film. In this case, the rust can also damage the substrate and the
anticorrosion coating will be bubbling, then the anticorrosion coating
will lose its effect. By contrast, RC-GAE can react with rust and convert
the rust into an inert dense protective film completely (Fig. 5) Herein,
the polymer composite coating which contains RC-GAE and Haloflex
202 can avoid the bubbling phenomenon and has higher corrosion re-
sistance than the polymer composite coating which only contains Ha-
loflex 202.
acids and are non-soluble, and may damage the substrate plate and
cause pitting corrosion. The as-prepared RC-GAE presents an obvious
contrast against the traditional rust converters since it exhibits better
water solubility and compatibility with the water-based anticorrosion
coating than the traditional rust converters, such as GA, due to the fact
that RC-GAE can dissolve in water indefinitely while one g GA can
dissolve in 87 g water, so it can be well dispersed in the polymer
composite coating. Therefore, no organic solvents (isopropyl alcohol
[26]) or strong acids (phosphoric acid [29], sulfuric acid [48]) are
needed to increase the solubility and penetrability of the RC-GAE in the
polymer composite anticorrosion coating. On the basis that RC-GAE can
be well dispersed in the anticorrosion coating, and there is no excess
acid present in the polymer composite anticorrosion coating, the an-
ticorrosion coating based on RC-GAE polymer composites show no
damage on the surface of steel structure and can well avoid the pitting
corrosion and localized corrosion.
In this case, the RC-GAE composite coating film may present a good
corrosion resistance. Table 4 shows the coating film performances of
the anticorrosion composite coating. We concluded that the coating
film exhibited a good adhesion performance as the adhesion level of all
anticorrosion coating films reached 5B (Table 4). From Table 4, the
corrosion resistance of the samples in different coating thicknesses is
improved during the same time, this is due to the active composition
(RC-GAE) in the polymer composite coating film increased from lower
coating thickness to higher coating thickness. Moreover, the corrosion
resistance for the same coating thickness decreased, due to the corro-
sion of NaCl on the surface of the polymer composite coating film. The
salt spray corrosion resistance test is a key indicator of the corrosion

Fig. 8. XPS spectra of the plate samples before and after the treatment with the rust converter.

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J. Li et al. Colloids and Surfaces A 537 (2018) 334–342

Scheme 2. Transformation of Fe2+/Fe3+ chelate.

Table 4 without any cosolvent. Moreover, gallic ester shows no damage on the
Coating films' performance of the anticorrosion coating. surface of steel structure when used for steel structure surface with
large difference in corrosive status. This method can be used for pre-
Coating thickness/μm Adhesion level Rp/96 h Rp/168 h Rp/240 h
paring multifunctional polymer composites coating for various appli-
21 5B 9 8 6 cations [49–56].
39 5B 10 9 7
57 5B 10 10 8 Acknowledgement
81 5B 10 10 9
104 5B 10 10 10
119 5B 10 10 10 The authors wish to acknowledge Jiangxi Boshiming Technology
Industry Co., Ltd. (Shangrao, China) for financial support of this study.

resistance, localized corrosion and pitting of the coating, and it is also
the most classic and most widely used accelerated corrosion test
method to predict the useful life of the coating by evaluating the cor-
rosion resistance, localized corrosion and pitting of the coating in the
world. As the neutral salt spray corrosion resistance showed a high
protection rating (Rp/240 h = 10) and the protection rating did not
decrease obviously as time goes on, indicating that the coating film not
only can well avoid the pitting corrosion and localized corrosion but
also exhibits a superior salt spray resistance.
4. Conclusion
Novel RC-GAE was successfully prepared though an esterification
method. The mass ratio of PG and GA was studied to obtain the optimal
anticorrosion performance, which was confirmed by the Tafel curves.
The as-prepared RC-GAE shows superior rust removal, antirust, and
corrosion resistance capacities. The use of RC-GAE is expected to in-
crease the barrier properties and protective capacity of the water-based
residual rust coatings, and decrease the penetration of aggressive spe-
cies promoting corrosion when the coated metal is exposed to a cor-
rosive environment. Importantly, the gallic ester, used as the rust
converter, presents an excellent water solubility and compatibility with
the water-based anticorrosion coating than gallic acid. Therefore, it can
avoid pitting corrosion and be used directly in the anticorrosion coating
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