Progress in Organic Coatings 117 (2018) 35–46

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Progress in Organic Coatings

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Study of zinc tannates prepared with Tara powder (Caesalpinia spinosa) as T

anticorrosive pigments in alkyd paints and wash primer formulations
⁎
A. Hadzicha, S. Floresa, , J. Caprarib, R. Romagnolib
a
ICP-PUCP. Instituto de Corrosión y Protección, Pontificia Universidad Católica del Perú PUCP, Avenida Universitaria 1801, Lima 32, Peru
b
CIDEPINT. Centro de Investigación y Desarrollo en Tecnología de Pinturas, Calle 52 e/121 y 122, 1900 La Plata, Argentina

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

Keywords: The aim of this research was to evaluate the anticorrosive properties of alkyd paints and wash primers for-
Paint coatings mulated with zinc tannates containing Tara tannins. Their inhibitory efficiency was compared with paints
Tannate pigmented with well-known anticorrosive pigments by accelerated corrosion tests (salt spray test, Prohesion test,
Testing and sulphur dioxide test), natural exposure tests and some electrochemical techniques (corrosion potential,
Atmospheric corrosion
polarization resistance and impedance measurements). It was demonstrated that the capacity of inhibiting
Inhibitors
corrosion of zinc tannates is equivalent to that shown by most commercially available conventional pigments,
EDS analysis
such as zinc phosphate and zinc chromate.

1. Introduction
The use of organic coatings is the most commonly employed method
to protect metal structures against corrosion [1–7]. Anticorrosive pig-
ments are dispersed homogeneously throughout the paint film in order
to enhance protection by any of these three main mechanisms: barrier
effect, cathodic protection and inhibitory effect [6,8–10]. The com-
mercial value of all anticorrosive pigments is calculated with certain
quality parameters: level of toxicity, inhibiting efficiency and price
[11].
Nowadays, the paint industry is in search of environmentally
friendly pigments that could substitute the widely used conventional
anticorrosive pigments [3,4,10–13], such as lead or chromate, because
of their harmful toxicity [14–16]. Even at present, the use of phos-
phates, pigments with an equivalent anticorrosion behaviour
[1–5,8,13,17–20] with a lesser level of toxicity [21], has increased the
environmental concern, because they cause eutrophication of fresh-
water reserves [22].
Paint trends are constantly changing as health and safety legisla-
tions multiply. Although phosphate pigments dominate the market
[23], other inhibitory compounds are being developed [22–27]. Metal
tannates, compounds containing tannins, have received special atten-
tion in recent years [27–34]. Vegetal tannins are non-toxic, biode-
gradable organic compounds that can be obtained at reduced costs
[35]. Tannic acid can act as a ligand, forming soluble or insoluble
complexes with several metals, etc. [36,37]. Tannins are distributed in
two groups according to their structure: hydrolysable and condensed.
The use of hydrolysable tannins has been limited; only few researches
have been published in the field of antifouling paints [28,29,32] and
rust converters [38–41]. However, it has been shown that tannins could
improve the corrosion behaviour of a coating system [42,43].
The aim of this research is to validate the use of zinc tannates
prepared with Tara (Caesalpinia spinosa) hydrolysable tannins as an-
ticorrosive pigments in alkyd paints and wash primer formulations, in
order to study their inhibitory efficiency. The low cost, high ease of
application and good adhesion of alkyd-base coatings have turned them
into the most important and widely applied protection method against
corrosion [44–46], specifically in moderate corrosive environments
[46]. Meanwhile, wash primers are reported as traditional formulations
prepared with a polyvinylbutiral resin, an anticorrosive pigment and
phosphoric acid [47–49]. These pre-treatment coatings are responsible
for preventing or retarding the spread of corrosion until the topcoat is
applied, and effectively act as a tie-coat, improving the adhesion of the
subsequent coat with the metal substrate [47,48].
Accelerated corrosion tests (salt spray test, Prohesion test, and sul-
phur dioxide test), natural exposure tests and electrochemical tests
(corrosion potential and polarization resistance measurements) were
performed to assess the corrosion protection properties of paints pig-
mented with zinc tannates. For comparative studies, paints containing
conventional pigments (zinc chromate and zinc modified phosphate)
were prepared and evaluated in parallel.

⁎
Corresponding author.
E-mail address: sflores@pucp.edu.pe (S. Flores).

https://doi.org/10.1016/j.porgcoat.2017.12.019
Received 18 April 2017; Received in revised form 12 December 2017; Accepted 21 December 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.
A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

2. Experimental
2.1. Materials and films preparation
2.1.1. Pigments
Zinc tannates prepared with Tara powder and zinc oxide were used
to manufacture alkyd paints and wash primers. Tara powder was ob-
tained from SILVATEAM Peru (Callao, Peru). Zinc oxide (ZnO) was
purchased from Industrias Electroquímicas S.A. (Callao, Peru). Yellow
zinc chromate and a zinc phosphate modified with molybdenum were
also employed as commercial well-known anticorrosive pigments for
comparison purposes.
2.1.2. Paints manufacture and application
Paints were formulated employing high-speed disperser equipment.
Pigment concentration was changed according to the volume of zinc
chromate used to ensure the same pigment volume concentration (PVC)
in all formulations. All pigments were incorporated in accordance with
their increasing oil absorption. In all cases, paints were applied using a
spray gun (2 coats). Environmental conditions were controlled during
application.
In all cases, the average dry film thickness was measured with a
Deltascope MP30 equipment, brand Fischer (Tables 1 and 2). The edges
of the coated panels were protected with a grey, waterproof poly-
ethylene tape (Brand 3M, model 3939). According to ASTM D1654-05
standard, a linear incision was applied to one of the plates of each
paint/painting system, at the bottom of the specimen with a scribing
tool (brand Erichsen).
2.1.3. Wash primers
Four types of two-pack wash primers (WP) were prepared with the
following anticorrosive pigments: zinc chromate (WCr), zinc phosphate
modified with zinc molybdate (WF), zinc tannate TZn3 (WTZ3) and
zinc tannate TZn4 (WTZ4). The weight percentages of the components
used in the formulation of the wash primer are shown in Table 3. Both
fractions, part A and part B, were mixed in a 4–1 ratio, before paint
application.
For accelerated and natural exposure tests, panels (JIS G3141, SPCC
grade) of 10 cm x 15 cm were previously polished using a grinder with
an emery paper No. 100, and then polished manually in two directions
with emery paper No. 100. They were finally degreased with ethanol
and then coated. The composition of JIS G3141 mild steel is as follows:
C: 0.15%, Mn: 0.60%, S: 0.05% and P: 0.10%.
Four specimens were painted for each type of wash primer. Two
coated panels were selected to apply a top layer of synthetic, white,
commercial alkyd paint, and were identified with a letter S at the end of
its name (e.g., WP-S). The mean value of the dry film thicknesses is
reported.
For electrochemical measurements, JIS G3141 (2 cm x 6 cm x 3 mm)
mild steel panels, were abraded with No 100 emery paper, degreased
with ethanol, and finally coated. A square zone of 1 cm2 was delimited
with paraffin to use as working electrodes.
2.1.4. Alkyd paints
Four types of alkyd paints (AP) were prepared with the following
anticorrosive pigments: yellow zinc chromate (ACr), zinc phosphate
modified with zinc molybdate (AF), zinc tannate TZn3 (ATZ3) and zinc
tannate TZn4 (ATZ4). The weight percentages of the components used
in the formulation of alkyd paints are shown in Table 4.
Test panels (JIS G3141, SPCC grade) of 10 cm x 15 cm were sand-
blasted, meeting the requirements of the standard ASTM D4940. An
average roughness of 2.3 mils was attained. Panels were cleaned up and
then coated.
For the accelerated tests, salt spray test and Prohesion test, as well
as for the natural exposure tests, six specimens were painted for each
type of alkyd primer. A top layer of synthetic, white, commercial alkyd
paint, was applied to half of the samples and were identified with a
letter S (e.g., AP-S). For the SO2 salt fog test only two coated panels
with each type of primer, alone and in a paint system, were tested. The
mean value of the dry film thicknesses is reported.
2.2. Characterization of zinc tannates
The Fourier spectrums of zinc tannates and Tara powder were ob-
tained using the potassium bromide disc technique and a Perkin–Elmer
Spectrum 100 FTIR Spectrometer. The following physicochemical
properties were analysed according to international standards: Oil
Absorption by Spatula Rub-Out (ASTM D281), pH of aqueous extract
(ISO 787/9), specific gravity (based on ASTM D153), residue on sieve
(based on ASTM D185), matter solubility in water at 25 °C (ISO 787/8)
and ≥100 °C (ISO 787/3), and loss of ignition (ISO 6745/7).
Filtrated suspensions prepared to determine matter solubility in
water at different temperatures (ISO 787/8 and ISO 787/3) were used
to calculate the amount of soluble chlorides and sulphates in metal
tannates by EPA Method 300.0. A LaChrom Merck-Hitachi ion exchange
chromatography equipment coupled with a LaChrom L-7470 Merck-
Hitachi detector was employed. To analyse the amount of zinc in the
synthesized tannates, the preparation of the test solutions was carried
out in accordance with the standard test method ISO 6745/8, and the
content of zinc in aqueous solutions was quantified with a OPTIMA

Table 1
Dry film thicknesses of mild steel specimens painted with wash primers and alkyd paints used in accelerated corrosion tests.

Sample Salt spray test Prohesion test SO2 test

Primer (μm) System (μm) Primer (μm) System (μm) Primer (μm) System (μm)

WCr 16.8 – 14.5 – – –

WF 20.4 – 21.6 – – –
WTZ3 17.0 – 19.1 – – –
WTZ4 18.2 – 18.7 – – –
WCr-S 16.1 48.1 13.0 46.7 – –
WF-S 13.7 39.8 17.8 53.7 – –
WTZ3-S 13.9 54.9 15.5 52.6 – –
WTZ4-S 15.2 50.5 15.7 53.8 – –
ACr 40.9 – 29.5 – 31.4 –
AF 40.6 – 43.7 – 48.5 –
ATZ3 40.6 – 30.9 – 31.9 –
ATZ4 41.2 – 44.5 – 28.4 –
ACr-S 24.7 71.6 15.8 67.6 19.1 67.6
AF-S 21.9 71.9 33.1 85.8 32.8 82.5
ATZ3-S 24.9 79.1 27.3 76.7 30.3 74.6
ATZ4-S 22.7 72.5 37.5 85.6 35.9 84.6

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A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

Table 2
Dry film thicknesses of mild steel specimens painted with wash primers and alkyd paints used in natural exposure tests.

Sample Lima Chimbote Trujillo

Primer (μm) System (μm) Primer (μm) System (μm) Primer (μm) System (μm)

ACr 48.8 – 34.7 – 36.5 –

AF 48.2 – 35.2 – 38.5 –
ATZ3 34.4 – 34.9 – 37.0 –
ATZ4 45.7 – 40.6 – 42.9 –
ACr-S 14.3 61.4 19.7 66.5 22.2 71.5
AF-S 27.9 76.0 31.2 76.9 29.9 87.1
ATZ3-S 26.5 79.2 29.2 74.8 30.3 85.0
ATZ4-S 31.4 77.0 28.4 74.6 34.9 77.9

Table 3 research stations: 1) Lima, at the Corrosion and Protection Institute,

Zinc chromate based wash primer components. ICP-PUCP, an urban area near the sea; 2) Chimbote, in Nuevo Chimbote
district, a fishing town near the port; 3) Trujillo, in Buenos Aires dis-
Part A Part B
trict, characterized for having a high sea breeze, because of its proxi-
Component wt.% Component wt.% mity to the sea.
Isopropanol 57.6 Isopropanol 62.5
Ethanol 20.5 Water (maximum) 16.7
Water (maximum) 2.4 Phosphoric acid 20.8
Modified bentonite 0.3
2.5. Electrochemical tests
Polyvinyl butyral resin 8.6
Dispersing additive 0.3 Corrosion potential (Ecorr) was measured during a 24 h period with a
Zinc chromate 4.4 two electrode electrochemical cell, containing a silver chloride elec-
Iron oxide 1.6
trode (Ag/AgCl/KCl 3 M) as a reference and a working electrode
Titanium dioxide 3.3
Talc 1.0 (Section 2.1.3). NaCl 0.1 M solution was used as the conducting elec-
trolyte, with constant stirring. Control samples were obtained in the
same way with uncoated panels.
Table 4 Polarization resistance determinations (Rp) of coated panels with
Zinc chromate based alkyd paint components. wash primer formulations were obtained after 3, 6 and 24 h of im-
mersion. An electrochemical cell with three electrodes, a silver chloride
Component wt.% Component wt.%
electrode (Ag/AgCl/KCl 3 M) as a reference, a mild steel coated spe-
Turpentine 21.3 Iron oxide 18.8 cimen (Section 2.1.3) as the working electrode and a counter electrode
Toluene 6.7 Talc 8.0 of platinum plate of 0.8 × 0.8 cm was employed. Sweep amplitude
Alkyd soja resin 29.9 Zirconium octoate 0.7 of ± 25 mV was applied, starting from the corrosion potential at a scan
Modified bentonite 1.0 Cobalt octoate 0.4
Dispersing additive 0.1 Calcium octoate 0.5
rate of 1 mVs−1. The same electrolyte solution (NaCl 0.1 M) was used.
Antifoaming agent 0.4 Methyl ethyl ketone 0.3 Tests were carried out in duplicate.
Zinc chromate 11.9 Impedance measurements were carried out with a three-electrode
flat cell in a Faraday cage with a working electrode (coated steel;
16.9 cm2 of the exposed area), a stainless steel (SS 316) counter elec-
3000 DV Perkin-Elmer inductive coupled plasma optical emission trode and a Ag/AgCl/KCl 3 M reference electrode. All impedance
spectrometer (ICP-OES), following the EPA Method 200.7. spectra were performed in the potentiostatic mode at the corrosion
potential, in the frequency range of 100 kHz–0.1 Hz with an ac signal of
2.3. Accelerated tests on painted panels amplitude of 10 mV for different immersion time in 3% NaCl.
All electrochemical tests were carried out by using a potenciostat/
Mild steel panels coated with wash primers and alkyd paints were galvanostat AUTOLAB, model PGSTAT204. The data was analysed with
evaluated in accelerated corrosion tests. In all cases, the panels were the software NOVA 1.10. Methrom Autolab. B.V.
periodically observed, without removing the coating. Salt spray test and
Prohesion test was performed with a Q-FOG cyclic corrosion chamber,
model CCT600, as stated by standards ASTM B-117 and ASTM G85-A5, 2.6. Corrosion product analysis
respectively. Sulphur dioxide test was done with a VLM GmbH auto-
matic water condensation test chamber with manual gas dosing system, The composition of ATZ3 paint layer, after Prohesion test (2016 h),
model CON 300-FL AIR CWC AWFR. SO2 gas was generated in situ with was analysed with a scanning electron microscopy (SEM) FEI Quanta
analytical-grade sodium sulphite and an excess of sulfuric acid. 200 equipped with an energy dispersive X-ray (EDS) system for che-
The degree of rusting and the degree of blistering throughout time mical analysis. ACr sample was also evaluated for comparison purposes.
of the coated panels were qualified according to ASTM D610 and ASTM In addition, after Prohesion test (2016 h), black spots (TnFe ATZ3)
D714 standards, correspondingly. At the end of each test, the antic- were removed from the paint surface to examine its composition on
orrosive performance near the incision was evaluated in accordance Perkin–Elmer Spectrum100 FTIR spectrophotometer (KBr pellets). The
with ASTM D1654 standard. paint film without signs of corrosion or blisters (ATZ3), as well as iron
tannate synthesized with Tara powder (TnFe) and non-adherent rust
2.4. Natural exposure tests obtained from Prohesion humidity chamber treated with Tara extract
(FeOx + TT) were used to identify and compare principal bands in the
Panels coated with alkyd paints and alkyd paint systems were FTIR spectra.
placed on wooden racks with 45° tilt, looking north, according to ISO
8565 standard. Three locations in the Peruvian coast were chosen as

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A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

Table 5 performance were those pigmented with zinc chromate (WCr). This
Physicochemical characteristics of zinc tannates. primer showed a high degree of rusting only after 24 h of exposure (3G
degree) and a greater density of blistering at the end of the test (8D
Characteristic Zinc tannate
degree). Despite zinc chromate is a commercial pigment with effective
TZn3 TZn4 Analysis method anticorrosive properties and fairly used, the wide range of solubility of
commercial chromates, between < 0.01% and 0.1% [53], converts it
Oil absorption by Spatula Rub-Out 74.40 55.80 ASTM D281
into the pigment with the least efficiency against corrosion in moisture
Sieve residue, 45 μ (%) 24.90 0.00 ASTM D185A
pH aqueous extract, 25 °C 6.99 7.07 ISO 787/9 conditions.
Specific Gravity 2.93 2.89 ASTM D153 The wash primers prepared with zinc tannate TZn3 (WTZ3) ex-
Chlorides (Cl−), 25 °C (% m/m) < 0.01 < 0.01 ISO 787/8 – EPA 300.0 hibited a similar variation in the degree of oxidation to that shown by
Chlorides (Cl−), ≥100 °C (% m/m) 0.013 0.010 ISO 787/3 – EPA 300.0 the samples WCr during time of exposure, and an approximate density
Sulphates (SO42−), 25 °C (% m/m) < 0.01 < 0.01 ISO 787/8 – EPA 300.0
of blistering (8MD degree at the end of the test). Paints formulated with
Sulphates (SO42−), ≥100 °C (% m/ 0.03 0.028 ISO 787/3 – EPA 300.0
m) modified zinc phosphate (WF) and zinc tannate TZn4 (WTZ4) had the
Water solubility, 25 °C (% g/g) 2.83 2.72 ISO 787/8 best anticorrosive behaviour. However, WF samples exhibited the
Water solubility, ≥100 °C (% g/g) 4.88 4.53 ISO 787/3 lowest adherence near the incision area (No 3 °), after 672 h in the salt
Loss of ignition (% m/m) 49.7 38.6 ISO 6745/7
spray chamber.
Zinc content (% m/m) 38.60 47.13 ISO 6745/8 – EPA
200.7 The thin protective coating containing zinc tannate TZn4 showed
violet spots during the first 48 h of testing, corresponding to the for-
mation of iron tannates complexes. An interaction between parts of
3. Results and discussion polyphenols of tannins with iron oxides and oxyhydroxides takes places
in humidity conditions, preventing the spread of rust beneath the
3.1. Characterization of metal tannates coating. This phenomenon was also observed in the wash primers
WTZ3, but with less intensity. Comparing the behaviour of both tan-
The technical data sheet for each zinc tannate can be found in nates, it is presumed that the wash primer prepared with the pigment
Table 5. For comparative purposes we emphasize that TZn3 was pre- TZn4 presented a better performance, because of its slightly more al-
pared with a lesser quantity of the zinc source than TZn4. The Fourier kaline composition, as it has more quantity of the zinc source.
spectrums of zinc tannates and Tara powder are shown in Fig. 1. The Wash primers are used for the treatment of bare metal surfaces prior
conversion of tannins to zinc tannates was bear out according to the to painting to inhibit corrosion and increase paint adhesion [49], by
descriptions reported by Noor Idora [50] and Bellotti [51]. giving integrity to protective coating systems [48]. They are not in-
The peak at 1710 cm−1 decreased by the stretching of the carbonyl tended to be used as single isolated protective coatings, and they need
group and a clear expansion of the peak at 1610 cm−1 was satisfactorily to be recoated to achieve a good anticorrosive performance [54]. In
achieved because of the formation of ionized carboxyl groups in the order to understand the influence of a topcoat on corrosion behaviour, a
hydrolysis of ester linkages, ratifying the formation of a metal tannate. group of panels were painted with wash primers and top coats of
Tara powder (TT) had a broader intense band around commercial alkyd paints.
3400–3600 cm−1, attributed to stretching of the OH group [52], which Most systems with wash primers reached degrees of rusting between
might indicate the presence of a larger number of hydrogen bonds. On 4G-6G and developed medium to dense frequencies of blistering,
the other hand, tannate spectrums showed narrower bands, since the reaching in some cases No 6 sizes of blisters at the end of the exposure
OH groups interact to form metal complexes. period. Systems with wash primers pigmented with modified zinc
phosphate (WF-S) showed a slightly lower anticorrosive efficiency (4G
3.2. Accelerated tests degree), while WTZ3-S systems had the best performance against cor-
rosion (6G degree), in regards to rust development during exposure
3.2.1. Salt spray test time. Systems with wash primers formulated with zinc chromate (WCr-
Results obtained after 672 h in the salt spray cabinet test are ex- S) developed the smallest blisters (8D degree) and presented a higher
hibited in Table 6. The wash primers with the worst anticorrosive degree of adhesion (No 7°), compared to the other samples.
Alkyd zinc chromate primers (ACr) showed the highest degree of
blistering (2MD degree) due to the high solubility of the anticorrosive
pigment. These samples among with alkyd paints containing the mod-
ified zinc phosphate (AF) exhibited an aggressive oxidation process
throughout time. AF specimens presented the smallest blisters; how-
ever, they had the worst anticorrosive behaviour, achieving a high
degree of rusting (2G degree) at only 168 h of testing.
Alkyd primers with zinc tannates, TZn4 (ATZ4) and TZn3 (ATZ3),
showed similar characteristics, and a superior anticorrosive behaviour
to those observed in paints prepared with conventional pigments, due
to the formation of small black dots of iron tannates complexes, which
encapsulated the rust generated by breaking blisters. According to
Rahim and Kassim [35], these highly insoluble complexes formed on
the metal surface provide a barrier protection. The latter effect allowed
the paints prepared with zinc tannates to have similar adhesions near
the incision line (No 3–4°) as the ones formulated with conventional
pigments. Dark spots occupied at 48 h of testing only 1% of the surface
of the coated panels, but they incremented in 120 h in more than 50%.
ATZ3 samples presented the lower size of blisters (No 8°), compared to
the other samples.
Regarding systems with alkyd primers, those with modified zinc
Fig. 1. FTIR spectrum of zinc tannates and Tara powder.
phosphate pigment (AF-S) exhibited a lower degree of oxidation (9G

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A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

Table 6
Salt spray test: Rusting and blistering degrees. Degree of failure near the incision, 2016 h.

Sample Degree of Rusting Degree of Blistering Degree of failure near incision

24h 48h 96h 168h 672h 24h 48h 96h 168h 672h

WCr 3G 2G 1G 1G – < 8F 8MD 8D 8D – 4

WF 7G 4G 2G 1G – 10 10 10 8F – 3
WTZ3 5Gb 2Gb 1G 1G – < 8F 8M 8M 8MD – 4
WTZ4 6Gb 4Gb 2G 1G – < 8M < 8M 8M 8M – 4
WCr-S 10 10 10 10 5G 10 10 10 10 8D 7
WF-S 9P 8P 8G 8G 4G 10 < 8F 8F 8F 6M 3
WTZ3-S 9P 9P 9G 9G 6G 10 10 8F 8F 6M 4
WTZ4-S 10 9P 9G 8G 5G 10 10 8F 8F 6D 4
ACr 9P 8P 7P 6P 1G < 8F 8F 8M 6M 2MD 3
AF 10 8G 6G 2G 1G < 8F 8M 6M 6MD 6D 3
ATZ3 10 10a 9Ga 6Ga 1Ga 10 8F 8M 8MD 8D 4
ATZ4 10 10a 9Ga 7Ga 1Ga < 8F 8M 8MD 6MD 6D 3
ACr-S 10 10 10 9P 7G < 8M < 8M 8M 8MD 8MD 4
AF-S 10 10 10 10 9G 10 10 10 8F 8D 3
ATZ3-S 10 10 < 9G 8G 7G 10 10 10 8F 8MD 4
ATZ4-S < 9P 9P 9P 8G 7G 10 10 10 8F 8M 3

a
Black dots.
b
Violet spots.

degree), but a higher density of blistering (8D degree). Systems with
tannates and zinc chromate showed similar degrees of rusting and
blistering. Most systems had a degree of failure near incision between
No 3 and No 4.
3.2.2. Prohesion test
Results obtained after 2016 h in the Prohesion chamber test are
shown in Table 7. Within the group of specimens painted with wash
primers, those with the best performance were pigmented with zinc
chromate (WCr). They exhibited a lower tendency to oxidize, smaller
blisters (No 8 size) and a better adhesion to the metal substrate near the
incision area (No 6°). Both WTZ3 primers and paints formulated with
the commercial phosphate (WF) presented similar characteristics.
WTZ4 exhibited the worst anticorrosive performance.
With respect to wash primer systems, the WCr-S samples exhibited
the best anticorrosive behaviour. Systems with primers pigmented with
commercial phosphate (WF-S) and zinc tannates, TZn3 (WTZ3-S) and
TZn4 (WTZ4-S), showed a similar inhibitory capacity. Nevertheless, the
samples containing the modified zinc phosphate (WF-S) had a higher
frequency of blistering at the end of the test (4MD degree) and a lower
degree of adhesion near the incision area (No 2°).
Specimens with alkyd primers revealed interesting differences.
Primers with zinc chromate (ACr), as well as those with zinc tannate
TZn3 (ATZ3) presented big blisters. The blisters of the samples ATZ3
began to form in rusted areas. At the end of the test, rust became
widespread, but the areas that had black spots, characteristic of the
formation of iron tannate complexes, were not affected.
As for the degree of rusting, panels painted with alkyd primers with
commercial zinc phosphate (AF) achieved an optimal anticorrosive
protection, very similar to the one achieved by ATZ4 primers. ATZ4
specimens presented black spots of iron tannate complexes, which
backward the oxidation process. These spots appeared after a week of
evaluation and increased until they occupied about 10% of the surface
of the coated panel. ACr samples had the worst anticorrosive properties,
by having a significant increase of the amount of rust through time. In
this test, paints ATZ3 did not show an appropriate behaviour. It is
presumed that ATZ4 primers, containing a slight excess of ZnO (alkaline
compound), counteracted the acidity of the medium (pH 5.0-5.4, ASTM
G85-A5).
Panels with systems with alkyd primers presented almost no da-
mage. Only systems with paints pigmented with zinc chromate (ACr-S)
developed small blisters with a limited distribution (8F degree) and an

Table 7
Prohesion test: rusting and blistering degrees. Degree of failure near the incision, 2016 h.

Sample Degree of Rusting Degree of Blistering Degree of failure near incision

24h 48h 168h 840h 1512h 2016h 24h 48h 168h 840h 1512h 2016h

WCr 6G 4G 1G – – – 10 10 8D – – – 6
WF 4G 1G 1G – – – 10 10 6MD – – – 4
WTZ3 5G 1G 1G – – – 10 8F 6M – – – 3
WTZ4 2G 1G 1G – – – 10 8M 6D – – – 4
WCr-S 10 10 10 10 9P 9P 10 10 10 < 8F < 8F < 8F 6
WF-S 8P 8P 6P 5G 5G 5G 10 10 10 6M 4MD 4MD 2
WTZ3-S 9P 8P 8P 7G 5G 5G 10 10 10 6F 4M 4M 4
WTZ4-S 9P 8P 7P 7G 6G 6G 10 10 10 6F 4M 4M 3
ACr 10 9P 9P 7P 6P 5P < 8F < 8F < 8F 8F 4F 4F 5
AF 10 10 10 10 10 10 < 8F 8F 8F 8M 8M 8M 4
ATZ3 10 10 10 1G 1G 1G 10 10 10 8MDb 2D 2D 5
ATZ4 10 10 10a 8Ga 8Ga 8Ga 10 10 10 8D 8D 8D 9
ACr-S 10 10 10 10 9P 7P 10 10 10 10 8F 8F 8
AF-S 10 10 10 10 < 9P 9P 10 10 10 10 10 < 8F 6
ATZ3-S 10 10 10 10 < 9P < 9P 10 10 10 10 10 10 10
ATZ4-S 10 10 10 10 10 < 9P 10 10 10 10 10 < 8F 9

a
Black dots.
b
Blistering in rusted area.

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A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

Fig. 2. Scraped area near the incision line of panels coated with alkyd
primers (left) and systems with alkyd primers (right), after Prohesion test
(2016 h).

intermediate degree of oxidation (7P degree). Other paints showed ef-
fective anticorrosive properties. Systems containing zinc tannates de-
monstrated to have an optimum adhesion, because after scratching the
incision line (ASTM D1654-05), only a fraction of the coating was re-
moved, obtaining the lowest degree of failure near the incision (No
9–10°) in comparison with systems with conventional pigments
(Fig. 2.).
Both systems with alkyd primers and alkyd paints prepared with
zinc tannates showed the best adhesion after the final evaluation.
During the inspection, the incision lines of the samples pigmented with
tannates did not exhibit the formation of protuberant corrosion pro-
ducts. Zinc tannates bring to the film an ideal adhesion, probably due to
the formation of iron tannate complexes.
3.2.3. Sulphur dioxide test
Results acquired after 1176 h in the sulphur dioxide chamber test
are presented in Table 8. In this test, only alkyd primers and paint
systems with alkyd primers were studied. The alkyd paints prepared
with zinc chromate (ACr) began to oxidize and form blisters from the
first week of testing, ending with an intermediate degree of rusting (7G
degree) and the worst degree of blistering (6D degree). Samples con-
taining the modified zinc phosphate gave to mild steel a good protective
efficiency (8G degree). For this last case, small blisters (8F degree)
started to form before 48 h of exposure in an acidic media.
The alkyd primer with tannate TZn3 (ATZ3) decreased its antic-
orrosive behaviour during the last weeks of evaluation, achieving the
lowest degree of rusting (6G degree). On the other hand, coated panels
with ATZ4 primers had the best anticorrosive performance, because of
the presence of few black spots, iron tannate complexes, in the last
weeks of the test. The visual inspection performed after the paint films
were removed near the incision line showed that those alkyd primers
pigmented with the modified zinc phosphate (AF) and zinc tannates
(ATZ3 and ATZ4) had the best adhesion.
The paint system with the modified zinc phosphate (AF-S) had a
good performance in the sulphur dioxide cabinet, as it showed few signs
of corrosion. Despite being a fairly used commercial inhibitor, zinc
chromate did not provide an efficient anticorrosive protection to the
paint system, having ACr-S panels approximately 10% of rust in its
surface (4G degree) and big blisters with a significant frequency (6MD
degree) at the end of the test.
ATZ3-S and ACr-S systems exhibited an analogous oxidation process
during the first 504 h (3 weeks) in the SO2 salt chamber. However,
weeks later, the formation of iron tannate complexes in the samples
containing zinc tannate diminished the amount of visible rust on the
surface. This phenomenon was contemplated during the final evalua-
tion, where some areas on the surface of coated panels presented violet
strains. This last observation was also noticed in ATZ4-S specimens.
Altogether, zinc tannates bring to alkyd paint systems a good corrosion
inhibition, being the most efficient in an acidic medium the tannate
TZn4. The anticorrosive behaviour of ATZ4-S systems could be com-
pared to that shown by AF-S systems. In general, all systems inferred an
excellent adhesion near the incision area.
3.3. Natural exposure test
Results obtained in the three research stations of natural exposure
tests of coated panels with alkyd primers and systems are shown in
Table 9. The corrosion rate of steel, as penetration per year, and cor-
rosivity categories of each research station are shown in Table 10.
Samples from Lima exhibited lower levels of oxidation through
time, because of the mild corrosivity of the environment (C3 category).
Only after 9 months, in some cases, significant changes were observed
on the panel’s surface.
Among alkyd primers, no significant differences were noticed
during the first 6 months of exposure. The presence of black dots, due to
the formation of zinc tannate complexes, is the principal reason why

Table 8
Sulphur test: rusting and blistering degrees. Degree of failure near the incision, 1176 h.

Sample Degree of Rusting Degree of Blistering Degree of failure near incision

24h 48h 168h 504h 840h 1176h 24h 48h 168h 50h 840h 1176h

ACr 9P 9G 8G 7G 7G 7G < 8F 8F 8M 8MD 6MD 6D 7

AF 10 10 10 10 9G 8G 10 < 8F < 8F 8F 8F 8F 9
ATZ3 10 10 10 10 9G 6G 10 10 10 10 < 8F 8F 9
ATZ4 10 10 10 10 < 9Ga 9Ga 10 10 10 10 10 8F 8
ACr-S 10 10 9P 7P 6G 4G 10 < 8F 8F 8MD 8MD 6MD 9
AF-S 10 10 10 < 9P 9P 8G 10 10 10 10 10 8F 9
ATZ3-S 10 10 < 9P 7P 6Pb 5Pb 10 10 10 10 8F 8F 10
ATZ4-S 10 10 10 9P 8P 7Pb 10 10 10 < 8F 8F 8F 9

a
Black spots.
b
Violet stains.

40
A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

Table 9
Natural exposure tests: rusting and blistering degrees. Degree of failure near the incision, 9 months.

Samples Lima Chimbote Trujillo Degree of failure near incision

4m 6m 9m 4m 6m 9m 4m 6m 9m Lima Chimbote Trujillo

Degree of Rusting
ACr 10 10 8G 7G 4G 3G 7G 4G – 6d 5 7
AF 9G 8G 7G 4G 1G 1G 5G 1G – 6d 6 7
ATZ3 10 9Pa 3G 7Ga 1Gb 1G 8Ga 1G – 5d 9 10
ATZ4 10 8Pa 3G 6Ga 1Gb 1G 6Ga 1G – 10d 5 10
ACr-S 9G 7G 6G 10 8G 4G 8G 4G 1G 5d 6 4
AF-S 10 9G 8G 10 9G 7G 8G 5G 4G 4d 6 4
ATZ3-S 10 10 10 9G 7G 6G 8G 5G 4G 8d 5 6
ATZ4-S 10 9G 9G 9G 7G 5G 7G 5G 4G 8d 6 5

Degree of Blistering
ACr 8F 8F 8F 8F 6F 6M 6F 6Mc –
AF 8F 8F 8M 10 8M 6MD 8M 6D –
ATZ3 10 8F 8Fb 10 8M 6D 8MD 6D –
ATZ4 10 8M 8M 10 8F 6M 8M 6D –
ACr-S 10 8F 8F 10 6F 6F 10 6M 6Mc
AF-S 10 8F 8F 10 6F 6F 10 6M 6M
ATZ3-S 10 10 10 10 6F 6F 10 8M 6M
ATZ4-S 10 10 10 10 8F 6F 10 6M 6M

a
Black dots.
b
Dark rust.
c
Blisters located in rusted areas.
d
Analyzed 12 months after being exposed.

Table 10
Corrosion rate of steel as penetration per year and corrosivity categories of testing sta-
tions.
Station Corrosion rate (μm/year)
Lima 36.92
Chimbote 83.70
Trujillo 551.77
primers ATZ3 and ATZ4 gave to mild steel a good anticorrosive beha-
viour. However, after 9 months, these paints pigmented with zinc
tannates did not show the expected corrosion resistance, as a higher
amount of rust was visually detected (3G degree) on their surface. In
respect to blistering, in general, all samples contained small size blis-
ters.
This last tendency was reversed in the case of primers with a syn-
thetic top coat, because paint systems having zinc tannates offered the
best anticorrosive protection, even without producing blisters through
testing time. Systems with the modified zinc phosphate (AF-S) pre-
sented small blisters (8F degree) and a few signs of corrosion (8G de-
gree). Instead, systems containing zinc chromate primers (ACr-S) had
the worst anticorrosive behaviour, obtaining an intermediate grade of
rusting (6G degree) at the end of the test.
In Chimbote (C5 category), in the same way as in Lima, alkyd pri-
mers prepared with zinc chromate showed the best anticorrosive per-
formance. This was notably observed after 6 months of testing, where
the other paints had more than 50% of their surface oxidized, while
samples ACr only 10%. The inhibitory efficiency of AF primers against
corrosion was poor in comparison with paints containing zinc tannates.
It is worth noting that after 4 months of testing, ATZ3 and ATZ4 primers
provided a better inhibitory effect on mild steel due to the complexa-
tion of tannins with the iron from the metal substrate. Black dots oc-
cupied approximately 40% of the surface of painted panels in 4 months.
Two months later, paints containing tannates reached the worst degree
of rusting as AF samples; however, the formed rust was notably darker.
At the end of the test, all alkyd primers exhibited big blisters with
size No 6 and high blistering frequencies, being the ATZ3 paint the one
that developed more blisters. Nevertheless, this last alkyd primer re-
vealed an outstanding adhesion (No 9 °), as only paint traces were
removed near the incision line. Other samples showed an inferior an-
ticorrosive performance near the incision, achieving intermediate de-
grees of failure (No 5–6°).
Category
Besides having the best anticorrosive performance as primers,
without a top protective coat, paint systems containing zinc chromate
C3 (ACr-S) exhibited the greatest tendency to oxidize. On the other hand,
C5 the anticorrosive protection provided by the modified zinc phosphate
> C5
systems (AF-S) was highly effective. Systems with zinc tannates were
not far behind, since they presented intermediate degrees of rusting,
being ATZ3-S the system with a similar protective efficiency to that
reported for AF-S coatings.
All panels with alkyd systems showed the same tendency to form
blisters, with the exception of ATZ4-S samples, which had smaller
blisters after 6 months of testing. Moreover, at the end of the test, all the
paint systems presented a similar paint detachment near the incision
line.
In Trujillo, all alkyd primers suffered an accelerated corrosion
process, because of the aggressiveness of the environment (> C5 cate-
gory). For this reason, the evaluation lasted only 6 months. As in all
previous cases, alkyd primers containing zinc chromate (ACr) had the
best anticorrosive behaviour. Meanwhile, paints with zinc tannate
started competing with those with zinc chromate, but ended with the
same degree of rusting and blistering as AF samples. The formation of
black dots (3–10%) extended the lifetime of ATZ3 and ATZ4 coatings
during the first 4 months. Notwithstanding, paints with zinc tannates
exhibited an optimum adhesion, as no detachment of the film was ob-
served after the corresponding evaluation near the incision line. Paints
containing conventional pigments had between 1 and 2 millimetres of
loss of paint after completing the scraping near the incision (No 7°).
All alkyd systems developed a similar corrosion protection, ex-
cepting ACr-S panels, which had the lowest efficiency. Samples devel-
oped the same final degree of blistering. Near the incision line of all
coated panels, blisters were formed, increasing the degree of failure.
However, the paint systems pigmented with zinc tannate kept the best
anticorrosive behaviour.
Broadly, alkyd primers formulated with zinc chromate had the best
results; however, zinc tannates caused a significant improvement in the
adhesion of the paint with mild steel, and behaved in a similar way as a
second generation zinc phosphate. In alkyd systems, zinc chromate did

41
A. Hadzich et al. Progress in Organic Coatings 117 (2018) 35–46

because its corrosion potential turned into more positive values with
respect to the control sample [55]. Wash primers WTZ4 and WF ex-
hibited a similar performance, being the one containing the second
generation zinc phosphate, the sample with the closest value to the
control sample.
Results from polarization resistance tests are presented in Table 11.
The ratio Rp(Sample)/Rp(Control) was estimated with the polarization re-
sistance value obtained after 24 h of immersion in NaCl 0.1 M solution.
Wash primers prepared with zinc chromate (WCr) had the highest ratio
Rp(Sample)/Rp(Control), which indicates that is giving to the substrate an
outstanding protection [3]. WTZ4 coating also showed to have a good
anticorrosive behaviour as it achieved a ratio of more than 7 [3]. WF
and WTZ3 presented the lowest polarization resistances, but their va-
lues remained close to the one reported for WTZ4.
The EIS Bode diagrams (Fig. 4) of WF, WTZ3 and WTZ4 showed, at
low frequencies, the presence of a plateau in the modulus of impedance,
Fig. 3. Time dependence of Ecorr of coated steel with wash primers formulations in NaCl that could be attributed to the value of the charge transfer resistance
0.1 M for 24 h.
associated to a corrosion process [56], and at higher frequencies, very
low phase angles, close to −30°, which might indicate a resistive re-
Table 11 sponse [57]. This response is due to the fact that after 3 h of immersion
Polarization resistance determinations of coated steel panels, after being immerse in NaCl in a 3% NaCl solution, the corrosion potential of these wash primers
0.1 M solution, for different periods of time.
reached the substrate corrosion potential (Ecorr = −550 to −645 mV)
Sample Polarization resistance (KΩ cm−2) Rp
(Fig. 4).
(sample)/Rp(Control)
Otherwise, WCr exhibited a more positive corrosion potential at the
3h 6h 24 h beginning of the test (Fig. 4); however, it decreased through immersion
Control 0.5 ± 0.1 0.36 ± 0.01 0.34 ± 0.01 time, after reaching the steel corrosion potential (Fig. 5). EIS Bode
WCr 29.9 ± 1.9 19.0 ± 3.0 14.0 ± 1.0 41.18
diagrams (Fig. 5) showed that during the first 3 h, WCr had a general
WF 1.5 ± 0.3 1.6 ± 0.2 1.7 ± 0.1 5.00 capacitive behaviour (phase angle near −90° and a straight line), in-
WTZ3 4.0 ± 1.0 3.5 ± 0.9 2.0 ± 0.3 5.88 dicating that the primer was in good condition. Nevertheless, at low
WTZ4 6.2 ± 0.6 5.3 ± 0.1 2.5 ± 0.1 7.35 frequencies, it was observed that the phase angle started to decrease, an
indicative of the presence of conductive pathways that allows water and
other active species to penetrate the film [58] and consequently, begin
not provide the same positive effect against corrosion. The trend was
with the corrosion process.
reversed and zinc tannates yield a better protective capacity than
WCr showed a decreasing behaviour of phase angle (Fig. 5b), at-
samples with modified zinc phosphate in environments with medium
tributed to the partial solubility of zinc chromate in water [59], which
corrosivity, as Lima station (C3 category); and provided a similar be-
facilitated the leaching of the pigment from coating. The EIS spectra
haviour in aggressive corrosive surroundings, as Trujillo's coast.
(Nyquist forms) of WCr, after 48 h of immersion (Fig. 6), showed the
Apparently, the formation of iron tannate complexes was favoured in
presence of a loop at high frequencies with an oxygen diffusion tail (at
no severe environmental conditions, extending the lifetime of the
low frequencies), which indicated the loss of anticorrosion properties of
coating or improving the adhesion of the paint.
the paint [57]. This trend validated the results obtained after polar-
ization resistance measurements, where it was established that the
3.4. Electrochemical tests primer pigmented with zinc chromate gave better anticorrosive pro-
tection, while those containing zinc tannates and modified zinc phos-
The variation in time of corrosion potential measurements of coated phate maintained a similar behaviour.
mild steel panels in NaCl 0.1 M solution is illustrated in Fig. 3. Wash
primers WCr and WTZ3, pigmented with zinc chromate and tannate
TZn3 respectively, provided the best protection against corrosion,

Fig. 4. EIS diagrams for coated steel with WP, obtained after 3 h of ex-
posure in a 3% NaCl solution. a) Bode-magnitude plots; b) Bode-phase
plots.

42
A. Hadzich et al.
Fig. 6. Nyquist diagram for coated steel with WCr immersed in a 3% NaCl solution after
48 h of exposure.
Fig. 7. FTIR spectrum of corrosion product and comparison compounds. TnFe ATZ3:
Black spots; ATZ3: alkyd paint; FeOx + TT: transformed rust with tannin extract; TnFe:
Ferric tannate.
3.5. Corrosion product analysis
3.5.1. FTIR analysis
The FTIR spectra of the black spots from ATZ3 and comparison
compounds are illustrated in Fig. 7. TnFe ATZ3 sample exhibited two
broad adsorption bands between 3600 and 3000 cm−1, which represent
the presence of phenolic hydroxyl groups [60]. These peculiar bands
were also found in the FTIR profile of the synthesized iron tannate
43
Progress in Organic Coatings 117 (2018) 35–46
Fig. 5. EIS diagrams for coated steel with WCr immersed in a 3% NaCl
solution, obtained at different exposure times. a) Bode-magnitude plots; b)
Bode-phase plots.
(TnFe) and transformed rust with tannin extracts (FeOx + TT).
Characteristic peaks of alkyd resins were notably observed in the
FTIR spectra of the ATZ3 paint and TnFe ATZ3 sample, as expected.
Peaks at 2851.45–2927.54 cm−1 indicate CH2 symmetric and asym-
metric stretching vibrations respectively, the peak for C]O appears at
1730.71 cm−1, and the peak at 1266.9 cm−1, correspond to CeOeC
stretching vibrations attached with aliphatic and aromatic moiety [45].
A very pronounced peak at 1402.97 cm−1 was identified in the TnFe
ATZ3 and TnFe samples. This peak is associated with the adsorption of
a CeO vibration of benzoic acid, phenomenon that explains the coex-
istence of Fe3+ and Fe2+ in ferric tannates [60]. Typical bands from
lepidocrocite (1020–1124 cm−1) and goethite (796–885 cm−1) were
distinguished in the FTIR spectra of rust (obtained in humidity
chamber) treated with Tara tannin (FeOx TT), as indicated in our
previous work [41]. Among all the spectra, FeOx TT profile is the most
similar to that of the problem sample (TnFe ATZ3). This last assumption
indicates that the black spots would be iron tannates formed from rust
and tannins, compounds possibly released by the partial solubility of
zinc tannates.
3.5.2. SEM-EDS analysis
SEM micrographs of the ATZ3 paint layer, after Prohesion test
(2016 h), are shown in Fig. 8. Two characteristic areas of the surface
were analysed: 1) black spots; 2) not affected area. Surface elemental
analysis revealed that black spots (1 – zone A) are mainly constituted by
dark and grey regions composed of iron (78–86 wt percent), carbon
(4–13 wt percent), oxygen (2–4 wt percent), and zinc (4–12 wt per-
cent). The few white zones (1 – zone B) revealed the presence of iron
oxides, since more quantity of oxygen and iron were observed, in
stoichiometric proportions, and a negligible amount of zinc (less than 2
wt percent).
The area that did not have black spots showed the presence of
blistering, oval protrusions, and corrosion products, white agglomer-
ates (2 – zone A) that contained predominant similar amounts of iron
(38–42 wt percent) and oxygen (40-48 wt percent). The intact protec-
tive coating is composed of carbon (37 wt percent), oxygen (32 wt
percent), iron (20 wt percent), and zinc (5 wt percent), which makes us
presume that a black by-product has been formed in the paint surface,
reducing the presence of rust.
ACr paint layer, after Prohesion test (2016 h), was also examined for
comparison purposes (Fig. 9). Blisters developed on almost the entire
surface. Much of the surface contained white parts (1 – zone A), dis-
tinctive for having high percentages of oxygen (54–55 wt percent) and
iron (20–25 wt percent), typical composition of rust. Small amounts of
sulphur (3–8 wt percent), from chamber conditions, and chromium
(less than 1 wt percent) were also identified. It is necessary to em-
phasize that the presence of chromium in the surface is dangerous, due
A. Hadzich et al.
Fig. 8. SEM micrographs of ATZ3 paint layer, after Prohesion test (2016 h). General view of the test section protected with ATZ3 paint (left); micrograph of the area with black spots
(800X) showing two zones of analysis (zones A and B) (centre); micrograph of non-affected surface (800X) showing one characteristic zone of analysis (zone A) (right).
to its high toxicity and carcinogenic properties [14–16]. In the dark
zones (1–zone B), the percentage of chromium is lower (less than 0.5 wt
percent), and the presence of carbon and oxygen is higher than the
amount of iron, as in the ATZ3 case.
4. Conclusion
Efficient anticorrosive wash primers and alkyd paints were for-
mulated satisfactorily with new green corrosion inhibitors: zinc tan-
nates containing Tara tannins and conventional pigments for com-
parative purposes. All tests indicated, in general, that wash primers,
alone and as a part of a paint system, prepared with zinc tannates had a
similar anticorrosive behaviour with those primers containing a second
generation zinc phosphate. Wash primer with zinc chromate exhibited
the best inhibitory corrosion capacity and a superior adhesion with the
substrate.
Regarding alkyd primers, zinc tannates provided a similar antic-
orrosive protection in comparison with conventional pigments, often
surpassing its anticorrosive action. In natural environments, the antic-
orrosive behaviour of primers with zinc chromate was not overcome. As
part of paint system, alkyd primers with zinc tannates among with
phosphate paints presented the best inhibitory properties, and the
tendency observed in alkyd primers in natural exposure tests was sa-
tisfactorily reversed. Alkyd primers and systems prepared with zinc
tannates had an outstanding adhesion in contrast with formulations
containing commercial pigments.
44
Progress in Organic Coatings 117 (2018) 35–46
Fig. 9. SEM micrographs of ACr paint layer, after
Prohesion test (2016 h). General view of the test
section protected with ACr paint (left); micrograph
of the surface (800X) showing two zones of analysis
(zones A and B) (right).
A sub-reaction involving the formation of iron tannate complexes is
the protection mechanism responsible for inhibiting rust proliferation
in paints pigmented with zinc tannates. This process is presumed to be
favoured in environments with a lower corrosivity category and when
the primer containing the zinc tannate is part of a paint system. This last
assumption is based on the fact that the moderate anticorrosive beha-
viour of primers containing zinc tannates is reversed and experienced
an outstanding performance when they are used in a paint system. For
all these reasons, zinc tannates could be considered as appropriate
pigments for replacing chromate or modified zinc phosphates, with the
advantage of obtaining a better adhesion, and by contributing to health
and environmental world-wide concerns.
Acknowledgements
This research was supported by FINCyT (Fondo para la Innovación,
la Ciencia y la Tecnología), [grant No 158-FINCyT-IA-2013], and
agreement PUCP (Pontificia Universidad Católica del Perú) –
FONDECYT (Fondo Nacional de Desarrollo Científico y Tecnológico)
[grant No 012-2013]. The authors would particularly like to thank
PUCP Chemistry Section for the FTIR analysis, PUCP Material
Characterization Centre for the SEM-EDS analysis, and the UNIVERSAL
COLORS Company for the supply of materials and commercial coatings,
and for the painted service. We also thank to Dr. Pablo Aguilar,
Professor at the National University of Trujillo (Peru), for providing
information about the environmental conditions of Chimbote research
A. Hadzich et al.
station.
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