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Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Zinc tannate and magnesium tannate as anticorrosion pigments in epoxy

paint formulations
Ariane V. Zmozinskia,⁎, Rafael S. Peresb, Kelly Freibergerb,c, Carlos A. Ferreirac,
Silvia Margonei Mesquita Tamborima, Denise S. Azambujaa
a
Instituto de QUÍMICA, UNIVERSIDADE FEDERAL do Rio GRANDE do Sul, 91501-970, Porto Alegre, RS, BRAZIL
b
Instituto FEDERAL de EDUCAÇão, CIÊNCIA e TECNOLOGIA do Rio GRANDE do Sul – IFRS, 95770-000, CAMPUS Feliz, RUA PRINCESA ISABEL , 60, BAIRRO VILA RICA, Feliz, RS, BRAZIL
c
LAPOL/PPGE3 M – LABORATÓRIO de MATERIAIS Poliméricos, UNIVERSIDADE FEDERAL do Rio GRANDE do Sul, Av. Bento GONÇALVES 9500, 91501-970, Porto Alegre, RS, BRAZIL

ARTICLEINFO ABSTRACT

Keywords: Vegetable tannins are natural, non-toxic, water-soluble polyphenols present in the roots, branches, leaves,
Black wattle tannin flowers, fruits, and seeds of various trees. Tannins can remove rust and inhibit corrosion. Because the high
Corrosion solubility of tannins in water may impair their use as an anticorrosion pigment, a reduction in solubility is
Zinc tannate necessary. In this work, two tannin-based anticorrosive pigments were synthetized by the reaction of black
Magnesium tannate wattle tannin with zinc and magnesium salts to form zinc tannate and magnesium tannate, respectively. Pigment
Organic coatings
synthesis was verified by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR).
Epoxy coatings containing both tannates were formulated and their corrosion performance was evaluated using
electrochemical impedance spectroscopy (EIS) and salt spray tests. Corrosion tests showed that zinc tannate was
an excellent anticorrosive pigment in neutral saline media making it an environmentally friendly option for
anticorrosive coatings.

1. Introduction
Corrosion protection refers to optimization of factors that prevent
corrosion, mainly through use of protective paints. However, it was
only in the nineteenth century that corrosion was recognized as a
problem of great economic significance [1]. Anticorrosive paint is a
mixture of insoluble particles called pigments in an organic or aqueous
continuous vehicle called a resin or matrix [2]. The pigments must have
anticorrosive properties so that the coating protects against corrosion
[2]. Due to the high toxicity of many anticorrosive pigments, green
alternatives have been developed in recent years [3,4].
Naderi and Attar [3] proposed use of strontium aluminium poly-
phosphate as an anticorrosive pigment for an epoxy coating. Darvish
et al. [5] reported better performance of zinc aluminium phosphate
than conventional zinc phosphating. Sanaei et al. [6] developed an
anticorrosive pigment with a zinc acetate-cichorium complex that had
excellent anticorrosive properties. Wahba et al. [7] tested complexes
derived from methoxy-tolidine and salicylaldehyde against corrosion.
Tannins are polyphenolic substances used in the defence mechan-
isms of plants and for tanning animal hides [8,9]. These compounds
have been used for more than four decades in boiler feed-water and
water cooling systems to prevent corrosion of internal parts of these
equipment [10,11]. Tannins are highly soluble in water, but their me-
tallic complexes have limited solubility when synthetized in the pre-
sence of oxygen [12]. An insoluble ferric complex acts as a barrier
against oxygen diffusion, but it is not formed in strongly acidic media
[13,14]. Thus, tannins are responsible for reducing the oxygen con-
centration in aerated aqueous medium and producing a protective film
[10]. Jaén et al. [15] attribute the inhibitory action mechanism of
tannins to the transformation of iron corrosion products (lepidocrocyte
and goethite) into inert and stable products. The transformation of le-
pidocrocyte (γ –FeOOH) to magnetite (Fe3O4) in the presence of mi-
mosa tannin was also reported by Ross et al. [16].
According to Martinez et al. [13,14], tannins can act as corrosion
inhibitors due to the physical or chemical adsorption. At low pH values,
chemical adsorption occurs through the free pair of electrons (from the
OH− group present in the polyphenols) and the metal surface [13]. The
adsorption free energy values suggest the mechanism of physical ad-
sorption at high pH values [13]. Dargahi et al. [11] confirmed the ef-
ficiency of a tannin blend as corrosion inhibitor for mild carbon steel in
alkaline medium. Rahim et al. [17] described a reduction in the in-
hibition efficiency of mangrove tannin with increasing alkalinity of the
medium. Different studies have shown the applicability of the pure
tannins as corrosion inhibitors [11,13,14,16–20]. However, their direct

⁎
Corresponding author.
E-MAIL ADDRESS: arianezmozinski@gmail.com (A.V. Zmozinski).

https://doi.org/10.1016/j.porgcoat.2018.04.007
Received 5 January 2018; Received in revised form 7 March 2018; Accepted 9 April 2018
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application as anticorrosion pigments is challenging due to their water Table 1

solubility. Some authors have reported the use of tannin solutions in Coatings composition.
waterborne primers [21,22]. Sample Abbreviation Components Mass (%) PVC (%)
Addition of complexing metals such as zinc and magnesium to
tannins may improve their anticorrosive properties. These complexes Blank BL Epoxy resin 43.0 25
Curing Agent 9.0
can also decrease the solubility of tannins in water, improving their
TiO2 48.0
anticorrosive properties. The goal of this study is to verify the efficiency Zinc Tannate Coating ZnT Epoxy resin 56.0 25
of two tannin complexes as anticorrosive pigments: zinc tannate and Curing Agent 12.4
magnesium tannate. Both pigments have a low metals content and are Zinc Tannate 29.0
environmentally friendly, using tannins obtained from the black wattle TiO2 2.6
tree. Epoxy coatings containing the synthetized pigments were pre- Magnesium Tannate MgT Epoxy resin 56.0 25
pared and tested in neutral and acidic saline environments. Coating Curing Agent 12.4
Magnesium 29.0
Tannate
2. Experimental TiO2 2.6

2.1. MATERIALS
All solutions and samples were prepared with analytical grade re-
agents. To prepare the tannate pigments, Zn(NO3)2·6H2O (synth, Brazil)
powder, Mg2SO4 (Vetec, Brazil) powder, HCl (Vetec, Brazil), NaOH
(Synth, Brazil) and black wattle tannin (Tanac, Brazil) were used. NaCl
(synth, Brazil) and HCl (Vetec, Brazil) were used for preparation of
electrolyte solutions. Araldite® GZ 7071 × 75 (Hunstsman, USA) epoxy
resin and Aradur® 450 (Hunstsman, USA) curing agent were used as a
matrix for preparation of coatings. TiO2 (Polimerum, Brazil) was used
as a pigment for coating preparation. Carbon steel samples (0.108% C,
0.42% Mn, 0.12% Cr, 0.053% S, and 0.016% P) were used in all tests.
2.2. PREPARATION of ANTICORROSIVE pigments
2.2.1. Zinc TANNATE
First, 20 g of black wattle tannin were weighed in a Becker and
dissolved in 1000 mL of deionized water. After dissolution of the
tannin, 20 mL of a 1 M Zn(NO3)·6H2O solution was added. The pH was
then adjusted to 7.5 with a NaOH solution and the mixture was stirred
for 1 h [23]. After stirring, the solution was filtered and dried at 110 °C
for 6 h.
2.2.2. MAGNESIUM TANNATE
First, 20 g of black wattle tannin were weighed in a Becker and
dissolved in 1000 mL of deionized water. After dissolution of the
tannin, 40 mL of a 1 M MgSO4 solution was added. The pH was then
adjusted to 8.0 with a 0.5 M NaOH solution and the mixture was stirred
for 1 h. After stirring, the solution was filtered and dried at 110 °C for
6 h.
The zinc and magnesium tannates were milled and sieved in a 20 μm
sieve before coating dispersion. The particle size of both pigments was
between 6 and 7 Hegman (25 μm and 13 μm), measured with a grind
gauge (BYK, Germany). According to the particle size distribution
(Tegape sieves, Brazil), the mean particle size for zinc tannate pigment
was 18 μm and for magnesium tannate was 16 μm. There are no sig-
nificant morphological differences between the two pigments.
added and the mixture was kept in the disperser for 1 h. Coating
compositions and pigment volume concentrations (PVC) are given in
Table 1. PVC values were kept constant to allow comparison between
anticorrosive pigments.
After the coating preparation, steel samples were degreased with
acetone, polished with #150 sandpaper, and degreased again. The
curing agent was then mixed with the coatings and the steel samples
were brushed with the paints.
2.5. Corrosion experiments
Electrochemical impedance spectroscopy (EIS) was carried out
using an AUTOLAB PGSTAT 302N potentiostat coupled to a frequency
response analyser. All measurements were performed in potentiostatic
mode at the open circuit potential with an amplitude of 10 mV and
frequencies ranging from 100 kHz to 10 mHz. The working electrode
(coating) size was delimited by an electrochemical cell (4 cm2). A sa-
turated calomel electrode (SCE) was used as a reference electrode and a
platinum wire (spiral geometry) was used as an auxiliary electrode. The
electrolyte used in the EIS measurements was 3.5% NaCl (w/v). In the
acidic medium experiments, the pH of the 3.5% NaCl (w/v) solution
was adjusted to 2. Coating thicknesses for EIS experiments were:
142 ± 10 μm for MgT, 148 ± 13 μm for ZnT, and 141 ± 11 μm for
BL.
Salt spray tests were performed according to the standard ASTM
B117 [24] and ASTM D714 [25]. A central cut was made in all coatings
to determine electrolyte migration. The dry paint film thickness was
measured with a Byko-test 7500 electromagnetic film thickness gauge
(BYK Gardner, Germany). The mean value of six different areas of the
steel samples was used to calculate the final dry film thickness. Steel
samples (50 mm × 50 mm) were painted with BL, ZnT, and MgT
coatings until reaching a thickness of: 134 ± 7 μm for MgT,
131 ± 13 μm for ZnT, and 135 ± 6 μm for BL.
2.6. COATING CHARACTERIZATION

2.3. Pigment CHARACTERIZATION
The zinc and magnesium tannates were characterized by TGA, and
FTIR. The FTIR spectrum was measured using a Perkin Elmer Spectrum
1000 spectrometer with KBr pellets. TGA (TA Instruments TGA 2050)
analyses were performed with approximately 20 mg of sample heated at
20 °C/min in a nitrogen atmosphere.
2.4. COATING AND SAMPLE PREPARATION
The epoxy resin was added in the jacketed reactor of a Dispermat N1
(VMA-Getzmann GmbH of Reichshof, Germany) disperser equipped
with a Cowles disk and stirred for 15 min. The solid pigments were then
Adhesion measurements were made according to the ASTM D3359
standard test [26]. Orthogonal cuts (1 mm) were made over the coat-
ings. The surface was cleaned and Scoth-880 (3 M, USA) tape was at-
tached over the cuts. The tape was pulled off at an angle close to 180° in
relation to the coating plane. The detached area (without coating) was
used to measure the degree of adhesion. The coatings adhesion was also
measured with a PosiTest® AT-A pull-off adhesion tester (DeFelsko,
USA). Dollies (14 mm diameter) were glued over the coatings (six re-
plicates) and pulled off the surface. Coating adhesion was measured in
MPa using a pull rate of 0.25 MPa s−1. Tests were in accordance with
ASTM 4541 [27].
Optical microscopy images were obtained by a Dino-lite model
AD7013MT USB digital microscope.

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Fig. 1. FTIR spectra of tannin, magnesium and zinc tannates.
3. Results and discussion
3.1. Pigments synthesis
The FTIR spectra of zinc tannate and magnesium tannate pigments
are given in Fig. 1 and show broader peaks than pure tannin, due to the
amorphous nature of tannin complexes [28]. The shift of peaks to high
wavenumbers for tannate FTIR spectra compared with pure tannin also
supports the formation of metallic chelates [29]. Characteristics tannin
peaks can be observed in Fig. 1 for all compounds at wavenumbers
[30]: ∼3400 cm−1 (eOH stretch), 1031 cm−1 (CeO stretch),
1618 cm−1 (C]C stretch in aromatic ring), 1508 cm−1 (C]C stretch in
aromatic ring), and 1452 cm−1 (C]C stretch in aromatic ring).
The TGA curves of tannin, zinc, and magnesium tannates are shown
in Fig. 2. At 900 °C the residue is greater than 30% for all samples,
indicating the high thermal stability of tannin and tannates due to the
presence of aromatic structure in polyphenols [31]. The main difference
in the DTGA between the tannates and pure tannin is an additional peak
(between 834 °C and 510 °C) for zinc tannate and magnesium tannate,
suggesting the presence of metals in the pigments (Fig. 2b).
3.2. ELECTROCHEMICAL tests
The anticorrosive behaviour of the tannates pigments was evaluated
in acidic and neutral media.
3.2.1. NEUTRAL pH
Fig. 3 shows EIS plots of BL, ZnT, and MgT after 28 days of
Fig. 2. (a) TGA of tannin, magnesium and zinc tannates. (b) DTGA of tannin, magnesium and zinc tannates.
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immersion in neutral NaCl solution. The overall impedance modulus of
the ZnT coating is two orders of magnitude higher than that of BL and
MgT. The maximum phase angles (Fig. 3b) are close to −90° at high
frequencies for all samples, which is characteristic of epoxy coatings.
However, the ZnT coating maintains a capacitive behaviour over a
wider range of frequencies, compared to BL and MgT coatings.
Another important difference in the EIS spectrum of ZnT is the
presence of two overlapping time constants. In the EIS spectra of MgT
and BL these two time constants are separated, depressed semicircles at
lower frequencies, which has been attributed to the onset of corrosion
triggered by electrolyte penetration through pores in the coatings [32].
The presence of only one time constant was observed in all samples
(electrolyte does not react with the metal surface) in the initial im-
mersion times [33]. However, two well-defined time constants ap-
peared after 7 days of immersion in the blank and MgT samples. For
ZnT, the second time constant (two overlapping time constants) ap-
peared after 21 days.
The EIS fittings parameters confirm the presence of two time con-
stants in all samples, labelled (R1Q1) and (R2Q2), where the parentheses
indicate that the elements are in parallel (Fig. 3). The equivalent circuit
chosen (Figs. 3 and 5) represents the model described by Hinderliter
et al. [33] and Olivier et al. [34], which considers the electrolyte dif-
fusion into the coating after 28 days of immersion. The first time con-
stant (at high frequency) refers to the organic coating layer, while the
second (at low frequency) refers to the creation of a new interface
generated by the reaction of the electrolyte with the metal substrate
[34]. In the equivalent circuit given in Fig. 3, Rs represents the elec-
trolyte resistance, CPE1 represents the coating capacitance, R1
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Fig. 3. (a) Nyquist and (b) Bode plots of BL

(black circle), ZnT (red circle) and MgT (blue
circle) coatings after 28 days of immersion in
neutral 3.5% NaCl solution. The insets re-
present the approximation of Nyquist area and
the equivalent electrical circuit. Lines in both
plots represents the fitting data. (For inter-
pretation of the references to colour in this
figure legend, the reader is referred to the web
version of this article.)

represents the coating pore resistance, CPE2 represents the double layer impedance of the ZnT coating is more than 100 fold higher than that of
capacitance and R2 represents the faradic impedance [34]. The use of BL and MgT, demonstrating the excellent anticorrosive properties of
constant phase element (CPE) instead of pure capacitance was due to zinc tannate in neutral media (Fig. 4b).
considering the system non-ideal [34,35].
The symbol Q is the impedance in terms of a CPE and n [35]. Ac-
3.2.2. Acid pH
cording to the simulation, n ∼ 1 for all samples in the high frequency
The behaviour of ZnT, MgT, and BL in acid 3.5% NaCl were in-
semi-circle (n1 = 0.98 for ZnT, n1 = 0.96 for BL, and n1 = 0.94 for
vestigated and the EIS spectra are given in Fig. 5. Similar to neutral pH
MgT), which means they behave similarly to a capacitor [35]. The
analyses, in the initial immersion times the equivalent circuit is re-
semicircles at low frequencies for BL and ZnT samples have n ∼ 0.5,
presented by only one time constant (electrolyte does not react with the
which represents diffusional processes in the electrode [35,36]. After
metal surface) [33]. After 7 days of immersion, a second time constant
28 days of immersion, the resistance (R1) of the ZnT coating
appeared for all samples. All diagrams show similar shapes, with two
(383.12 MΩ cm2) is higher than BL (2.42 MΩ cm2) and MgT
separate time constants. The first one at a high frequency is related to
(1.19 MΩ cm2), demonstrating the effective anticorrosive properties of
the coating with capacitive characteristics, and the second at lower
zinc tannate in neutral media. The CPE1 of ZnT
(8.12 × 10−11 F cm−2 sn−1) is smaller than BL(1.49 frequencies is attributed to development of corrosion [34,40]. The de-
× 10−10 F cm−2 sn−1) and MgT (5.42 × 10−10 F cm−2 sn−1) preciation of the phase angle at low frequencies and the presence of a
samples, confirming the high corrosion resistance of ZnT in neutral resistive character indicates a conductive path for the electrolyte [40].
The ZnT coating has the lowest impedance value after 28 days of
media.
immersion, indicating inferior corrosion protection compared to BL and
Fig. 4a shows variations in the corrosion potential (Ecorr) of all
MgT in acidic media. Thus, zinc tannate and magnesium tannate pig-
samples versus time for 28 days in neutral NaCl. The Ecorr decreases
ments were inefficient in acidic environments.
with time due to electrolyte penetration. The Ecorr values after 28 days
are −0.541 V, −0.673 V, and −0.698 V for BL, MgT and ZnT, re- Based on EIS simulation, all samples have two time constants
((R1Q1) and (R2Q2)) and the semicircles at high frequencies has
spectively (Fig. 4a). Jagtap et al. [37] measured the corrosion potential
n1 = 0.94 for ZnT, n1 = 0.97 for BL, and n1 = 0.96 for MgT. The ele-
in coatings with small amounts of zinc. The authors found that these
ments of the equivalent circuit have the same physical meanings as
potentials are close to the corrosion potential of steel in neutral 3.5%
NaCl due to the small anodic area (small amount of zinc present in the those described in the basic pH. The ZnT coating has the lowest re-
sistance (2.15 MΩ cm2) after 28 d of immersion, indicating inferior
ZnT pigments) [37,38]. According to previous work [39], tannins can
corrosion protection compared with BL (9.12 MΩ cm2) and MgT
act as barrier against the electrolyte at neutral pH, keeping Ecorr values
around −0.7 V. Data for the ZnT coating indicate pore blocking by zinc (9.35 MΩ cm2) in acidic media. The CPE1 of ZnT
(1.26 × 10−9 F cm−2 sn−1) and MgT (1.49 × 10−9 F cm−2 sn−1) are
tannate.
higher than BL (5.77 × 10−10 F cm−2 sn−1), proving that zinc tannate
Variations in sample impedance (measured at 10 mHz) during
and magnesium tannate are ineffective in acidic environments.
28 days of immersion are shown in Fig. 4b. Impedance decreases with
Fig. 6 shows the variation in corrosion potential (Ecorr) versus time
time for all samples. However, after 28 days of immersion the overall
for 28 days in acidic NaCl. During the test, Ecorr values decreases

Fig. 4. (a) Variation of Ecorr and (b) variation of impedance (measured at 10 mHz) during 28 days of immersion in neutral 3.5% NaCl solution. BL (black circle), MgT
(blue circle) and ZnT (red circle). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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Fig. 5. (a) Nyquist and (b) Bode plots of BL

(black circle), ZnT (red circle) and MgT (blue
circle) coatings after 28 days of immersion in
acid 3.5% NaCl solution. The insets represent
the approximation of Nyquist area and the
equivalent electrical circuit. Lines in both plots
represents the fitting data. (For interpretation
of the references to colour in this figure legend,
the reader is referred to the web version of this
article.)

immersion times. BL and MgT samples had more positive Ecorr values Table 2
initially, indicating preliminary pore blocking. The ZnT coating showed Degree of blistering and delamination values.
a more negative potential from the beginning of immersion, indicating Sample Blister size Blister frequency Delamination (mm)
poor anticorrosion properties in the acidic 3.5% NaCl (w/w) medium.
The different behaviours of zinc and magnesium tannates in dis- BL 8 Medium dense 10.4
similar media shows the importance of pigment water solubitility. MgT 6 Medium 11.2
ZnT 8 Few 5.1
Magnesium tannate is more soluble than zinc tannate, which con-
tributes to the ZnT coating having better protection in neutral media
than MgT. This is because zinc tannate is a more stable complex than (larger bubble size). The blister frequency represents the total of bub-
magnesium tannate, which can provide pore blocking for ZnT paint.
bles detected on the coating surface [25]. The ZnT coating presented
Due to the high solubility of magnesium tannate, preferential flow
lower blister frequency (also smaller size) and lower delaminated area
paths are rapidly formed in the MgT coating, facilitating electrolyte
when compared to the other samples, indicating a better anticorrosive
penetration and consequently decreasing corrosion resistance [13,41]. efficiency.
In acidic media, the more soluble tannate (MgT) shows a slight better
Fig. 7 shows the micrographs of three tested coatings after 700 h in
anticorrosion performance than ZnT, due to the tendency of tannins to
a salt fog chamber. For BL (Fig. 7a) and MgT (Fig. 7c) coatings, the
adsorb on metal surfaces by chemisorption [14]. However, the perfor-
electrolyte migrated through the cut below the paint layer, creating
mance of MgT and BL are similar, indicating poor anticorrosion pro-
bubbles in the coating surface. The presence of several pores was ob-
tection of the MgT coating as well.
served at higher magnification for BL (Fig. 7b) and MgT (Fig. 7d)
The stability of the tannates can be associated with the medium
samples. This explains the poor anticorrosive properties of both coat-
where they are present. According to Martinez et al. [13,14], the for-
ings as measured by EIS. However, bubbles and large pores were not
mation of metallic tannates occurs at high pH values and the presence observed in ZnT samples (Fig. 7e and 7f), confirming EIS results that the
of an acid medium may compromise its stability. Slabber [42] reported ZnT coating offers better corrosion protection.
the formation of zinc tannate at pH = 6.1 and the magnesium tannate
at pH = 8.8. This fact can explain the better efficiency of TZn in rela-
tion of TMg in neutral media, since an alkaline medium would be ne- 3.4. Adherence tests
cessary to maintain the stability of magnesium complex (pH > 8.8).
An adherence test was performed to measure the influence of zinc
tannate and magnesium tannate to coatings adherence. Results are
3.3. SALT SPRAY tests given in Table 3.
All coatings had similar behaviours in both adherence testes. The
To verify the corrosion resistance of BL, MgT, and ZnT coatings in samples showed 5 B degree in ASTM D3359 test [26], indicating no
saline fog, salt spray tests were performed. The degree of blistering and coating removal. The pull-oafflso
tessthowed similar adherences,
delamination values are given in Table 2. According to ASTM D714 proving that zinc tannate and magnesium tannate pigments do not af-
[25], the blister size is given on a scale from 10 (no bubbles) to zero fect the final coatings adherence.

Fig. 6. (a) Variation of Ecorr and (b) variation of impedance (measured at 10 mHz) during 28 days of immersion in acid 3.5% NaCl solution. BL (black circle), MgT
(blue circle) and ZnT (red circle). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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Fig. 7. Micrographs of (a,b) BL, (c,d) MgT and (e,f) ZnT coatings after 700 h in salt fog chamber.

Table 3 Acknowledgements
Adherence tests.

Sample Tape Test Pull-off Test (MPa)

The authors are grateful to CAPES, FAPERGS and CNPq for A.V
postdoctoral scholarship (CNPq process n° 150108/2017-6) and for the
BL 5B 2.17 ± 0.3 financial support.
MgT 5B 2.15 ± 0.5
ZnT 5B 2.08 ± 0.3
References

4. Conclusion
In this work, the anticorrosion performance of two coatings for-
mulated with pigments synthetized from black wattle tannin (zinc
tannate and magnesium tannate) was tested. FTIR and TGA experi-
ments confirm the synthesis of both tannates via reaction of zinc and
magnesium salts with black wattle tannin. EIS and salt spray tests show
that zinc tannate when used in an amount of 29% in mass (paint with
PVC = 25%) is an excellent anticorrosion agent in neutral saline en-
vironments, while both pigments used ate same PVC have poor antic-
orrosive properties in acidic media. Thus, this work has developed a
sustainable, environmentally friendly and low- zinc content antic-
orrosive pigment.
[1] E. Ghali, V.S. Sastri, M. Elboujdaini, Corrosion Prevention and Protection Practical
Solutions, first ed., Wiley, Chichester, 2007.
[2] P.A. Sørensen, S. Kiil, K. Dam-Johansen, C.E. Weinell, Anticorrosive coatings: a
review, J. Coat. Technol. Res. 6 (2009) 135–176.
[3] R. Naderi, M.M. Attar, Effect of zinc-free phosphate-based anticorrosion pigment on
the cathodic disbondment of epoxy-polyamide coating, Prog. Org. Coat. 77 (2014)
830–835.
[4] S. Roselli, N. Bellotti, C. Deyá, M. Revuelta, B. del Amo, R. Romagnoli, Lanthanum-
exchanged zeolite and clay as anticorrosive pigments for galvanized steel, J. Rare
Earth 32 (2014) 352–359.
[5] A. Darvish, R. Naderi, M.R.M. Attar, Improvement in polyurethane coating per-
formance through zinc aluminium phosphate pigment, Pigm. Resin Technol. 45
(2016) 419–425.
[6] Z. Sanaei, T. Shahrabi, B. Ramezanzadeh, Synthesis and characterization of an ef-
fective green corrosion inhibitive hybrid pigment based on zinc acetate-Cichorium
intybus L leaves extract (ZnA-CIL.L): electrochemical investigations on the sy-
nergistic corrosion inhibition of mild steel in aqueous chloride solutions, Dyes Pigm.
139 (2017) 218–232.
[7] O.A.G. Wahba, A.M. Hassan, A.M. Naser, A.M.-E. Gabr, Green synthesis and spec-
troscopic studies of some complexes compounds as pigments and their applications
in paints, Pigm. Resin Technol. 46 (2017) 286–295.

2
8
A.V. Zmozinski et AL.
[8] E. Onem, G. Gulumser, S. Akay, O. Yesil-Celiktas, Optimization of tannin isolation
from acorn and application in leather processing, Ind. Crop. Prod. 53 (2014) 16–22.
[9] I. Glazer, L. Salame, L. Dvash, H. Muklada, H. Azaizeh, R. Mreny, A. Markovics,
S. Landau, Effects of tannin-rich host plants on the infection and establishment of
the entomopathogenic nematode Heterorhabditis bacteriophora, J. Invertebr.
Pathol. 128 (2015) 31–36.
[10] A. Berk, W. Schroeder, Determination of tannin substances in boiler waters, Ind.
Eng. Chem. Anal. Edit. 14 (1942) 456–459.
[11] M. Dargahi, A.L.J. Olsson, N. Tufenkji, R. Gaudreault, Green technology tannin-
based corrosion inhibitor for protection of mild steel, Corrosion 71 (2015)
1321–1329.
[12] J. Gust, J. Suwalski, Use of Mössbauer spectroscopy to study reaction products of
polyphenols and iron compounds, Corrosion 50 (1994) 355–365.
[13] S. Martinez, Inhibitory mechanism of mimosa tannin using molecular modeling and
substitutional adsorption isotherms, Mater. Chem. Phys. 77 (2003) 97–102.
[14] S. Martinez, I. Štern, Inhibitory mechanism of low-carbon steel corrosion by mimosa
tannin in sulphuric acid solutions, J. Appl. Electrochem. 31 (2001) 973–978.
[15] J.A. Jaén, E.Y. Araúz, J. Iglesias, Y. Delgado, Reactivity of tannic acid with common
corrosion products and its influence on the hydrolysis of iron in alkaline solutions,
Hyperfine Interact. 148 (2003) 199–209.
[16] T.K. Ross, R.A. Francis, The treatment of rusted steel with mimosa tannin, Corros.
Sci. 18 (1978) 351–361.
[17] A.A. Rahim, E. Rocca, J. Steinmetz, M. Kassim, R. Adnan, M. Sani Ibrahim,
Mangrove tannins and their flavanoid monomers as alternative steel corrosion in-
hibitors in acidic medium, Corros. Sci. 49 (2007) 402–417.
[18] A.A. Rahim, J. Kassim, Recent development of vegetal tannins in corrosion pro-
tection of iron and steel, Recent Pat. Mater. Sci. 1 (2008) 223–231.
[19] A.A. Rahim, E. Rocca, J. Steinmetz, M. Jain Kassim, Inhibitive action of mangrove
tannins and phosphoric acid on pre-rusted steel via electrochemical methods,
Corros. Sci. 50 (2008) 1546–1550.
[20] R.S. Peres, E. Cassel, D.S. Azambuja, Black wattle tannin as steel corrosion inhibitor,
ISRN Corrosion 2012 (2012) 1–9.
[21] G. Matamala, W. Smeltzer, G. Droguett, Use of tannin anticorrosive reaction primer
to improve traditional coating systems, Corrosion 50 (1994) 270–275.
[22] O.R. Pardini, J.I. Amalvy, A.R. Di Sarli, R. Romagnoli, V.F. Vetere, Formulation and
testing of a waterborne primer containing chestnut tannin, J. Coat. Technol. Res. 73
(2001) 99–106.
[23] N. Bellotti, C. Deyá, B. del Amo, R. Romagnoli, Antifouling paints with zinc tannate,
Ind. Eng. Chem. Res. 49 (2010) 3386–3390.
[24] ASTM B117-16 – Standard Practice for Operating Salt Spray (Fog) Apparatus, ASTM
International, West Conshohocken, PA, 2002.
[25] ASTM D714-02 – Standard Test Method for Evaluating Degree of Blistering of
Paints, ASTM International, West Conshohocken, PA, 2017.
[26] ASTM D 3359-02 – Standard Test Methods for Measuring Adhesion by Tape Test,
(2018).
[27] ASTM D4541-09 – Standard Test Method for Pull-Off Strength of Coatings Using
2
9
P
rogressinO
rgA
N icC
oAtin
gs12
1(20
18)2
3–29
Portable Adhesion Testers, ASTM International, West Conshohocken, PA, 2009.
[28] R. Zhang, L. Li, J. Liu, Synthesis and characterization of ferric tannate as a novel
porous adsorptive-catalyst for nitrogen removal from wastewater, RSC Adv. 5
(2015) 40785–40791.
[29] M. Magro, E. Bonaiuto, D. Baratella, J. de Almeida Roger, P. Jakubec,
V. Corraducci, J. Tuček, O. Malina, R. Zbořil, F. Vianello, Electrocatalytic nanos-
tructured ferric tannates: characterization and application of a polyphenol nano-
sensor, ChemPhysChem 17 (2016) 3196–3203.
[30] L. Falcão, M.E.M. Araújo, Tannins characterization in historic leathers by com-
plementary analytical techniques ATR-FTIR, UV–vis and chemical tests, J. Cul.
Herit. 14 (2013) 499–508.
[31] S.-H. Cheng, S.-H. Hsiao, T.-H. Su, G.-S. Liou, Novel aromatic poly(amine-imide)s
bearing a pendent triphenylamine group: synthesis, thermal, photophysical, elec-
trochemical, and electrochromic characteristics, Macromolecules 38 (2005)
307–316.
[32] V. Dalmoro, J.H.Z. dos Santos, D.S. Azambuja, Corrosion behavior of AA2024-T3
alloy treated with phosphonate-containing TEOS, J. Solid State Electrochem. 16
(2012) 403–414.
[33] B.R. Hinderliter, S.G. Croll, D.E. Tallman, Q. Su, G.P. Bierwagen, Interpretation of
EIS data from accelerated exposure of coated metals based on modeling of coating
physical properties, Electrochim. Acta 51 (2006) 4505–4515.
[34] M.G. Olivier, M. Poelman, M. Demuynck, J.P. Petitjean, EIS. evaluation of the fi-
liform corrosion of aluminium coated by a cataphoretic paint, Prog. Org. Coat. 52
(2005) 263–270.
[35] M.E. Orazem, B. Tribollet, Time-constant dispersion, Electrochemical Impedance
Spectroscopy, John Wiley & Sons, Inc., 2008, pp. 233–263.
[3u6p]onM
D t,.FS..W. Donne, Charge storage mechanisms in electrochemical capaci-
tors: effects of electrode properties on performance, J. Power Sources 326 (2016)
613–623.
[37] R.N. Jagtap, P.P. Patil, S.Z. Hassan, Effect of zinc oxide in combating corrosion in
zinc-rich primer, Prog. Org. Coat. 63 (2008) 389–394.
[38] O.Ø. Knudsen, U. Steinsmo, M. Bjordal, Zinc-rich primers—test performance and
electrochemical properties, Prog. Org. Coat. 54 (2005) 224–229.
[39] R.S. Peres, E. Cassel, D.S. Azambuja, Black wattle tannin as steel corrosion inhibitor,
ISRN Corrosion 2012 (2012) 1–9.
[40] S.M. Tamborim, A.P.Z. Maisonnave, D.S. Azambuja, G.E. Englert, An electro-
chemical and superficial assessment of the corrosion behavior of AA 2024-T3
treated with metacryloxypropylmethoxysilane and cerium nitrate, Surf. Coat.
Technol. 202 (2008) 5991–6001.
[41] M. Magnani, P.H. Suegama, A.A.C. Recco, J.M. Guilemany, C.S. Fugivara,
A.V. Benedetti, WC-CoCr coatings sprayed by high velocity oxygen-fuel (HVOF)
flame on AA7050 aluminum alloy: electrochemical behavior in 3.5% NaCl solution,
Mater. Res. 10 (2007) 377–385.
[42] N. Slabbert, Complexation of condensed tannins with metal ions, in:
R.W. Hemingway, P.E. Laks (Eds.), Plant Polyphenols: Synthesis, Properties,
Significance, Springer, US, Boston, MA, 1992, pp. 421–436.