Nano iron oxide dispersed alkyd coating as an efficient anticorrosive coating for

industrial structures
⁎
K. Jeyasubramanian , V.S. Benitha, V. Parkavi
Centre for Nano science and Technology, Mepco Schlenk Engineering College, Sivakasi, 626 005, Tamilnadu, India

ARTICLEINFO ABSTRACT
Keywords: This report describes the preparation and characterization of nano iron oxide impregnated alkyd coating (NIAC) displaying
Iron oxide nanoparticles excellent anticorrosive ability. Fe2O3 nanoparticles prepared via gel combustion method were used as pigments and dispersed
Alkyd paint in alkyd resin using high-energy ball milling method. The physical properties such as spreading ability, solid content, glossiness
A36 steel and wetting abilities were evaluated by following standard protocols. The corrosion inhibition property of NIAC was studied
Corrosion inhibition by weight loss method, potentio-dynamic polarization and electrochemical impedance spectroscopy techniques in 3.5% NaCl
solution. The quantity of iron content leached into the corrosive medium was assessed using inductively coupled plasma
spectrometer. It was revealed that the dissolution of iron from steel was prevented by NIAC coating. Further, the corrosion
inhibition nature of the coating was proved from potentiodynamic polarization and impedence spectroscopic techniques.

1. Introduction E-mail address: kjeya@mepcoeng.ac.in (K. Jeyasubramanian).

https://doi.org/10.1016/j.porgcoat.2019.03.023
In recent times, nanosized materials have been used in the development of
commercial products owing to their multifunctional characteristics in contrast
an efficient coating, and also successfully protect the underlying metal from
to the bulk materials [1]. One of the thrust areas amidst the use of nanoparticles
corrosion and other environmental hazards. Recently, Balanand et al. [14]
in a wide range of applications, is the prevention and protection of metallic
prepared ZnO based paint and described the NIR light shielding applications.
corrosion. Numerous researchers have been working in this field, since
TiO2 based paint has been prepared and studied for the clean environment owing
corrosion is a universal problem. Nearly 4% of the annual GDP is spent all over
to its photo-catalytic activity [15]. Karthikeyan et al. [16] studied the use of
the world for mitigating the corrosion of metallic structures employing anti-
graphene sheets as electrically conductive pigment in alkyd resin matrix and
corrosion coating technology [2]. One of the simplest corrosion protecting
reported its remarkable characteristics. Spherical ZnO nano particles in least
methods adopted by the human community is by applying paint coating over
amount (0.5%) as pigment in the alkyd resin, isolated from sunflower oil in a
the metallic structure which is being exposed to open atmosphere such as air or
polyesterification approach display superior durability, anti-corrosion ability,
water [3,4]. Of course, paint is a viscous suspension consisting of a variety of
materials, on coating over any substrate results in the formation of etc [17,18]. Silver, silver vanadate, CuO and V2O5 in nanoform are dispersed in
macromolecular films on the surfaces, where they were applied [5]. Dry paint and their antibacterial activities are examined [6,19–21]. Earlier, the use
of graphene oxide based paint for corrosion resistant applications under acidic
pigmented film exhibits pleasing colour and possesses protecting ability against
and marine environments had been reported. Most of the paint works reported
dry/wet harsh environment, thus safeguarding the metal from the corrosion.
in the literature have focused on the photo-catalytic and antibacterial
Traditionally, paint-makers employ the utilization of different varieties of
applications [22]. Banvase et al. [23] also discussed the use of calcium, zinc
micron sized metallic particles, metal oxides, etc.,as pigments with varieties of
phosphate nanoparticles towards corrosion resistant coating. However, use of
additives [6,7]. However, utilization of nano particles for developing an
nontoxic, nano Fe2O3 particles dispersed in alkyd resin as paint has not been
efficient coating is a fascinating trend, for which numerous records are available
reported so far.
[8–13]. In combination with polymer chemistry, nano particles-dispersed paint
Evidently, iron oxide (Fe2O3) nanoparticles are known for their applications
coating may provide
in catalysis, gas sensors, solar energy harvesting, magnetic properties and also
in biomedicine [24–26]. Another noteworthy feature of nano Fe2O3 is that, while
using this as a pigment for making paints, it provides a pleasing reddish brown
⁎ Corresponding
colour. Based on all the
author.

Received 10 November 2018; Received in revised form 18 January 2019; Accepted 11 March 2019 Available online 21
March 2019
K. Jeyasubramanian, et al. Progress in Organic Coatings 132 (2019) 76–85

0300-9440/ © 2019 Elsevier B.V. All rights reserved.

Fig. 1. Fe2O3 nanoparticles (a) X-ray diffraction pattern (b) FESEM (Inset figure: Histogram of particle size distribution).
positive feedbacks of nano Fe2O3, this work has aimed at preparing nano iron
oxide particles dispersed in alkyd resin employing high energy ball-milling
technique. The chemical and the structural analysis of the prepared paint have
been examined by spectroscopic studies and the anti-corrosive properties have
been interpreted based on the results gathered from acid immersion test, linear
polarization analysis and electrochemical impedance analysis. The results
obtained from this study are more encouraging due to the uniform distribution
of nano iron oxide particles existing in the alkyd resin matrix and in future, the
NIAC paint can be used as a multifunctional paint.
2. Materials and methods
2.1. Materials
Iron nitrate nanohydrate, citric acid, and ammonia are obtained from Merck
Chemicals Ltd., India. The additives used in the preparation of Fe2O3 nanopaint
are Linseed alkyd resin (Sunny Paints and Tar Products, India), Thickener A
(Vigneshwara Paints Ltd, India), Soya lecithin (Shreenidhi Oils and Foods
Ingredients Pvt. Ltd., India), Toluene (Merck Chemicals Ltd., India),
aluminium stearate and Cobaltnaphthenate (Sigma Aldrich, India) purchased
from the reputed suppliers. The zinc oxide nanoparticles (ZnO) and zirconia
nanoparticles used in this study are synthesized using reported literature
[27,28]. The Fe2O3 nanoparticles used as pigment are synthesized by gel
combustion method (S1) [26].
2.2. Preparation of nano Fe2O3 based alkyd paint
Fe2O3 nano particles prepared through gel combustion method followed by
calcination at 700 °C in bulk amount is used as a pigment for making alkyd
paint by high energy ball-milling technique.Various compounds namely, Fe2O3
nanoparticles 20 wt.% (pigment), alkyd resin 60 wt.% (binder), cobalt
naphthenate 0.6 wt.% (outer coat drier), nanosized ZrO 2 0.6 wt.% (inner coat
drier), nano sized ZnO 0.2 wt.% (stabilizer), Thickener A 0.2 wt.%, aluminium
stearate 0.8 wt.% (antisettling agent) and soya lecithin 0.6 wt.% (wetting agent)
are used to formulate the paint. These compounds are milled for a period of 6 h
in a tungsten carbide bowl with tungsten carbide balls (ball to powder ratio,
10:1) at a speed of 300 rpm. Subsequently, the thinner 17 wt.% (Mineral
Turpentine Oil) is added to maintain the consistency of paint. Finally, reddish
brown colored Fe2O3 particles-dispersed paint is obtained, which can be used to
coat on substrates like glass, mild steel, structural elements, wood surface, etc.
2.3. Instrumentation
The crystal structure and orientation of the nanoparticles are determined by
Rigaku X-ray diffractometer (XRD) operated at 40 KeV and 40 mA with Cu
Kα radiation in the range of 0°−80°. The Fourier Transform Infrared
Spectroscopy studies (FTIR) are done using Bruker Optics, Germany to ensure
the chemical identity of nanoparticles and the paint film, with an average of 24
scans. The surface topography of the nanoparticles and the paint coatings are
characterized through an AFM instrument (XE70 Park Systems, South Korea)
at ambient conditions, using non-contact mode probe at a scan rate of 0.5 Hz.
The nanoparticle morphology is recorded using FESEM-Carl Zeiss
MA15/EVO 18 electron microscope. Surface morphology and particle size
evaluation are performed using TEM-FEI Tecnai G2 300 kV microscope. The
gloss measurement of the painted film is carried out using a Rajdhani digital
gloss meter RSPT-200 model, India. The water contact angle measurement is
performed using Data physics Instruments, Germany with a dosing volume of
5 μL at a dosing rate of 1 μL/s. Corrosion resistant nature of the coating is
assessed by Electrochemical Workstation CHI600 series, CH Instruments,
USA. Leaching Studies are perfromed using inductively coupled plasma-optical
emission spectrometer ICPOES, Perkin Elmer, US.
3. Results and discussion
3.1. Pigment characterisation
Fig. 1(a) shows the X-ray diffraction pattern of Fe2O3 nanoparticle
synthesized by gel-combustion techniques. The diffraction peaks found at 2θ
=24.35°, 33.04°, 35.51°, 40.78°, 49.38°, 53.907°, 57.99°, 62.37°, 63.92°,
71.96°, and 75.32° are attributable to the planes corresponding to Miller indices
(012), (104), (110), (113), (024), (116), (122), (214), (300), (1010), and (217)
respectively [29,30]. As per the JCPDS standard 87–1164, the interplanar
spacing supports the formation of rhombohedral α-Fe2O3 crystal geometry.
Absence of peaks other than the characteristic α-Fe2O3 suggests its purity. The
average crystallite size of the Fe2O3 nanoparticle is calculated using Debye
Scherrer equation
D = 0. 9λ/βcosθ (1)
where, D is the crystallite size, λ is the wavelength of X-rays used (CuKα), β is
the broadening of diffraction line measured at half of its maximum intensity in
radians and θ is the angle of diffraction. From the obtained parameters, the
crystallite size of the Fe2O3 nanoparticles is calculated as 21 nm.
The FESEM micrograph of iron oxide nanoparticles is shown in Fig. 1(b).
From the SEM image, it is clear that the particles are in agglomerated state,
individually the sizes of particles are evaluated using the ImageJ software as 23
nm (inset figure).

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Fig. 2. FTIR spectra of alkyd resin and NIAC.
3.2. Physical characteristics of NIAC
3.2.1. FTIR analysis of alkyd resin and NIAC
The FTIR spectra shown in Fig. 2 highlight the vibrational modes of various
types of constituents present in the alkyd resin and the dried coating. The FTIR
spectrum of bare alkyd resin shows the characteristic bands attributed to in-
plane vibrations at 1062 cm−1 and out of plane bending vibrations of unsaturated
phenolic ring at 713 and 747 cm−1. The in-plane vibrations of CeH are found at
1120 cm−1, CeOeC groups at 1255 cm−1, a pyrrole ring at 1452 cm−1 and 1585
cm−1, carboxylic group at 1725 cm−1, the aliphatic stretch at 2924 cm−1, aliphatic
vibration at 2856 cm−1 and the vibration of hydroxyl peak are seen around 3507
cm−1 [31]. All these characteristic vibrations of alkyd resin are also observed in
nano iron oxide dispersed alkyd coating with some additional bands
corresponding to Fe-O vibrations in the lower wave number region (500-600
cm−1) [26]. These data support the fact that Fe2O3 nanoparticles are strongly
bound and uniformly distributed along with the alkyd resin matrix.
3.2.2. Gloss measurements
Glossiness is one of the important characteristics of paint which provides
an aesthetic and decorative appearance to the paint. The glossiness of NIAC is
evaluated by applying 1 g of paint over an opacity drawdown chart of model
opacity F - 2C with a controlled thickness of about 150 μm using multi-
functional film applicator (Fig. 3). After the application of paint, it is dried in
air for 24 h at room temperature. The glossiness is measured by following the
procedure mentioned in ASTM D523-14. The NIAC exhibits a greater gloss
level of 112, lying in the gloss unit of level 7 that puts forward the good surface
finishing of the
Fig. 3. NIAC applied on a drawdown card using thin film applicator.
Progress in Organic Coatings 132 (2019) 76–85
prepared Fe2O3 nanopaint coatings. Such high gloss paints have added
advantages like easy to clean, pleasing appearance, high protecting ability and
excellent stain resistance, etc.
3.2.3. Surface roughness through AFM
Fig. 4(a) is the 3-D topographical image of the painted film obtained through
AFM. It clearly reveals the film like topography characteristics for the painted
film. The image is not representing any individual particles since during drying
process the particles are well locked in the painted film. Fig. 4(b) is the 2D
image of the painted film, from which the surface characteristics of film like
surface roughness is usually explored from the line profile analysis drawn
through XEI software. On the 2D image, a horizontal line is drawn at 7.5 μm
(red line) and from this, it is clear that the surface is smooth having a very small
roughness of 21.205 nm (Fig. 4(c)). Similarly, a vertical line (green) drawn at
the 2D image at 4.1 μm, prove its lower surface roughness of 22.717 nm (Fig.
4(d)). The lower roughness value is attributable to the uniform dispersion of
nano Fe2O3 particles in the alkyd resin matrix.
3.2.4. Film thickness analysis through AFM
In this work, AFM technique is used to elucidate the thickness of the dry
pigmented film obtained after applying over a glass substrate of 7.5 cm× 2.5 cm
specimen. The cantilever of the AFM is adjusted to scan the interface of the film
where painted and uncoated region exist on the glass substrate. About 2.5 μm
×2.5 μm of the area covered the coated and uncoated position is scanned during
imaging. Fig. 5(a) represents the 2D-AFM image of the painted/non painted
segment scanned by the cantilever. Fig. 5(b) is the line profile image obtained
by drawing a line horizontally at about 1.7 μm across the paint film. The peak
profile indicates the pathway of line that travels across the painted and the
unpainted portions. The line profile starts at 2.5 μm, takes a dip and reaches −1
μm (Fig. 5(b)). From the difference in the height of the line profile at the
interface, the coating thickness is evaluated as 3.5 μm. Such a least thickness of
paint film is only possible by dispersing nano Fe2O3 as pigments in alkyd resin.
Commercially available paint produces a film thickness of 25 μm, obviously
required more material for obtaining the protective coating. In contrast to this,
the NIAC forms a thickness of only 3.5 μm consumes lesser material but
produces an efficient coating. Fig. 5(c) is the optical image obtained from the
microscope (AFM) before the approach of the cantilever on the paint coated
/uncoated steel specimen and it clearly reveals the painted and the unpainted
portions.
3.2.5. Evaluating the wetting ability of painted film
The wettability of a surface or a liquid suspension (paint) is one of the
prominent factors which greatly influences the characteristics of paint like
spreading, coverage, adhesive nature. It is well known that, the alkyd resin is a
film forming constituent, used to hold all other things together in a form of a
matrix. In fact, without any additives, 100% pure alkyd resin (binder or vehicle
or medium) is able to form a film over a susbstrate like metal or glass or wood
after application and subsequent exposure to atmospheric air. Under aerial
oxidation, the constituents present in the alkyd resin interlocked with each
other, forms oxide, peroxide linkages and produces a 3D macromolecular film
with a WCA of around 130° - a hydrophobic type [32,33]. Without any
additives, oxidation of alkyd resin is a slow process. In actual practice, during
making alkyd coatings, so many additives like pigments (metal oxides), driers
(accelerating oxidation), etc. are added which are all in hydrophilic in nature.
Due to the intimate mixing of pigments, driers, etc. the contents are able to
interact with the constituents of alkyd coating through van der Waals forces and
hydrogen bonding, make the coating as hydrophilic [34]. Owing to the variety
of fillers, the hydrophobic nature of the plain alkyd resin (130°) is changed to
hydrophilic type (73.3°). The change in wettability is further supported by the
critical surface tention studies.
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Fig. 4. (a). AFM 3D image of the NIAC of coated sample (b). 2D image of the paint coated specimen (c), (d) and (e) line profile analysis data.
To determine the correlation existing between the wettability and adhesion, it
is necessary to measure the contact angle and the surface energy of the paint
sample. William Zisman described the wetting ability of liquid with the solid
surfaces in terms of contact angle. In that study, they briefed that the cos θ
(contact angle) increased linearly as the surface tension (γLV) of the liquid
decreased. Using various liquids, the critical surface tension (γc) of the
substrate can be evaluated and the graph is plotted between the contact angle
and the surface tension of the liquids used for the study.
By employing similar experimental stratergy, the contact angle
measurement is done with three base fluids, namely isopropanol, ethylene
glycol and water on NIAC coated steel. Fig. 6(a) shows the contact angle image
of water, isopropanol and ethylene glycol dropped over the Fe2O3 pigmented
film. The contact angle measured using the different test liquids by dropping 1
μl on the test surface. The measured contact angles of water, isopropanol and
ethylene glycol dropped over the painted film are 73.3°, 16.4°, and 64.4°
respectively (Fig. 6a).
The cosine of the measured angles is plotted against the surface tension of
the corresponding liquid, shown in Fig. 6(b). To find the critical surface tension
(γc) of a painted film, the surface tension value is extrapolated to cosθ =1. From
the intercept and slope value, the γc is found to be 15.30 mN/m. Any coating,
whose γc lies in lower value, wets the surface well and spreads smoothly [35].
If the film displays excellent wetting ability, naturally its WCA becomes less
with respect to water. The WCA of as obtained coating is evaluated and
corroborated to its wetting ability as per the standard ASTM D7734-08. WCA
measurement shows a value of 73.3° for the iron oxide dispersed alkyd

Fig. 5. Paint coated and uncoated regions of A36 steel (a). 2D AFM (b). Line profile analysis of interfacial region (c). Camera view.

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Fig. 6. (a) Contact angle results of test fluids: Water, isopropanol and ethylene glycol on NIAC respectively. (b) Critical surface tension determination of NIAC using
Zisman plot.
based paint film after drying, exhibit hydrophilic nature. A lower WCA reveals
a strong wetting nature of the film, helps in improving the spreading rate,
thereby increasing the surface contact, adhesion, coverage area and the
protecting ability of the coating.
3.2.6. Spreading ability
Another important criterion of paint is its spreading ability/rate against the
chosen metallic/non-metallic substrate. As per ASTM D 34411, the spreading
rate is evaluated employing the opacity drawdown chart. Fig. 3 represents the
photographic image of NIAC-coated drawdown chart which revealed the
formation of uniform coating. The background colour (both black and white) is
completely hidden revelas the fact that the NIAC have an excellent hiding
power. The spreading rate and wet film thickness are computed using the
following Eqs. (2) and (3) respectively [36].
10M g( ) (2)
104M g( )
T(μm) =
A cm( 2). N D kg L.( / ) (3)
A cm( 2). N D kg L. ( / ) H m L( 2/ ) =
where, A =film area in cm2, N =fractional Non-volatile content, D =density
(kg/L), M = dry film weight, T = film thickness in μm. The spreading rate and
wet film thickness are calculated to be 10.22 m2/L and 97.77 μm respectively.
Eventually, the higher the spreading rate, the lower the cost of the paint.
3.2.7. Volatile organic compound measurements
The volatile organic compound (VOC) present in the paint creates problems
to the human beings if it exists beyond the permissible level [37]. VOC slowly
evaporates from the coating at ambient conditions and may cause harmful effect
when used in interior or exterior paint coatings. Low boiling constituents like
Progress in Organic Coatings 132 (2019) 76–85
thinners and thickeners added during paint formulation are responsible for such
VOCs. So, it is necessary to find the percentage of volatile and non-volatile
content of the NIAC paint. This is determined by following the standard ASTM
D 5201-05a. After subtracting the value of VOC from the total mass of the paint
taken for the analysis, the value of non-volatile constituents are obtained. This
is retained on the coating in the form of dry painted film. 1 g of paint taken in a
clean watch glass is dried in a hot air oven at 110 °C for 1 h. The percentage of
non-volatile content is calculated using the following Eq. (4),
Massofdriedpaintresidue
%ofnon − volatilecontent = × 100
MassofWetpaintsample
(4)
Normally, solvent based paint complying with the regulatory limits of 52%
of solid content are considered as high solid content paints. As per the
experiment conducted, the non-volatile content available in NIAC is found to
be 331 g/L (53%) which lies in the limit of high solid paint. The high solid
content facilitates high paint film thickness with the reduction in emission of
VOC, reduction in the application cost, consumption of paint, etc. [38].
According to Environmental Protection Agency (EPA), the maximum
affordable limit of VOC emission is forecasted as 380 g/L. The VOC content
found in the paint obtained by dispersing nano iron oxide particles is only 294
g/L which is more advantageous for the coating to be used in interior since this
value is lesser than the permissible level as per EPA. Such a reduction in VOC
content is due to the uniform distribution of nano iron oxide particles present in
the painted film. While drying, since the particles are in nano range, the particles
completely fill the voids that exist in the film, rendering the emission of lesser
amounts of VOC. Some of the VOC level of the alkyd coatings available in the
literatures are compared given in Table. 1.
3.3. Corrosion studies
3.3.1. Wet corrosion studies
The stability and the reactivity of NIAC under acidic conditions are
examined using the acid immersion tests. The corrosion inhibition efficiency of
the coating is calculated by employing weight loss method [42]. Herein, the
painted and bare A36 mild steel are immersed in three different acidic mediums
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viz 0.1 M HCl, 0.1 M H2SO4 and 0.1 M HNO3 over a period of 24 h. The weights induce weight loss to the NIAC coated sample. From the weight loss values, the
of bare steel and steel coated with NIAC are noted before and after immersing corrosion inhibition efficiency (%) of NIAC is calculated using the expression,
in acid. The percentage of

Inhibition efficiency %= (Wuncoated − Wcoated) × 100

Wuncoated (5)

where,Wuncoated is loss in weight of bare substrate, and Wcoated is loss in weight of

substrate being coated with Fe2O3 nanopaint. Corrosion inhibition efficiency of
NIAC coated substrate is about 89.52%, 97.28% and 99.40% for 0.1 M HCl,
0.1 M H2SO4 and 0.1 M HNO3 respectively. All these results, confirm the
remarkable protecting ability of NIAC coated A36 Steel in acidic environment.

3.3.2. Leaching studies

Coatings and paints protect iron based structural elements, alloys, steel,
galvanized steel, aluminum surfaces, etc., from corrosive environments. It also

Table 1
VOC level of various commercially available coating.
Sl.No Coating VOC level Permissible Level Reference
(EPA)

1. NIAC 294 g/L 380 g/L Present study

2. Automative alkyd coating 360 g/L 380 g/L [39]

3. Three interior alkyd enamel paints (Paint A; Paint B, Paint C) – purchased at local retail outlets for the Paint A: 347 g/L, Paint B: 380 g/L [40]
research program. Used by homeowners for application to walls or woodwork in residences. 350 g/L, Paint C: 421 g/L

4. Solvent-based interior clears 601 g/L 380 g/L [41]

5. Solvent-borne architectural & decorative wood care products 425 g/L to 635 g/L 380 g/L [41]

Fig. 7. Weight loss of bare and iron oxide coated steel in different acid environments.
weight loss of NIAC steel displays exceptionally reduced values in all the three
acidic environments than that of the bare steel (Fig. 7). The SEM images of the
painted and uncoated steel specimen recorded after wet corrosion studies. Fig.
8 reveals a very homogeneous, crack free surface of the NIAC coated A36 steel
sample. Fig. 8(b–d) is the SEM images of the surface of the samples subjected
to different acid treatments. These images show the formation of cavities
associated to the acid attack, delamination, formation of pores, formation of
protects the concrete and wooden surfaces; however, it sometimes facilitates
corrosion, owing to the delamination. Any coating that lacks in adhesion and
blistering effects leads to delamination from their position, thereby the
underlying surface may get exposed to corrosive environment. The most
common type of chemically induced deterioration of organic binder (alkyd
resin) is hydrolysis, which involves the reaction of the binder with corroding
medium like water, alkali, acid, etc. It generally occurs at either high or low pH
and in saline environments. The corrosion protecting ability of the coating can
be effectively interpreted from the analysis of the metallic elements concerned

Fig. 8. (a). SEM micrographs of NIAC (b–d). Worn surfaces of NIAC after acid treatment in HCl, H2SO4 and HNO3 respectively.
bubbles and blistering effect. The acids penetrate into the cavities of NIAC and present in the corrodant medium if the specimen is exposed to the corrodant for

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a longer period. Corrosion process actually converts the metallic element into
its ionic format, dissolved in the corrodant media. On analysing the corrodant
media through inductively coupled plasma-optical emission spectrometer (ICP-
OES), it is possible to quantify the extent of corrosion being concentrated on
the base metal. Using ICP, the quantity of the metal element being dissolved in
corrosive medium can be analyzed even in ppm level. To determine this, three
different specimens viz., bare A36 steel, NIAC coated steel, and NIAC coated
glass substrates are used. Obviously, bare steel undergoes fast dissolution in
various acids and the presence of Fe in the media is naturally high whereas, in
the case of NIAC owing to the protecting ability, the leachant possess lesser
amount of Fe in corrodants. In the case of paint coated glass specimen, the Fe
content present in the corrodant is only possible from the dissolution of Fe
existing in the coating. In the case of NIAC, the nano iron oxide particles are
well bounded in the alkyd resin with the quantity of iron leached in the
corrodants being very less. In the leaching experiments the bare steel, NIAC Fig. 9. Optical image of NIAC coated samples (a) Before immersion in 3.5% NaCl (b)
coated steel and NIAC coated glass substrates are dipped in 0.1 N HCl, 0.1 N After 24 h of immersion.
HNO3, 0.1 N H2SO4 and 3.5% NaCl for a period of 7 days. After 1 day and 7
days, the aliquots (1 ml) of the respective corrodant medium are removed and
made upto 100 ml in a standard measuring flask in 2% HNO3. The quantity of
iron content present in the medium is analysed through ICP and the obtained
results are given in Table. 2.
From the Table 2, it is clear that the iron leached into various corrodants are
high, if the steel is not covered by the coating. At the same time, the Fe present
in 3.5% NaCl is very less (0.927 mg) since it is not a harsh corrodant like 0.1 N
acids. After a week, the iron content present in all the media is found to be
enhanced. This is attributable to the fact that the prolonged exposure attacks
more and more iron, dissolves higher amount in the corrodant. Obviously, the
NIAC protects the steel from corrosion to a maximum extent; visualised from
the quantity of iron present in the leachant. On placing NIAC steel in various
corrodants in a similar manner, the Fe present in the media is least in
comparison to bare steel [0.1 N HCl: 114.8 mg for bare and 2.270 mg for NIAC
steel]. Similar trend is noticed in the case of 0.1 N H2SO4 and 3.5% NaCl. [0.1
N H2SO4: 364.5 mg for bare, 2.284 mg in painted condition], [3.5% NaCl:0.927 Fig. 10. Potentiodynamic polarization curve.
mg in bare steel, 0.292 mg in painted steel]. The quantity of Fe present in the
corrodant after a week is high, since during the ageing process, the delamination [0.1 NHCl: 0.008 mg; 0.1 N H2SO4: 0.002 mg; 0.1 N HNO3: 0.123 mg and 3.5%
of paint film is facilitated by the corrodants. Owing to the delamination of paint NaCl: 0.002 mg]. These results clearly confirm the fact that the iron present in
film, the steel surface in contact with corrodant is high and influences leaching nano form is not leached out on dipping the specimen for a day. Even after
of Fe into corrodant [0.1 N HCl:190.5 mg; 0.1 N H2SO4: 392.4 mg; 0.1 N dipping the glass substrate coated with paint for a week also, it has exhibited
HNO3:164.5 mg; 3.5% NaCl 2.239 mg]. very low quantity of iron. [0.1 NHCl: 0.018 mg; 0.1 N H2SO4: 0.033 mg; 0.1 N
In the paint coating, nano iron oxide particles are uniformly dispersed, HNO3: 27.34 mg and 3.5% NaCl: 0.025 mg]. Owing to the impounding nature
impregnated well in the alkyd resin matrix. To evaluate the impregnating ability of the nano iron oxide in alkyd resin matrix, the dissolution of iron in acid
of Fe in the matrix, the paint suspension is coated on a precleaned glass medium is not significant.
substrate. After drying, the paint coated glass specimen is also subjected to
leaching studies and the quantity of Fe present in various corrodant media is
analysed as before through ICP. The values are given in Table 2. 3.3.3. Cross cut test
After a day, the iron present in various acids and 3.5% NaCl is least. The cross cut test is performed on the NIAC coated steel plate by immersing
two specimens having a dimension of 75 mm ×25 mm in 3.5% NaCl solution
Table 2 for 48 h. After 24 h, one of the specimen is taken out, washed with distilled
Quantity of iron present in the corrodant media after 1 and 7 days. water, air dried and the increase in weight of corrosion product formed on the
specimen cut is accurately weighed. Fig. 9a represent the photographic image
of the specimen in which the cut is made. After 24 h, along the cross cut, the
formed corrosion product is deposited in dark brown colour (Fig. 9b). From the
increase in weight, the corrosion rate of the steel after coating NIAC is
calculated using the relation: Corrosion rate = K W/ρAt, where W is the weight
gain (mg) after exposure time t (24 h); ρ and A represent the density (g/ cm3)
and exposed specimen area (cm2) respectively and K is a constant, its magnitude
N HNO depends on the system of units used. The corrosion rate of steel after coating
3. 0.1 N H2SO4 364.5 398.8 2.284 392.4 0.002 0.033 the NIAC is found to be 921.8 μm/year. Longer exposure time of the NIAC
4. 3.5% NaCl 0.927 1.499 0.292 2.239 0.002 0.025 coated specimen in 3.5% NaCl leads to the blisters as close to the cross cut
owing to the penetration of the corrodant and finally leads to the detachment of
film from the substrate.

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K. Jeyasubramanian, et al. Progress in Organic Coatings 132 (2019) 76–85

Fig. 11. (a) Nyquist plot of NIAC coated steel in 3.5% NaCl solution. Inset: Nyquist plot of bare steel in 3.5% NaCl solution. (b). Bode impedance plot of bare and
NIAC coated steel (c). Bode phase plot of bare and NIAC coated steel. (d) Equivalent Circuit Model employed to simulate corrosion protecting performance of NIAC
coated steel. In the case of NIAC, the measured Ecorr value increased from -625.0 mV
[steel] to -598.5 mV. The observed positive shift in the Ecorr value of about 26.5
3.3.4. Potentio-dynamic polarization analysis mV and the decrease in Icorr values (0.001866 A to 0.00008365 A) is the
Potentio-dynamic polarization curve of NIAC and bare steel are recorded in indication of corrosion inhibition property of NIAC. It revealed that the anodic
3.5% NaCl aqueous solution as shown in Fig. 10. A conventional three- current density of NIAC is less than one order of magnitude, in comparison to
electrode cell is used with a platinum wire as counter electrode, Ag/AgCl as the bare substrates which highlight the use of NIAC as an excellent corrosion
reference electrode and the test sample (bare and painted A36 mild steel) as protection coating. The presence of homogeneously dispersed Fe2O3 in a alkyd
working electrode. Prior to polarization measurements, the open circuit matrix acts as a strong barrier, inhibiting the diffusion of corrosive ions to the
potential (OCP) is obtained by keeping the working electrode in a 3.5% NaCl metal coating interface, thus, providing a tortuous pathway for the corrosive
solution and monitored for 1 h to ensure stability. Once a stable OCP is ions to reach the metal surface. Further, the presence of oxygen in ferrite
determined, the upper and lower potential limits of linear sweep voltammetry facilitates the adhesion between coating and metal substrate. Thus, Fe 2O3
are set to +200 and -200 mV respectively relative to the OCP values. The nanoparticles protect the metal surfaces by acting as a strong barrier. The
polarization measurements are then carried out at a sweep rate of about 1 mVs−1. protection efficiency (%) of the NIAC is calculated using the following equation
The corrosion potential (Ecorr) and the corrosion current (Icorr) are determined [44].
from the Tafel extrapolation method [43].

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K. Jeyasubramanian, et al.
⎡ Icorr ⎤
ProtectionEfficiency %= 1 − × 100
⎢ I'corr⎥ ⎦
⎣ (6)
where, Icorr is the corrosion current of NIAC and I’corr is the corrosion current of
A36 mild Steel. The protection efficiency of NIAC is calculated and found to
be 96% which highlights the promising application of NIAC in corrosion
protection application.
3.3.5. Electrochemical impedance spectroscopy analysis
EIS analysis is performed to get detailed information of corrosion protection
mechanism provided by NIAC coating to steel specimen. The coated specimen
is dipped in the 3.5% NaCl solution for a period of 24 h. Typical Nyquist plots
(real impedance vs imaginary impedance) and Bode (log frequency vs log |Z|)
plots obtained are shown in Fig. 11(a) & (b) respectively on a linear scale. The
impedance value of NIAC specimen is found to be around 220 Ω at the low-
frequency end of the semicircle arc with the real axis (Fig. 11(a)). The inset in
Fig. 11(a) shows the impedance curve of the bare steel which has a very low
resistance of 6.8 Ω. Compared to the uncoated specimen, the impedance value
of NIAC coated steel is very high, thereby indicating its excellent corrosion
protection ability. The impedance data of the coated specimen confirms the
capacitive loops formed in the high frequency region. In the low frequency
region, the semi-circular loops appeared like a depressed type, supporting the
existence of surface heterogeneities. Similarly, the capacitive loops found in the
high frequency region are also found to be flattened. This confirms the formation
of a compact and continuous inner film providing good protection to the steel
specimen [45].
Bode impedance and Bode phase plots obtained for A36 mild steel
(uncoated) and NIAC coated steel specimen are shown in Fig. 11(b,c). The data
is obtained by keeping the specimen at 3.5% NaCl solution for 1 h. From the
Fig.11(b), it is clear that the decrease in AC impedance value of NIAC coated
steel confirms the corrosion resistance of the painted film [46]. Apart from Bode
impedance plot, it is also possible to evaluate the characteristics of corrosion
inhibition nature of NIAC coating through Bode phase plot. Phase angle found
in the Bode phase plot (Fig. 11(c)) is also used to evaluate the coating properties
of NIAC. It indicates the absence of defects or presence of discontinuities, in
different interfaces of the coating [47–49]. The phase angle maxima (single time
constant) is very high in the low and middle frequency range confirming the
exceptional corrosion resistance nature of the NIAC coating.
Further, Electrical equivalent circuits are employed to simulate the obtained
EIS curves to analyze the impedance data in a quantitative manner [11,50,51].
Proposed equivalent circuit model for the NIAC coated system in 3.5% NaCl
solution is shown in Fig. 11(d). Here, Rs is the resistance corresponding to the
ohmic resistance of the electrolyte. Rct and Cdl represent the charge transfer
resistance and double layer capacitance, while R l1 (Rl2) and Cl1 (Cl2) represent
the resistance and capacitance of porous corrosion product layer and micro
cracks respectively. The value Rct reveals the total corrosion resistance
performance. The values of all elements represented in equivalent circuit model
obtained by fitting are listed in Table S1. The simulated impedance plot shown
in Fig. 11(a), shows a good agreement with the experimental data odtained for
NIAC coated steel. This leads to the conclusion that the equivalent circuit model
provides a consistent description for the corrosion system. All these results
ensured the protection of A36 steel by NIAC, from electrochemical degradation
in an aggressive chloride ion environment.
4. Conclusion
This paper reported on the preparation and the evaluation of the
characteristics of nano iron oxide pigment dispersed in alkyd resin in the form
of paint. The surface morphology and FT-IR analysis revealed a uniform
distribution of Fe2O3 nanoparticles in the alkyd resin matrix. The hiding power,
gloss measurements, volatile and non-volatile constituents, spreading ability,
etc., of NIAC provided an insight into the better surface finishing characteristics
Progress in Organic Coatings 132 (2019) 76–85
and the quality of paint. NIAC exhibited excellent corrosion
inhibition/protection properties under acidic environment. Potentiometric
polarization results and EIS data displayed the corrosion resistance of NIAC
against bare steel in 3.5% NaCl solution. Further, the corrosion protecting
ability of NIAC coating was proved by analysing the quantity of Fe content
present in various corrodants after 1 day and 7 days through ICP-OES.
Acknowledgements
The authors would like to thank the Principal and the Management of
Mepco Schlenk Engineering College, Sivakasi, Tamilnadu, India. Extended
thanks are proposed to M/s. The Vigneswara Paints Pvt Ltd, Sivakasi, Tamil
Nadu, India.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the online
version, at doi:https://doi.org/10.1016/j.porgcoat.2019.03.023.
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