Progress in Organic Coatings 162 (2022) 106571

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Advances and future outlook in epoxy/graphene composites for

anticorrosive applications
Jesiya Susan George a, b, Poornima Vijayan P c, Jibin Keloth Paduvilan a, b, Nisa Salim d,
Jaka Sunarso e, Nandakumar Kalarikkal b, f, Nishar Hameed d, Sabu Thomas a, b, g, *
a
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India
b
International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India
c
Department of Chemistry, Sree Narayana College for Women (Affiliated to University of Kerala), Kollam 691001, Kerala, India
d
Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Victoria 3122, Australia
e
Research Centre for Sustainable Technologies, Faculty of Engineering, Computing and Science, Swinburne University of Technology, Jalan Simpang Tiga, 93350
Kuching, Sarawak, Malaysia
f
School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala, India
g
School of Energy Materials, Mahatma Gandhi University, Kottayam, Kerala, India

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

Keywords: Coatings are the prevailing, practical and preferred way to safeguard metals from corrosion. Graphene based
Corrosion protection organic polymer coatings are extensively used as corrosion fortification aids in this era. This short review
Epoxy highlights the importance of diverse features of such engineered coatings. Graphene has engrossed momentous
Functionalization
responsiveness in many industrial fields due to its superior anti-corrosion and barrier properties. The current
Graphene
Metal coating
review honestly debated the recent works and reports on epoxy/graphene coatings for metal protection from
extensive corrosion and oxidation. The various methodologies to acquire stable-homogenous graphene/epoxy
dispersion, covalent functionalization of graphene, doping of graphene with other nanofillers and their effect on
corrosion protection of epoxy/graphene coatings along with detailed corrosion protection mechanism are dis­
cussed. This review also outlines the integration of potentially relevant multifunctionalities in epoxy/graphene
coatings for self-healing, antifouling, self-cleaning and corrosion protection with suitable examples.

Abbreviations: A-GO, APTES modified Graphene oxide; APTES, 3-aminopropyltriethoxy silane; ASTM, American Society for Testing and Materials; ATMP, ami­
notrimethylphosphonic acid; BIIR, Bromobutyl rubber; BLc, blank epoxy resin; BTA, Benzotriazole; CNT, Carbon Nano Tube; CVD, Chemical Vapour Deposition; DA,
dopamine; DGEBA, Bisphenol A diglycidyl ether; EGDE, epoxy monomer ethylene glycol diglycidyl ether; EIS, Electrochemical Impedance spectroscopy; EP, epoxy;
EPN, epoxy Polydimethy Siloxane neat coatings; EPG, epoxy Polydimethy Siloxane graphene oxide composite coatings; FESEM, Field Emission Scanning Electron
Microscopy; FG, fluoro graphene FGc, fluorographene coatings; GLGO γ-(2,3-glycidoxy), propyltrimethoxysilane functionalized silica nano- particles grafted lysine-
modified graphene oxide hybrid; GNP, Graphene Nano platelets; GOE, epoxy monomer ethylene glycol diglycidyl ether functionalised graphene oxide; GOH, 1-
hydroxyethylidene-1,1-diphosphonic acid functionalised graphene oxide; GPTMS, glycidoxy propyl triethoxy silane; G-GO, GPTMS modified graphene oxide; GO,
Graphene oxide; GOc, GO/epoxy coatings; GO-SiO2, graphene oxide silica hybrid; GP0.05, Polypyrrole doped graphene oxide epoxy coatings; GO-PPy-Zn extract,
graphene oxide polypyrrole zinc hybrid reinforced epoxy coating; GO-Ti hybrid, graphene oxide titanium hybrid; HB, Hyper branched; HNT, Hallocyte nanotube;
HEDP, 1-hydroxyethylidene-1,1-diphosphonic acid; HF, Hydrogen fluoride; Ly-GO-EP, lysine functionalised graphene oxide reinforced epoxy coating; LPPS, Low
pressure plasma spraying; M-Gel-EP, modified gelatin reinforced epoxy; MGel/GO-EP, modified gelatin modified graphene oxide reinforced epoxy; MMT, mont­
morillonite; NSS, Neutral Salt Spray; PANI, Poly Aniline; PANI-DBSA, polyaniline doped with dodecyl benzene sulfonic acid; PDA, poly dopamine; PDA/PANI-GO/
WAV, polydopamine modified polyaniline-graphene oxide hybrid in water based alkyd vanish; PDMS, Polydimethy Siloxane; PAMAM, poly amidoamine dendrimer;
PBH, benzotriazole-loaded hallocyte nanotube hybrids; Ppy, polypyrrole; PS, Polystyrene; PVA, polyvinyl alcohol; PU, poly Urethane; PDA@HNT, polydopamine
coated hallocyte nano tubes; NaCl, Sodium chloride; TEM, Transmission electron microscopy; rGO, reduced Graphene Oxide; TiO2-GO-f-EP, GPTMS modified TiO2-
GO/epoxy; UP, unsaturated Poly ester; WEP, water borne epoxy.
* Corresponding author at: School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India
E-mail address: sabuthomas@mgu.ac.in (S. Thomas).

https://doi.org/10.1016/j.porgcoat.2021.106571
Received 2 August 2021; Received in revised form 15 October 2021; Accepted 15 October 2021
Available online 8 November 2021
0300-9440/© 2021 Elsevier B.V. All rights reserved.
J.S. George et al.
1. Introduction
Metallic structures are of great importance in the field of construc­
tions, aerospace, automobiles, oil/gas industries and so on, because of
their desirable multiple properties such as low cost, recyclability, high
strength etc. Infrastructures such as steel pipes, ship hulls and bridges
are susceptible to corrosion when they are exposed to harsh environ­
ments [1]. Metallic corrosion not only causes economy loss but also
results in safety hazard and environmental consequences to a large
extent. Corrosion of steel bridges and ship parts can negatively impact its
performance, service life, aesthetic appearance and safety of human [2].
The collapse of silver bridge into the Ohio river in the United States cost
40 lives and millions of dollars [3]. So far various methods have been
reported by researchers to prevent the extent of corrosion. Electro
deposition [4], electroless plating [5], gas phase deposition [6] and
organic coatings [7] are some of the widely used methods of corrosion
protection. Among the aforementioned methods, applying an organic
anti-corrosion coating over the metal surface is an effective and
economical way to prevent corrosion [8]. Covering the metal surface of
submerged ship parts and gas/oil pipes with an organic coating en­
hances the fouling resistance and extends its service life. Hence, the
long-term corrosion protection of metallic parts still need to rely on
organic anticorrosive coatings [9]. At present organic coatings, metallic
coatings and organic- inorganic hybrid coatings are frequently used for
corrosion protection [10].
On comparing the current trends in the literature, there is an
increased interest in anticorrosive coatings prepared by incorporating
nanoparticles into the polymer matrix [11], [12], [13]. Some reviews
have been published in recent years which are extremely devoted to
different aspects of achieving corrosion protection by means of various
nanostructures, polymers and nanocomposites [14]. Ding et al. [15]
explored the corrosion protection of graphene films from different an­
gles. The current article is the first review article on epoxy/graphene
composites debate its corrosion protection performance. This review
concisely discusses the effect of graphene and graphene oxide in epoxy
matrix towards corrosion resistance by citing relevant reports in this
area. The review also prospects the potential of epoxy/graphene to deal
with future corrosion challenges.
2. Basics of corrosion and corrosion protection
Corrosion is defined as the surface disintegration of metals and alloys
when exposed to a harsh environment, resulting in a deterioration of its
properties due to certain electrochemical reaction via oxidation [16].
Corrosion is a spontaneous natural phenomenon, which drives the ma­
terials to their lowest possible energy states [17–18]. Corrosion of the
metallic parts creates a substantial economic loss to the society and
threatens life too, especially in the industries. The diffusive chloride ions
in the seawater serve as an extensive corrosive agent to the submerged
metallic parts of ships such as hull and ballast tank [19].
Coatings are considered as one of the most effective way to protect
metal surfaces from corrosion due to its simplicity and ease of applica­
tion. Protective coatings create a barrier between the metal surface and
the exposed environment, thereby preventing the base metal from
extensive corrosion [20]. The homogeneity of the coating, the degree of
the porosity, and the adhesion to the substrate are the key factors
affecting the service life and performance of the coatings [21]. The
performance and durability of anticorrosive coatings in turn depend on
various parameters such as nature of the substrate, the pre-treatment
process, the coating thickness, the adhesion between substrate and
coating, and the external environment [22]. Understanding the in­
teractions between the individual components and the external exposing
environment is important in developing high-performance anticorrosive
coating. A corrosion protection coating can function via any of the three
mechanisms, i.e., barrier protection, chemical inhibition, or sacrificial
protection. Barrier protection is achieved by isolating the metal to be
2
Progress in Organic Coatings 162 (2022) 106571
protected from the external environment. While in chemical inhibition,
the chemical can suppress the corrosion process. Whereas in the case of
sacrificial protection, an active metal is coated to the metal which is to
be protected [23]. Coatings can be broadly classified into three classes, i.
e., metallic coatings, inorganic coatings and organic coatings [3].
2.1. Metallic coatings
Thin metallic coatings are applied to metallic substrates for corrosion
protection, provides a new metallic composite by combining the prop­
erties of both substrate and the coating. For e.g. mild steel has excellent
mechanical properties with poor corrosion resistance which restricts
their application in corrosive environment, this can be avoided by
alloying them with corrosion resistant metals such as chromium and
nickel [24]. Metallic coatings can be classified into noble metallic
coatings and sacrificial metallic coatings. The concept of applying a
noble metallic coating (Au, Ag, or Pt) to a more active metal takes the
advantage of greater corrosion resistance by the noble metal [25]. A
noble metallic coating is more corrosion resistant than the substrate.
Thus, it can provide excellent protection when it exists as pore-free
barrier coating. Sacrificial coating, on the other hand, is more active
than the substrate. It provides protection via combined action of barrier
action and sacrificial action. In galvanized steel for example, zinc
coating corrodes preferentially and protects the steel [3]. Jayaweera
et al. [26] investigated powder coatings of Si, Ti, Ni and alloy of Ni and
Ti (Ti-Ni 70:30 wt%) over low carbon steel. They exhibited reduced
corrosion rate of the coated carbon steel in chloride environment,
expecially Ti-Ni alloy showed exceptionally good corrosion protection.
Metallic powder coatings are non-sacrificial in nature with excellent
corrosion protection for a long time and are widely accepted for many
practical applications. Priyantha et al. [27] reported a cost-effective
metallic coating for the protection of metals from corrosion. Fluidized
bed reactor chemical vapour deposition was chosen to prepare diffusion
coatings of Cr, Ni, Si and Ti on carbon steel and stainless steel surfaces.
Cr and Ni coatings on stainless steel showed better corrosion protection
moreover, they didn't show any visible damage on the coatings other
than slight discoloration even after exposure to high temperature ab­
sorption fluids. Very recently, Chen et al. [28] introduced a novel green
sol gel method to introduce aluminium metallic coatings to protect
carbon steel. Silica sol mixture of a spherical and flaky Al powder to
make bottom coating and silica sol with Al fakes to prepare top coating
(double layer). These Al coatings showed an average adhesive strength
of 11–12 MPa and the corrosion current density of the single layer and
double layer specimen was 31 μA cm− 2 and 5 μA cm− 2 respectively. Liu
et al. [29] explored low pressure plasma spraying (LPPS) to fabricate
iron-based metallic glass coatings over steel substrate. They have found
that at higher hydrogen flow rate, denseness of the as-sprayed coatings
increases. Amorphous coatings obtained by maintaining a low hydrogen
flow (4–6 L/min) while partially crystalline coatings are obtained by
maintaining the hydrogen flow at 8 L/min. They reported an improve­
ment in the corrosion protection of steel by the partially crystallized
coating than amorphous one.
2.2. Inorganic coatings
Besides good corrosion protection, high thermal and mechanical
stability could be offered by several inorganic coatings. In recent years
considerable developments have been achieved in the field of inorganic
protective coatings. The continuous and extensive research on inorganic
coatings suggested that nanosilica based coating systems are considered
as a potential candidate to replace phosphate- chromate conversion
coatings. However, several inorganic coatings exhibited low adhesion to
the metal substrate especially at high temperature, this can be solved by
creating a conversion layer over the metal surface prior to the applica­
tion of coating. Bamoulid et al. [30] deposited titanium oxide coatings
on stainless steel surface by sol –gel process followed by the
J.S. George et al.
Fig. 1. Statistics of the number of published papers on epoxy coatings in the last 20 years [Source: PubMed database].
functionalization of the substrate in a conversion bath ceramic protec­
tive barrier on metal surface. Better corrosion protection of the fabri­
cated coatings was due to the synergistic effect of both conversion layer
and TiO2 coating. On the other hand, hybrid inorganic materials are
frequently employed as a best route to impart excellent corrosion pro­
tection by combining the properties of individual nanostructures. For
instance, Cheraghi et al. [31] introduced TiO2–NiO hybrid nanocoating
on stainless steel substrate via sol gel process followed by dip coating
and heat treatment. They found that composite coatings contain 80%
TiO2–20%NiO exhibited better corrosion resistance. Anatase and nickel
titanate phases are in a uniform surface hence the corrosion current
density reduced from 186.7 nA⋅cm− 2 (bare steel) to 34.21 nA⋅cm− 2. Yu
et al. [32] also investigated the effect of CuO/SiO2 and NiO/SiO2 hybrid
coatings for corrosion protection in Al alloy. On comparing the protec­
tive nature of NiO/SiO2 and CuO/SiO2 nanocomposite coatings, NiO/
SiO2 coatings demonstrated exceptional protection to Al alloy.
In the current scenario, several strategies have been explored to
introduce hierarchical structures on the surface of the inorganic coat­
ings. Recently, Xiang et al. [33] fabricated nature inspired slippery zinc
phosphate coatings with homogenous pores of 250 mm diameter. Zinc
phosphate coatings exhibited an exact honeycomb like heirarchial
structures. Homogeneous porous structure hinders the transport of
corrodents into the metal surface.
2.3. Organic (polymeric) coatings
Organic coatings have been widely used to protect metallic bodies
from corrosion [34]. Recent research on polymer coatings has shown its
potential application as corrosion protection systems. They can form a
thin layer over the metal surface, which act as a barrier to protect the
metal from the external environment. Here the barrier function is ach­
ieved by blocking the entrance of moisture and other corrosive agents
into the substrate. Organic coatings inhibit the charge transfer from the
metal surface to the environment. The current research community is
focused on the development of anticorrosive polymeric coatings due to
its simplicity, efficiency, low cost, and ease of availability [15]. A
desirable coating should provide chemical resistance, adhesion, flexi­
bility, impact resistance, low moisture permeability, ease of application,
affordability and durability. The polymeric coating increases the me­
chanical flexibility and toughness of the coatings. Both thermoplastics
3
Progress in Organic Coatings 162 (2022) 106571
and thermosetting polymers are used as protective coatings. Corrosion
inhibition of poly(vinyl alcohol)(PVA) was reported by Alaoui et al.
[35]. PVA can be used as a mixed type corrosion inhibitor for carbon
steel and the corrosion inhibition properties were exponentially
increased by increasing the concentration of PVA. Garcia et al. [7] re­
ported the corrosion protection of poly urethane films. Diniz et al. [36]
compared the anticorrosive efficiency of poly urethane (PU) and epoxy
coatings containing polyaniline doped with dodecyl benzene sulfonic
acid (PANI-DBSA). Studies revels that the epoxy-based coatings exhibit
better protection efficiency than PU based coatings.
2.4. Organic-inorganic hybrid coatings
Organic–inorganic hybrid materials defined as a class of multi
component compounds having at least one of their organic or inorganic
components in the submicron level mostly in the nanometric size
domain [37]. The properties of this system do not simply results from
the synergistic action of the both the components but also from the
hybrid interface [38]. The use of organic inorganic hybrid materials
attracted a great deal of interest in the field of protective coatings. [1].
Application of these organic-inorganic coatings ensures a long term
protection [39]. New functional coatings can be achieved by adjusting
the proportion and nature of interaction between the two phases [10]. In
recent years, combining the properties of organic polymer and inorganic
materials resulted in extensive research in hybrid organic-inorganic
coatings for corrosion protection.
Ramezanzadeh and his co-workers [40] studied the corrosion pro­
tection performance of polyurethanes (PU) containing modified nano-
Fe2O3. Nanoparticles tend to form aggregates due to higher surface en­
ergy and specific surface area, starts to behave like larger sized particles
within the matrix, thereby reducing the efficiency of coating. But the
surface modification of nanoparticles increases the interaction between
filler and matrix. PU composites containing modified Fe2O3 shows better
corrosion protection and lower adhesion loss than composites with un­
modified one. The EIS measurements of the prepared composite in acidic
medium gave evidence of its excellent corrosion protection. Najibzad
et al. [41] reported the corrosion resistance performance of rare earth
element praseodymium (Pr) doped PANI based silane coatings for Mg
alloys. Pure silane coatings have been degraded in a very faster rate than
Pr-PANI coating in the salt spray test. Self-healing properties shown by
J.S. George et al.
Fig. 2. SEM images of a) SiO2, b and c) SiO2/MoS2 core shells c and d)TEM images of core shell, f) HR TEM images of MoS2 [55].
these coatings is due to the release of Pr3+ and convert to Pr4+ as
insoluble hydroxides around the scratch. Similarly, Rajkumar and Vedhi
[42] incorporated silica nanoparticles into acrylic resin and examined
their corrosion prevention in mild steel. Incorporation of silica nano­
particles remarkably enhances the corrosion inhibition and the corro­
sion inhibition efficiency silica nanoparticles were found to be 77% in
3.5% NaCl. Likewise, Yu et al. [43] studied the p-phenylenediamine
modified GO reinforced Polystyrene (PS) coatings for corrosion protec­
tion. Dispersion of GO in PS was enhanced due to the presence of ter­
minal vinyl groups on GO. The barrier properties of the PS was increased
by adding 2 wt% of GO. In addition to the aforementioned thermoplastic
coatings, thermosetting polymers like phenol formaldehyde resins, ep­
oxies and polyesters are also used for obtaining corrosion protection.
Salehon et al. [44] prepared Unsaturated Polyester/clay composites by
in situ polymerization method. Electrochemical corrosion resistance
studies and Tafel polarization studies reveal that the inclusion of clay
particles significantly enhances the corrosion resistance. Neat UP resin
exhibits a corrosion current value of (Icorr) 0.1125 nA/cm2 corre­
spondingly nanocomposites with 5 wt% of clay (UP 5) shows very low
Icorr value of 0.0067 nA/cm2 among all other compositions in alkaline
environment, which is attributed due to the good dispersion of nano­
layers of nanoclay particles in the polymer matrix, increases the diffu­
sion pathways of corrosive agents.
2.5. Epoxies as a coating material
Epoxy resins are a class of thermosetting polymers having a unique
combination of excellent properties [45]. One of the largest applications
4
Progress in Organic Coatings 162 (2022) 106571
of epoxy resins are as coatings, owing to its unique characteristics [46].
Epoxy-based coatings are frequently used on the account of their
excellent combination of properties like anticorrosive nature, chemical
resistance, superior fatigue strength properties and excellent adhesion to
various substrates [47]. Because of these incredible properties of epoxy
resin is widely used as anticorrosive coatings for marine articulates such
as in ship hull. Corrosion rate on these structures depends on the water
salinity, chloride content, water temperature and current environment
on which it is exposed also [46] [48]. Epoxy based corrosion resistant
coatings was extensively studied in the recent years and the number of
papers published per year in the last 20 years on epoxy-based coatings is
represented in Fig. 1, according to PubMed database. As shown in Fig. 1,
number of published research papers per year continues to increase,
especially after 2017, there is a rapid increase in the number of research
papers published on epoxy-based corrosion resistant coatings.
DGEBA (diglycidyl ether of bisphenol A) is the most widely used
epoxy resin, synthesized by the reaction between bisphenol A and
epichlorohydrin [49]. Significant amount curing agent/hardeners are
added to epoxy resin to form a three-dimensional cross-linked network
[50] [51]. Sometimes catalysts were added in small amount to epoxy/
hardener to system to accelerate the curing reaction. Insufficient amount
of curing agent will results in the presence of unreacted functional
groups in the cured system hence the expected set of properties will not
be exhibited by the cured system [52]. Therefore, the exact amount
curing agent required for curing should be estimated by the curing
chemistry of the system. Upon the addition of curing agent, viscosity of
the system increases drastically. As the curing reaction proceeds, mo­
lecular weight of the epoxy prepolymers starts to increase, results to
J.S. George et al.
form a gel at a certain point of reaction, so called gelation/gel point
[53]. It is the point at which the storage modulus and loss modulus
become equal also the weight average molecular weight becomes
infinite. Finally, the system undergoes vitrification (elastic gel to glassy
state) due to infinite three-dimensional network formation [54].
Curing of epoxy resin creates a high crosslink density in it, which
limits their application and the prolonged exposure of epoxy resins in
the corrosive environment results in the hydrolytic degradation due to
the hydrophilic hydroxyl groups in the cured network, paves a way for
corrosive ions [34]. Hence various approaches have been put forwarded
by researchers to impart a larger diffusive path for the corrosive agents
for a long-term application. Incorporation of various nanoparticles is an
efficient and effective way both in terms of cost and performance. Xia
et al. [55] modified MoS2 with SiO2, the incorporation of MoS2 increases
the tensile strength furthermore the hybrid action of wrinkled MoS2 with
SiO2 drastically increases the diffusion pathways of corrosive medium
than when they are used alone. MoS2/SiO2 hybrid forms a core shell
structure in which SiO2 is covered by MoS2 as shown in the TEM images
in the Fig. 2 and they have examined the corrosion resistance of these
core shell/epoxy composites. Found that the core shell nanostructure in
the epoxy matrix could effectively the block the several and micropores
in the coating which prevents the further diffusion of electrolyte, and
maximum corrosion resistance was exhibited by 3 wt% system with a
Icorr value of 0.035 × 10− 6 after 150 h of immersion in 3.5% NaCl.
Hang et al. [56] examined the corrosion resistance of amino­
trimethylphosphonic acid (ATMP) modified MMT (montmorillonite) in
epoxy matrix and the corrosion protection of the carbon steel was
considerably improved by the modification, this is because the ATMP
reacts with Fe2+ form a complex at the steel surface, which protects the
metal from excessive attack [57]. The extensive studies found that in­
clusion of nanofillers enhances the durability and performance of epoxy
coatings by increasing the diffusion path of corrosive ions also anticor­
rosive nature and lifetime of coatings simultaneously [58].
3. Graphitic structures for corrosion protection
Graphene and graphene oxide are the important two-dimensional
materials, derived from parental natural graphite by simultaneous
exfoliation and oxidation [59]. Graphene is an amazing material in the
universe because of its versatile and astonishing properties [60]. It was
discovered in 2004 by A.K Geim and K⋅S Novoselov. Graphene and
graphene oxide are the most investigated materials at this moment
because of their incredible mechanical, thermal, electrical and optical
properties [61] [62] [63]. Graphene oxide is the heavily oxygenated
form of graphene, could be prepared by the direct oxidation and exfo­
liation of graphite. Both modified and unmodified graphene oxides, in
conjugation with/without other nanomaterials are extensively used for
several applications [64]. Graphene-based composites are abundantly
used in anticorrosive coatings since it forms a natural impermeable
barrier between the substrate surface and corrosive agents [65] [66].
The remarkable chemical inertness of graphene to various chemicals
even to HF and its impermeability to gases and fluids make it a potential
unique material for corrosion protection [67]. In general, pure graphene
coatings on metals prevent the formation of the oxide layer over it,
thereby protecting it from the reactive environment. There were two
approaches for using graphene for anticorrosive applications [67]. The
first one is by creating a layer of graphene on the substrate, this can be
achieved either by Chemical Vapour Deposition (CVD) [68], Electro­
phoretic deposition [69] and electrodeposition [70], second approach is
by adding it as a reinforcing agent in organic coatings with the aim of
inhibiting the diffusion of electrolytes path by creating an increased
tortuous degree [62]. Stanković et al. [71] studied the anticorrosion
efficiency of pure graphene sheets on Ni substrates. The sheets are
deposited on the substrates by CVD using methane as a carbon source.
CVD technique produces defect-free few-layered graphene sheets on Ni
but the oxidation resistance of these coating is effective up to 500 ◦ C
5
Progress in Organic Coatings 162 (2022) 106571
Fig. 3. Mechanical transfer preparation of graphene films on silver foil [74].
only. Graphene sheets have high electron density which creates a
repulsive field and thereby act like a strong impermeable material [72].
Reports of Chen et al. [73] demonstrated the excellent performance
of graphene sheets as a passive layer for Cu and Cu/Ni alloys. Zaho et al.
[74] introduced an ultrathin protective layer for silver thin films using
graphene sheets. Monolayers of graphene films were deposited on the Cu
surface and finally transferred into Ag substrate as shown in Fig. 3.
Graphene layers on the Ag surface significantly protect the surface. Due
to the ultrathin impermeable graphene layers corrosion rate of coated
Ag is reduced by about sixty times than the uncoated one.
Arrangement of graphene sheets parallel to the metal surface can
create several multiple barrier layers and provides an extra advantage
due to high specific surface area to prevent electrolyte penetration.
However, due to high electrical conductivity of graphene sheets once the
coating is damaged, the base metal will experience a boosted corrosion.
Hence the pure graphene film is not suitable for long-term corrosion
protection. Graphene-based organic coatings have been widely used for
corrosion protection owing to its protection efficiency and simple
preparation method [75].
3.1. Epoxy/graphene oxide composites for corrosion protection
Effective anticorrosive coatings are a hot research area due to the
growing need to develop excellent corrosion protection materials with
multifunctionality. The active physical barrier property of graphene
oxide is explored for the preparation of anticorrosive composite coatings
[76]. Jiang et al. [77] reported the anticorrosive properties of epoxy/GO
composites on steel and the effect of sheet size and morphology towards
anticorrosive property was explained. GO sheets with different aspect
ratios were prepared by controlling the degree of oxidation during
synthesis and they are successfully incorporated into the epoxy matrix
via wet transfer method. The influence of aspect ratio of GO sheets to­
wards anticorrosion performance was examined via EIS and polarization
studies using 3.5% NaCl solution. They revealed that the aspect ratio of
GO significantly influences the corrosion resistance. Composites with
GO having high aspect ratio showed higher corrosion resistance than
other composites this is because, higher the aspect ratio, the higher
would be the barrier property and hence tortuous diffusion channel for
the corrosive ions.
Pourhashem et al. [78] studied the corrosion protection properties of
solvent-based epoxy-GO composites. They found that the preparation
process also affects the dispersion quality of GO in resin. Direct addition
of GO into the hardener followed by mixing with resin shows better
dispersion than those prepared by direct mixing GO in resin. 0.1 wt% of
GO is considered as the optimum wt% which shows the best corrosion
resistance, as the amount of GO increases the coatings tends more brittle
due to the agglomeration of nanosheets.
J.S. George et al.
Fig. 4. Schematic illustration of a) mixing GNPs into epoxy resin using ultrasonication and b) mixing GNPs into hardener using ultrasonication [88].
3.2. Dispersion of graphene and graphene oxide in organic anticorrosion
coatings
Graphene nanosheet shows poor dispersibility in polymer matrix due
to its insolubility in the matrix, owing to higher van der Waal forces and
ℼ-ℼ stacking between the sheets [79] [80]. The week bonding strength
between the graphene and polymer matrix is due to the low surface
activity of graphene. The surface of pristine graphene lacks active
functional group, hence surface modification or functionalization is
often necessary to perform prior to the application [81]. Usually, re­
searchers incorporated Graphene oxide (GO) or reduced Graphene
Oxide (rGO) in functional coatings due to the presence of reactive
functional groups on it. Improvements in mechanical and other prop­
erties are directly related to the quality of dispersion of nanoparticles in
the polymer matrix. Till date various mixing protocols have been
adapted by researchers to obtain a stable dispersion of graphene in
various polymer matrix. Obtaining a stable and uniform dispersion of
these materials are quite essential in anticorrosive coatings [82] [83]. A
number of parameters have to be considered for obtaining a good
dispersion of nanoparticle. The total free energy of any colloidal system
is depends on both interfacial tension and interfacial energy, the theo­
retical surface area of a monolayer graphene is around 2590 m2 g− 1,
consequently the conditions are limited under which it can be dispersed
using polar aprotic solvents typically by sonication.
Obtaining and maintaining a stable dispersion needs an energy
barrier to aggregation. This can be typically achieved by either elec­
trostatic or steric repulsion. If the energy barrier is sufficiently high then
Brownian motion will maintain the dispersion, this is achieved by sol­
vent selection and covalent/non-covalent functionalization of graphene
[84]. The dispersibility of graphene and its derivates are inversely
proportional to its properties and it follows a trend of graphene oxide >
reduced graphene oxide > graphene. Chemical functionalization of
these structures improves the dispersibility but it has a negative impact
towards the final property since it creates some defects into the structure
[85].
Coming to the preparation of epoxy/GO composites, various
dispersion methods of graphene within the epoxy matrix have been
6
Progress in Organic Coatings 162 (2022) 106571
considered. Among the reported methods, widely used method is the
dispersion of graphene using an organic solvent followed by the com­
plete removal of solvent from the system before curing, which is prac­
tically not simple and cause various difficulties in large scale production
[86]. Due to strong van der Waal forces of attraction between the sheets,
graphene dispersion in solvents has a high tendency to restack over a
period of time even after ultrasonication too. Therefore the direct
dispersion of graphene in epoxy resin/in harder by ultrasonication,
mechanical mixing, and shear mixing can solve these drawbacks [87].
Kilic et al. [88] studied the effect of dispersion technique on the final
properties of epoxy/graphene composites. The composites were pre­
pared by sonication or sonication in combination with high shear mix­
ing. They have prepared epoxy/graphene and hardner/graphene
dispersion. Most of the previous reports prefer the preparation of epoxy/
graphene dispersion rather than hardener/graphene dispersion as given
in Fig. 4a and b.
They have found that the dispersion of graphene nanoparticles in
resin shows overall better properties than dispersion in hardener and the
combination of high shear mixing and ultrasonication results in better
dispersion of nanoparticles. Similarly, Tang et al. [89] prepared epoxy/
rGO composites by a two-step process, in the first step, rGO were
dispersed in ethanol by ultrasonication followed by mechanical ball
milling. Ball milling can create a large shear force on graphene, the
collision of small zirconia balls in the ball milling process can fragment
the sheets and inhibits its agglomeration. On comparing the dispersion
level with the previous results dispersion of rGO does not change after
ball milling process, however the size of aggregate particles became very
small compared to other mixing protocols. Amirova [90] followed an
aqueous transfer method for the preparation of epoxy/GO composites.
Here they have transferred the GO sheets from water phase to epoxy
resin skillfully. Better improvements in the mechanical properties have
been achieved at 0.03 wt% of GO owing to its homogeneous dispersion
and strong interfacial interaction between epoxy and GO.
One of the main factors which affects the dispersion of graphene is
the viscosity of the epoxy resin. Pourhashem et al. [78] used low vis­
cosity polyamide curing agent for high viscosity epoxy resin and found
that GO dispersed uniformly in the harder rather than in the high
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 5. FESEM image of GO and silane modified GO sheets [95].

viscosity resin. Moreover, the large surface area and surface energy of
graphene and GO results in great tendency to form agglomerate within
the matrix. Modification of graphene reduces the surface energy and
thereby achieves sufficient compatibility and dispersion within the
polymer matrix. So far, a variety of graphene-based coatings were pre­
pared and applied to various substrates to protect them from corrosion.

3.3. Functionalization of graphene oxide

As we discussed earlier, aggregation of graphene sheets in the com­

posite is a major drawback in such application, and this is the direct
effect of strong van der Waals interaction. To solve this issue, chemical
modification of the graphene sheets or conjugation of a second particle
into the graphene sheets is the most convenient strategy employed [91].
Either non-covalent or covalent functionalization of nanosheets signif­
icantly enhances the interfacial interaction between the sheet and the
polymer matrix [92]. A lot of works has been already published on the
modification of graphene sheets using various chemicals, such as phytic
acid, DGEBA [93], polyacrylates [94] and so on. Pourhashem et al. [95]
modified GO sheets using an organosilane coupling agent, 3-amino
propyl triethoxy silane and the effect of silane modification of gra­
phene oxide towards corrosion resistance on mild steel was investigated.
The covalent bond between silane-modified GO and epoxy resin in­
creases the interfacial interaction between them as well as the dispersion
also.
It is very clear from the SEM image (Fig. 5) that the silane modifi­
cation makes the surface of GO rougher with wrinkle morphology. The
functionalization results in a better exfoliation of GO which prevents the
restacking of the nanosheets. GO contain reactive oxygen functional
groups such as hydroxyl, epoxy, carbonyl and carboxyl groups on sheet
edges and basal planes [96]. However, the ethoxy groups on APTES is
also highly reactive thus, it will form silanol (Si–OH) groups by hy­ Fig. 6. a) Bode plot and b) Nyquist plots pure epoxy, M-Gel-EP, MGel/GO-EP-
coated samples after 24 h of immersion in 3.5% NaCl [97].
drolysis. The silanol group and hydroxyl groups on GO and form
Si–O–Si bonds. The corrosion resistance of the coatings depends on the
quality of the dispersion as well as on the interfacial interaction between value of Epoxy gelatin composite has a lower value than gelatin modi­
the filler and matrix. Silane functionalization of GO in the epoxy coating fied GO composites, and there are no significant changes for the phase
enhances the compatibility and interfacial interactions. Hence, the angle values after prolonged immersion too as shown in Fig. 6.
coatings containing A-GO exhibit better corrosion resistance in the mild The improvement of corrosion resistance of epoxy coatings by add­
steel than the pure epoxy coatings with unmodified GO. ing hydroxyl terminated hyperbranched (HB) polyamine functionalised
Ranjitha et al. [97] modified GO using gelatin for the first time and GO was reported by Sari et al. [98]. Mild steel substrates were coated
they also found that, gelatin modification helps to obtain good disper­ with 0.25, 0.5, 1.0 and 2.5 wt% of functionalised/epoxy coatings. The
sion within the epoxy matrix. The hydrophobic nature of the coatings adhesion of epoxy resin into the steel substrates was found enhanced by
drastically enhanced by adding gelatin modified GO, the increment in incorporating polyamine modified GO particles. In the electrochemical
water contact angle can be attributed to the increased crosslinks. aspects, corrosion is a slow process; initially, corrosive ions diffuse into
Corrosion protection of the coatings was evaluated by EIS analysis. Neat the coating through inherent micro and macropores but do not reach the
epoxy has a low phase angle value among all. However, the phase angle surface of the substrate or the interface between coating and substrate,

7
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 7. Impedance values versus immersion time for neat epoxy and different
wt% of hydroxyl terminated hyperbranched polyamide functionalised GO after
850 h immersion in saline water [98].

but after a long time, corrosive products starts to accumulate on the

surface of the substrate results in the reduced adhesion and finally
detachment. The impedance value further supports this mechanism.
Fig. 7 represents the trend in immersion time versus impedance of the
composites after immersion in saline water. Impedance value of 0.5 and
1.0 compositions remain unchanged at all immersion time and all
remaining compositions have a decreasing trend. The highest compo­
sition (0.25) shows a very lowest impedance value among all composi­
tion. Improved corrosion resistance of modified GO was due to their
ability to form good dispersion in the matrix, which increases the
diffusive path of corrosive ions by creating a tortuous path.
Hayatgheib et al. [99] functionalised the GO nanosheets with PANI Fig. 8. Schematic illustration of modification of GO by dendrimer
nanofibers increase the dispersion of graphene in epoxy resin. Com­ (PAMAM) [100].
patability of GO in epoxy resin was effectively enhanced by PANI
modification and the composite shows enhanced barrier properties.
coupling agent. Amine functional groups present in the GPTMS modified
Correspondingly Ramezanzadeh et al. [100] introduced amino func­ GO(G-GO) are less active than the modified APTMS (A-GO) hence NH2
tionalised (polyamidoamine) dendrimers into GO as shown in Fig. 8.
groups in the A-GO are more prone to form hydrogen bonds with their
Bode plot for the samples after 56 days of immersion in 3.5% NaCl as unpaired electrons with the epoxy ring.
shown in Fig. 9, revels that the phase angle of the neat system decreases Cui et al. [102] functionalised GO with a corrosion inhibitor, 1-
with immersion time increases from 14 days to 56 days indicate the hydroxyethylidene-1,1-diphosphonic acid (HEDP) and with an epoxy
reduced barrier protection as a result of electrolyte diffusion. On the monomer ethylene glycol diglycidyl ether (EGDE), denoted as GOH and
other hand, dendrimer modified GO sheet doesn't show a change in GOE respectively. The addition of both HEDP and EDGE functionalised
phase angle even after 56 days of immersion. GO (GOEH) in the water borne epoxy matrix (WEP) significantly im­
Pourhashem et al. [101] evaluated the effect of different silane proves the corrosion protection by chemical inhibition and barrier ef­
coupling agents (APTES and GPTMS) towards corrosion resistance via fect. Neutral salt spray test was conducted as per the standard ASTM B
GO modification with them. Schematic representation of modification 117. After 16 days onwards, several corroded area were visible on neat
on Fig. 10. Silane modification of GO found to enhance the water contact WEP coatings and tiny black dots were appeared on both GOE/WEP and
angle and adhesion of epoxy coatings to metal substrates. Ultimately, GOH/WEP coatings as shown in Fig. 11. As proposed earlier GOEH/WEP
APTES modified GO coatings exhibit better corrosion resistance coatings show a smooth surface without pronounced on it even after 28
compared to GPTMS modified coatings. This improvement in corrosion
days.
inhibition is greatly affected by the organic structure of the silane Fluorographene (FG), one of the stable derivatives of graphene,

8
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

attracted remarkable attention of the research community on account of

Fig. 9. Bode plots of the (a) blank epoxy, GO/epoxy and GO-PAMAM/epoxy
composites [100].
its extra ordinary physical and chemical properties. Doping F atom in
graphene could destroy the electron conduction pathway in graphitic
structures, since the continuous π-π bond was converted to an isolated
π-π bonds in FG [103] [104]. In view of the excellent, barrier property,
low surface energy and superhydrophobicity (water contact angle 123◦ )
of the fluorographene [105] [106] they are widely used to fabricate
superhydrophobic, self-cleaning corrosion resistant coatings. In the
current scenario, fluorographene structures are extensively used and
accepted to achieve better corrosion resistance. On the other hand, high
hydrophobicity of the FG makes it extremely difficult to disperse in the
organic matrix. Lei et al. [107] reported the anti-corrosion and anti-
scratch properties of the epoxy/graphite fluoride coatings on steel.
They revealed that the synergistic enhancement in the corrosion resis­
tance and scratch resistance were attributed by the excellent electrical
insulating properties of the well dispersed graphite fluoride platelets in
the epoxy matrix. Recently, Shen et al. [105] extensively studied the
effect of degree of fluorination towards corrosion resistance. They
fabricated epoxy/F-doped rGO coatings with different degree of fluori­
nation. In general, electrical conductivity of the FG decreased with the
increased degree of F-doping and they found that the corrosion resis­
tance of EP/FG coatings was enhanced directly with the F-doping degree
of FG in the composite coatings. Yang et al. [106] used a liquid phase
exfoliation of the fluorographene to stack them over the epoxy coating
on the Cu surface, in order to introduce several micro/nanoscale
roughness on it. The enhanced superhydrophobicity by incorporation of
fluorographene results in the excellent protection of the Cu substrate in
3.5 wt% NaCl aqueous solution. For a change, Wu et al. [108] used CVD
to prepare FG coatings on Cu surface, for that they used convenient and
efficient gas phase fluorination technique to fluorinate graphene
sprightly. The theoretical modelling revels that the doping of fluorine in
graphene films are able to form some bond with carbon atoms, espe­
cially in the defect sites. This has a huge impact for the inhibition of the
entire corrosion process on the underlying metal substrate.

3.4. Graphene based hybrid filler for epoxy coatings

Graphene and its derivatives are widely used as corrosion protection

Fig. 10. Scheme for the modification of GO using APTES and GPTMS [101].
aid in conjugation with various resins and polymers. However, the
massive defects in the graphene reduce its long-term anticorrosive
properties. In addition to the above-mentioned problem agglomeration
of the nanofillers is a serious problem which deteriorates the anti-
corrosion performance. In order to overcome these problems, GO can
be anchored with other fillers like TiO2 [109], Ag [110], SiO2 [111] via
with/without chemical bonding. Table 1 represents the recently re­
ported graphene hybrid systems for corrosion protection in terms of
their corrosion current density.
The enhanced macroscopic properties in a polymer composite
directly affect the compatibility between polymer and filler [121]. The
ease of availability, corrosion resistance and low cost of aluminium
oxide (Al2O3) make it a potential corrosion resistance agent. The in­
clusion of GO/alumina hybrid helps to get a synergistic property on the
composites rather than using them individually. There are only a few
reports on epoxy/GO-Al2O3 for corrosion resistance. Yu et al. [122]
reported the anticorrosive performance of epoxy coatings with GO-
Al2O3 hybrids on steel substrates. GO-Al2O3 was fabricated with the help
of a silane coupling agent and the scheme was given in the Fig. 12.
Hybrid filler forms a stable dispersion in epoxy resin Coating composi­
tions with hybrid shows better corrosion resistance this was highly
supported by the data obtained from EIS studies. Better dispersion of
hybrid in epoxy resin inherently plugs the micropores performance. The
synergistic effect of GO and Al2O3 in the epoxy resin ultimately enhances
the corrosion resistance by creating a barrier for the corrosive ions,
prevents the coated metal from its attack.
The incorporation of silica particles provides thermal and mechani­
cal properties into the coatings. Large surface area and smooth surface of

9
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 11. a) Images of the steel substrates coated with WEP, GOH/WEP, GOE/WEP and GOEH/WEP coatings after NSS tests, b) adhesion strength of the coatings by
pull of test [102].

On the other hand Ramezanzadeh et al. [125] prepared GO-Silica

Table 1 conjugate using a mixture of silane coupling agents TEOS and APTES
Comparison of the graphene hybrids for corrosion protection. by two methods. The method I describe the simple mixing of GO in an
Sl. No Hybrid system Authors Corrosion current (Icorr) Ref. ethanol-water mixture along with the silane coupling agents whereas
1 GO/TiO2 Kumar et al. 105 nA/cm2 [112] the method II involves the mixing of the ethanol-water mixture along
2 TiO2–GO/EP Liu et al. 6.94 × 10− 10 A/cm2 [113] with the silane coupling agents for a time period followed by the addi­
3 GO–ZrO2/EP Haihui et al. 0.37 μA/cm2 [114] tion of GO. The corrosion resistance performance of these hybrids along
4 Ni/graphene Ding et al. 1.961 × 10− 8A/cm2 [115]
with epoxy resin on mild steel was examined. The effect of silanization
5 Cu/Gr/PPy Merisalu et al. 6.2 mA/cm2 [116]
6 PDMS/GO-ZnO Selim et al. 0.035 mA/cm2 [117]
time towards corrosion resistance explains that samples contain hybrids
7 PANI/graphene Jafari et al., 0.1 μA/cm2 [118] with silanization time 24 h and 48 h shows only one time constant, and
8 GLGO/WEP Wang et al. 1.115 × 10 × 8 A/cm2 [119] sample (the method I) with silanization time 72 h shows 2-time constant
9 Ti3C2/graphene/ Yan et al. 9.23 × 10− 11 A/cm2 [120] semicircles appeared for this sample after 60 days of immersion. Sam­
EP
ples with silanization time 48 h were the best for corrosion protection,
Graphene Oxide (GO), Titanium dioxide (TiO2), TiO2-GO-f-EP; GPTMS modified similarly samples with silanization 48 h only show single time constants
TiO2-GO/epoxy. Cu/Gr/Ppy graphene/polypyrrole hybrid coating on Cu. in the case of method II.
PDMS/GO-ZnO; polydimethylsiloxane/graphene oxide nano- sheets decorated Ramezanzadeh [126] and his co-workers evaluated the corrosion
with ZnO. PANI/graphene; polyaniline graphene coating. GLGO/WEP; γ-(2,3- protection efficiency of epoxy/GO-Ppy/Zn coatings. Fig. 14 represents
glycidoxy) propyltrimethoxysilane functionalized silica nano- particles (GSiO2)
the digital photographs of the coating after salt spray test. As the
grafted lysine-modified graphene oxide (LGO) hybrid in water borne epoxy.
exposure time increases huge quantity of corrosion products was
deposited near to the broken regions. Compared to neat epoxy coatings,
silica particles promote the interfacial interaction and dispersion be­ nanocomposite coatings exhibit less blisters and rusts. Because of the
tween polymer and filler, silica-based scratch resistant and corrosion improved barrier properties, functionalised GO coatings show few
resistant coatings were already reported in the literature. Ma et al. [123] corrosion spots. Coating containing GO-Ppy-Zn shows better corrosion
reported the anticorrosive properties of epoxy-GO/silica hybrids on steel resistance among all.
substrates. The correlation between morphology and water contact Chang et al. [127] successfully prepared GO/Fe3O4 @ poly(DA +
angle after 20 days of immersion in 3.5% of NaCl was recorded and are KH550). A hydrothermal route was used to prepare GO/Fe3O4 hybrid, it
given in the Figure 13. The water contact angle of epoxy coatings with 2 was then modified by dopamine (DA) and amino silane (KH550). The
wt% of GO-silica hybrid was 92◦ even after 20 days of soaking. aggregation of GO sheets within the matrix reduces the corrosion inhi­
Morphological analysis is considered as an important method for the bition as shown in Fig. 15. In all these figs. GO/epoxy composites show
selection of excellent coating systems, lesser the morphological changes smaller impedance radius than the neat epoxy due to the aggregation of
after immersion, considered as good candidates. It is evident from the sheets. However, GO@Fe3O4(DA+ KH550)/epoxy composites have a
below images all other samples show a considerable difference in the higher impedance radius than all other compositions indicate their
morphology except composites with 2 wt% of GO-silica hybrid. Wu et al. better anti-corrosion properties. This increased impedance radius was
[124] synthesized fluorinated rGO/CeO2 hybrid and evaluated their due to the improved interfacial adhesion and dispersion of the hybrid
effectiveness to enhance the corrosion protection of epoxy resin on mild system in the resin.
steel surfaces. Adsorption of CeO2 on the surface of mild steel lead to the Studies of Yuan et al. [128] reported the anticorrosion performance
formation of a passivation layer, which further restricts the corrosion on of GO nano titanium hybrids. These hybrids were prepared by simple
the steel. mixing of functionalised GO and functionalised titanium particles.

10
J.S. George et al.
Fig. 12. Synthesis route for the preparation of GO-Al2O3 hybrid [122].
Macropores in the organic coatings will not provide a long-term corro­
sion resistance; therefore, incorporation of nanoparticles will block such
pores and results in long-term corrosion resistance. Various studies
found that the loading of inorganic nanoparticles into the GO sheets
reduces aggregation and results in good dispersion. Fig. 16 represents
the scheme utilized for the preparation of hybrid filler.
Go sheets are agglomerated in the SEM image due to strong van der
Waals forces of attraction.
Similarly, nano Ti particles also in severe aggregated state; uniform
dispersion of these individual fillers in the polymer matrix is a serious
issue. However, the Figure 17 c, d and f represent SEM images of the
hybrids at different ratios, at 1:1 ratio Ti particles are aggregated on GO
sheets and at 2:1 (GO-Ti) ratio nano Ti particles are uniformly distrib­
uted on GO sheets but at 3:1 ratio Ti particles are randomly distributed
on GO sheets and probability of finding a particle at a given area is very
less, hence 2:1 is the appropriate ratio. Corrosion resistance studies of
the composites revels that GO-Ti/EP composites, especially 2:1 ratio
shows excellent corrosion resistance than other compositions due to the
synergistic effect of GO and Ti.
Corrosion current in most of the papers represented as corrosion
current density because this current density is an interfacial property.
Corrosion current density directly related to the penetration rate of the
metal. This Icorr is a kinetic parameter obtained from the Tafel plot,
smaller the corrosion current density value indicates a slow corrosion
rate of the coating.
Table 2 represents the comparison study of corrosion current density
of some reports. By comparing the values of corrosion current density,
PGT/WEP coating composition shows higher corrosion resistance, this
enhanced corrosion resistance of the systems can be ascribed by the
strong interfacial interaction between GO and epoxy resin. Modification
of GO with PDA helps to disperse uniformly in the matrix and creates a
dense barrier layer for corrosive ions. As well as TiO2/GO hybrids fill the
voids, cracks and other pinholes/interstitial sites in the system.
11
Progress in Organic Coatings 162 (2022) 106571
4. Mechanism of corrosion protection and practical problems
associated with graphene-based coatings
Graphene films are the thinnest material in the universe with
excellent corrosion resistance; hence these nanosheets are utilized as
corrosion inhibiting fillers in organic coatings in order to get the syn­
ergistic corrosion inhibition and enhanced mechanical properties [137].
Corrosion protection performance of an organic coating most often
depend on its barrier properties and the maintenance of adhesion be­
tween the coating substrate under the environment. The corrosion
initiation in a polymer coated metal is due to the penetration of water
molecules, ions and oxygen into the interface [138] [139]. Diffusion of
these species probably follows the small pores or paths within the
polymer matrix. However, severe corrosion process start at the local
defects within the coating, this can be generated during the fabrication
or during the working of the coated material, such as that happened by
stone shipping or by scratching. These defect leads to a direct contact
between the bare metal and corrosive agent, subsequently, detachment
of coated material from the metal surface happens [140].
The primary mechanism for corrosion protection using organic
coatings is barrier protection. The cracks and micropores in the organic
coatings formed by the solvent evaporation on the curing process
attenuate the barrier protection performance of these coatings [141].
The corrosion process on a coated metal consists of several stages. In the
initial stage, electrolyte/the corroding agents penetrate into the coating
via inherent micro-pores in it but they do not reach the surface of the
metal. As the reaction proceeds with time and accomplished by the
accumulation of corrosive products either on the metal surface or metal-
coating interface. The corrosion process in steel involves several oxi­
dations and reduction reaction as shown in the below equations.
As a result of these redox reactions, pH locally raises, hence the
chemical and physical bonding between the metal substrate and epoxy
coating results in the delamination of the coating. It is clear that oxygen
and water molecules are the key corrosion initiators in steel and they can
easily penetrate through the several micropores present in the epoxy
coating. The addition of graphene-based fillers into these organic coat­
ings prevents this penetration and thereby offers excellent anticorrosion
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 13. SEM images of coatings before and after soaking pure epoxy (a &a′ ), 2 wt% GO/epoxy (b &b′ ), 2 wt% silica/epoxy (c&c′ ) and 2 wt% SiO2/GO/epoxy
(d&d′ ) [123].

behaviour. Zhou et al. [142] reported the corrosion inhibition of zinc- electrical conductivity between steel and zinc particles thereby increases
rich epoxy/rGO coatings as shown in Fig. 18. It is clear that the inclu­ the cathodic protection.
sion of rGO sheets provided some additional advantage such as Coming to Fig. 19 corrosive agents can easily reach the metal surface
enhanced electrical conductivity of rGO sheets, thereby enhances the very rapidly without any delay in the epoxy resin. Higher the aspect

12
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 14. Digital photographs of the GO-Ppy coatings after salt spray test [126].

Fig. 15. Impedance spectra of various epoxy composite coatings GO-Fe3O4@poly (KH550 + DA) hybrid after soaking for different times: a) 12 h, b) 24 h, c)72 h, and
d) 144 h [127].

ratio of the added filler better the barrier property and more the tortuous corrosion protection efficiency through these defects. However, there
path for corrosive agents compared to those having lower aspect ratio. were different opinions on the protective the efficiency of graphene
Cracks and defects present in the graphene sheets are the major sheets explained by various researchers. The main challenge of using
problems associated with graphene coatings and they reduce the graphene oxide in most of the polymeric coatings is its poor

13
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 16. Scheme for the preparation of GO-Ti Hybrids [128].

Fig. 17. SEM images of GO (a), Nano-Ti particles (b), GO-Ti [1:1] (c), GO-Ti [2:1] (d), GO-Ti [3:1] (e) and TEM image of GO-Ti [2:1] (f) [128].

14
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Table 2 benefits. In the current scenario, multifunctional coatings gain an

Comparison of corrosion current density values of reported works. attraction over the scientific community [143] [144] [145]. Studies of
Hybrid system Icorr (A/cm2) Author Reference Kim et al. [146] suggests the prevention of corrosion fatigue of ship parts
− 8 in seawater using a self-healing system based on Bromobutyl rubber
Epoxy/GO 1.164 × 10 Jiang et al. [77]
Epoxy/M-gel-GO 6.836 × 10− 8 Rajitha et al. [97] (BIIR) and carbon nano tube. The CNTs can facilitate the self-healing at a
Ly-GO-EP 2.898 × 10− 8 Yang et al [129] much faster rate. Reports of Najmi et al. [147] also suggests the effective
Ppy-GO/EP 1.815 × 10− 8 Amirazodi et al [130] utilization of CNTs in epoxy resin for self-healing and corrosion pro­
PDA/PANI-GO/WAV 5.99× x10− 6 Wang et al [131] tection. Similarly epoxy/PANI/ZnO hybrid multifunctional coatings
GO/PCL 1.033 × 10− 8 Rajitha et al [132]
R+(H + GO) 0.22 × 10− 6 Pourhashem et al. [78]
have been introduced by Najjar et al. [148] for corrosion protection and
PGT/WEP 0.418 × 10− 9 Wang et al. [133] self-healing. Kumar et al. [149] reported the antifouling and anticor­
Epoxy/GO-SiO2 0.09 × 10− 6 Pourhashem et al. [134] rosive system based on silicon/phosphorous/epoxy hybrid coatings.
GP0.05 2.725 × 10− 8 Rajitha et al. [135] Quan et al. [150] prepared epoxy/p-aminophenol coatings with anti­
MoS2-RGO/epoxy 0.0049 Chen et al. [136]
microbial/antifouling and anticorrosive properties. Based on the
GO-PPy-Zn extract 3.22 × 10− 6 Khani et al. [126]
research conducted so far in the area of multifunctional epoxy coatings,
Epoxy/GO; epoxy/graphene oxide. Epoxy/M-gel-GO; epoxy/modified gelatin several epoxy systems have been used for fouling and corrosion pro­
graphene oxide. Ly-GO-EP lysine functionalised graphene oxide reinforced tection such as APTES modified TiO2/DGEBA, silicon/phosphorous/
epoxy coating GP0.05 Polypyrrole doped graphene oxide epoxy coatings PDA/
sulphur/DGEBA as reported by Saravanan et al. [151] and Kumar et al.
PANI-GO/WAV polydopamine modified polyaniline-graphene oxide hybrid in
[152]. In this section, we are discussing on the development of self-
water based alkyd vanish. GO/PCL modified graphene oxide – Polycaprolactone.
healing, super-hydrophobic and antifouling coatings based on epoxy/
R+(H + GO); dispersion of hardner followed by mixing with resin. PGT/WEP;
polydopamine@graphene oxide‑titanium dioxide/water borne epoxy. Epoxy/ graphene composites for the increased corrosion protection.
GO-SiO2, epoxy graphene oxide silica hybrid. GP0.05; polypyrrole functionalized
graphene oxide. MoS2-RGO/epoxy; molybdenum disulphide-reduced graphene
5.1. Super-hydrophobic self-cleaning -corrosion resistant coatings
oxide hybrid reinforced epoxy coatings. GO-PPy-Zn extract; graphene oxide
polypyrrole zinc hybrid reinforced epoxy coating.
There is an increased demand has been given to super hydrophobic
coatings for corrosion protection [115] [153]. Super hydrophobic
coatings are those which exhibits a water contact angle of at least 150◦
and are extremely difficult to wet. This anti wetting property of super
hydrophobic coatings boosts the corrosion prevention. Chang et al.
[154] gives an insight into the bio-inspired super hydrophobic epoxy/
GO coatings for corrosion protection. They have duplicated the surface
features of Xanthosoma Sagittifolium leaves with the help of PDMS

Fig. 18. Corrosion protection mechanism of zinc rich epoxy/rGO coat­

ings [142].

compatibility with non-polar solvents, resulting in the particle

agglomeration and phase separation [15].

5. Multifunctional smart epoxy/graphene coatings

Multifunctional coatings are a class of coatings that can be tailored

Fig. 20. Digital photograph of a) natural leaf, b) SEM images of the natural leaf
for many applications and exhibits an impressive array of performance and c) PDMS template [154].

Fig. 19. Corrosion protection mechanism of GO sheets with different aspect ratio [77].

15
J.S. George et al. Progress in Organic Coatings 162 (2022) 106571

Fig. 21. Self-cleaning test of the composite at an angle ⁓8◦ using graphite as dirt a) BLc, b) GOc and c) FGc [106].

templates. Fig. 20 shows the image of the natural leaf (a) and SEM im­ structures of the leaf. This confirms the PDMS temple effectively repli­
ages of the natural leaf and the prepared PDMS template. The cated the topologically inverse structures of the hydrophobic leaves. The
morphological analysis of the composite exhibits the similar topological corrosion protection performance of these coatings was measured and

Fig. 22. Self-healing protection mechanism of WEC coatings [162].

16
J.S. George et al.
Fig. 23. FESEM images of the coatings before and after corrosion (a&b) bare steel, (c&d) EPN coatings, (e&f) EPG-1 coatings [167].
the Icorr values of the coatings are 0.35 and 0.10 μA/cm2 respectively for
hydrophobic epoxy composites and neat epoxy composites.
Yang et al. [106] discussed the self-cleaning and anticorrosion
properties of the epoxy/fluro graphene coatings. Lotus leaf effect was
the inspiration behind the research on the self-cleaning polymer coat­
ings. The self-cleaning property of the composite was analysed by its
ability to remove the graphite powder from its surface. As shown in
Fig. 21, BLc represents blank epoxy resin, GOc represents GO/epoxy
coatings and FGc represents fluorographene coatings. After the self-
cleaning test of FGc with graphite and water, its surface remains same
as the freshly prepared FGC within the 25 s.however, in the case of BLc
and GOc surface the water droplet could neither roll off the surface or
clean. Therefore, the incorporation of fluorographene in the epoxy
coating enhances its self-cleaning property drastically. The corrosion
protection efficiency of the same coating was analysed in 3.5% NaCl
solution.
5.2. Self-healing corrosion resistant coatings
Continues exposure of the coated metallic parts in harsh environ­
ment may results in several cracks and damages in it. Self-healing is a
novel approach introduced by researchers [155], [156] [147] ‘Self-
healing’ coatings are those is the property of a material to reconstruct
from damages, which was inspired from nature where the biological
17
Progress in Organic Coatings 162 (2022) 106571
species heal cuts or wounds [157] [158] [159]. Epoxy coatings have
been specially designed with self-healing functionality to further assist
the protection of metal parts [160] [161]. Many researchers report the
self-healing epoxy/GO based coating for corrosion protection. Moham­
madkhani et al. [126] reported the self-healing and barrier properties of
epoxy/GO-Zn-polypyrrole composites (Ppy). Incorporation of GO-Zn-
ppy imparts the self-healing property to the system. Also, the higher
low impedance value |Z|0.01HZ of GO-Zn-Ppy revels its corrosion resis­
tance. In parallel, Chen et al. [162] demonstrated the multifunctional
water borne epoxy coatings (WEC) using GO and polydopamine (PDA)
coated hallocyte nano tubes (PDA@HNT). The prepared coating shows
corrosion resistance and self-healing ability. The mechanism of self-
healing was given in the Fig. 22. The local changes in the PH associ­
ated with corrosion process results in the stripping of PDA from the
surface of HNT, which results in the release of corrosion inhibitor ben­
zotriazole (BTA). Self-healing property of PBH/WEC was attributed to
the formation of BTA-Fe-BTA complex. Whereas GO@PBH/WEC coat­
ings exhibit the corrosion protection via reconnecting the detached PDA
polymer network by iron ion through catechol Fe3+ bonds.
5.3. Anti-fouling corrosion resistant coatings
Bio-fouling is a kind of pollution happened by the accumulation of
microorganisms, plants or algae on the floating surfaces. Various studies
J.S. George et al.
Fig. 24. a and b) Digital images of the coatings EPN and EPG-1 coatings before
immersion, c, d) after immersion and e, f) optical micrographs [167].
have been reported on dual functional anti corrosive and antifouling
coatings [163] [164] [165]. In this context, Shoukouhi et al. [166]
evaluated the efficiency of epoxy-PANI/P-phenylene functionalized GO
coatings for corrosion protection and fouling resistance. The percentage
of PANI was maintained as 2 wt% throughout the experiment. They have
found that the addition of 0.2 wt% of PGO shows outstanding corrosion
resistance and fouling resistance in a simulated environment.
Similarly Verma et al. [167] discussed the antifouling and corrosion
resistance properties of epoxy/hydroxyl terminated PDMS and GO
composites. Morphology of the bare steel, epoxy/PDMS (EPN) and
epoxy PDMS with 1 wt% of GO (EPG-1) was analysed before and after
corrosion by taking FESEM images. As shown in Fig. 23, bare steel ex­
hibits several defects in its surface after corrosion. For EPN coatings, a
swelled texture with numerous pores was observed, attributed by the
dissolution of Cl− ions. This failure morphology of the EPN coating was
in line with its high Icorr values, whereas EPG-1 shows the presence of
several nanoflakes in it after corrosion with an accumulated thin layer of
corrosion products. Field immersion study of the coatings was con­
ducted in sea water for 9 months. As shown in Fig. 24, several enormous
fouling was found in EPN coatings. EPG-1 coatings show good fouling
resistance. This may be due to the good antifouling property of the
system and excellent dispersion of the GNs in the blend.
6. Summary and conclusions
Studies and statistics show that marine corrosion is a sombre concern
in the last few decades and about 90% of ship catastrophes are credited
to corrosion fatigue. Underground and submarine coated structures like
oil and gas pipelines are at a high risk of failure due to localized
corrosion and stress corrosion cracking Organic polymeric coatings,
18
Progress in Organic Coatings 162 (2022) 106571
organic-inorganic hybrid coatings, and inorganic coatings and metallic
coatings display good corrosion resistance in practical applications.
Graphene and graphene-based composites have received extensive sci­
entific curiosity due to their astonishing physical and barrier properties.
Recently, the gifted barrier properties of graphene and its derivatives got
prodigious interest in anticorrosive coatings. Graphene possesses
excellent barrier properties likewise epoxy resin possesses good anti­
corrosion properties. GO has been successfully used to reinforce epoxy
resin to improve the barrier properties against corrosive agents effec­
tively. The dispersion and compatibility of graphene in the polymer
matrix is a serious concern. Doping of graphene with other fillers help to
form stable dispersion with less agglomeration to an extent with
improved corrosion protection, however, these challenges are more
obvious and serious for the fillers at nanoscale size level because of their
easy agglomeration and large specific surface area. Novel tailored
multifunctional epoxy/graphene coatings for corrosion protection was
explained. The findings in this review article potentially broadens the
applications of epoxy/graphene as smart coatings for corrosion
protection.
7. Future perspectives
Advancements in nanotechnology and material science pave a way
for the developments of effective anti-corrosive coatings. Tailoring of
polymer coatings with nanostructured materials help to obtain novel
coating systems for futuristic applications. New innovations in the
coating systems such as self-healing coatings with corrosion resistance
and fouling resistance, are capable of protecting the marine articulates
from severe damage and achieves their long-term application. Such
smart coatings will become more common in practical applications after
several improvements and modifications on the existing systems.
Among the dense 2D nanostructures for corrosion protection, such as
hexagonal boron nitride, molybdenum disulfide, graphene and molyb­
denum diselenide, graphene has been the most studied one. Graphene
derivatives have shown promising scope to develop nanostructures with
several tunable properties particularity barrier properties. Indeed,
detailed investigation on the 2D nanostructures such as MoS2 and BN
should be explored more for next generation smart coatings.
Although pristine graphene showed excellent corrosion resistance,
its high conductivity leads to galvanic corrosion and its control is still a
major challenge. Functionalization and conjugation of graphene sheets
with other nanostructures can reduce this problem to a large extent.
When the graphene sheet orientation is parallel to the metal surface, the
barrier effect is found to be maximum. However, more meaning full and
strong research outputs are required in this direction. Investigation on
the correlation between GO sheet alignment and barrier effect will be a
strong and promising research area in the coming years. A thorough
understanding of the protection mechanism and degradation mecha­
nism by mathematical models will be a new interesting area to explore.
More research on the sustainable development of multifunctional
coating based on epoxy/GO composites need to explore for a better
future.
Author statement
We confirm that this work is original and has not been published
elsewhere, nor is it currently under consideration for publication else­
where. We hereby confirm that all authors have seen and approved the
final version of the manuscript being submitted.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
J.S. George et al.
Acknowledgements
This work was supported by the Defence Research and Development
Organisation, India (DRDO), Naval Research Board under Grant (NRB-
429/MAT/18-19) and Department of Science and Technology, India
(DST), through Innovation of Science Pursuit for Inspire Research pro­
gramme under grant (INSPIRE-IF190284).
References
[1] C. Jiang, Y. Cao, G. Xiao, R. Zhu, A review on the application of inorganic
nanoparticles in chemical surface coatings on metallic substrates, RSC Adv. 7
(2017) 7531–7539, https://doi.org/10.1039/c6ra25841g.
[2] Y. Li, H. Yang, Y.H. Wang, F. Wang, Superior anticorrosion performance of epoxy-
based composites with well-dispersed melamine modified graphene oxide,
J. Appl. Polym. Sci. 138 (2020) 1–14, https://doi.org/10.1002/app.49866.
[3] M. Fontana, Corrosion Engineering, 1987.
[4] M.J. Kim, J.S. Kim, D.J. Kim, H.P. Kim, Electro-deposition of oxide-dispersed
nickel composites and the behavior of their mechanical properties, Met. Mater.
Int. 15 (2009) 789–795, https://doi.org/10.1007/s12540-009-0789-2.
[5] J. Novakovic, P. Vassiliou, Vacuum thermal treated electroless NiP – TiO2
composite coatings, Electrochim. Acta 54 (2009) 2499–2503, https://doi.org/
10.1016/j.electacta.2008.12.015.
[6] A. Aubert, J. Danroc, A. Gaucher, J.P. Terrat, Hard chrome and molybdenum
coatings produced by physical vapour deposition, Thin Solid Ftlms. 126 (1985)
61–67.
[7] Y. Gonza, S. Gonza'lez, R.M. Souto, Electrochemical and structural properties of a
polyurethane coating on steel substrates for corrosion protection, Corros. Sci. 49
(2007) 3514–3526, https://doi.org/10.1016/j.corsci.2007.03.018.
[8] J.R. Xavier, Effect of surface modified WO3 nanoparticle on the epoxy coatings
for the adhesive and anticorrosion properties of mild steel, J. Appl. Polym. Sci.
48323 (2019) 1–10, https://doi.org/10.1002/app.48323.
[9] S.B. Lyon, R. Bingham, D.J. Mills, Advances in corrosion protection by organic
coatings: what we know and what we would like to know, Prog. Org. Coat. 102
(2017) 2–7, https://doi.org/10.1016/j.porgcoat.2016.04.030.
[10] S. Pourhashem, F. Saba, J. Duan, A. Rashidi, F. Guan, E. Garmroudi, B. Hou,
Polymer/inorganic nanocomposite coatings with superior corrosion protection
performance: a review, J. Ind. Eng. Chem. 88 (2020) 29–57, https://doi.org/
10.1016/j.jiec.2020.04.029.
[11] Y. Jing, P. Wang, Q. Yang, Q. Wang, Y. Bai, MoS2 decorated with ZrO2
nanoparticles through mussel-inspired chemistry of dopamine for reinforcing
anticorrosion of epoxy coatings, Colloids Surf. A Physicochem. Eng. Asp. 608
(2021), 125625, https://doi.org/10.1016/j.colsurfa.2020.125625.
[12] A.M. Atta, G.A. El-mahdy, H.A. Al-lohedan, A.O. Ezzat, Synthesis and application
of hybrid polymer composites based on silver nanoparticles as corrosion
protection for line pipe steel, Molecules. 19 (2014) 6246–6262, https://doi.org/
10.3390/molecules19056246.
[13] M. Akbarian, M.E. Olya, M. Mahdavian, M. Ataeefard, Effects of nanoparticulate
silver on the corrosion protection performance of polyurethane coatings on mild
steel in sodium chloride solution, Prog. Org. Coat. 77 (2014) 1233–1240, https://
doi.org/10.1016/j.porgcoat.2014.03.023.
[14] G. Cui, Z. Bi, R. Zhang, J. Liu, X. Yu, Z. Li, A comprehensive review on graphene-
based anti-corrosive coatings, Chem. Eng. J. 373 (2019) 104–121.
[15] R. Ding, W. Li, X. Wang, T. Gui, B. Li, P. Han, H. Tian, A. Liu, X. Wang, X. Liu,
X. Gao, W. Wang, L. Song, A brief review of corrosion protective films and
coatings based on graphene and graphene oxide, J. Alloys Compd. 764 (2018)
1039–1055, https://doi.org/10.1016/j.jallcom.2018.06.133.
[16] P.P. Deshpande, N.G. Jadhav, V.J. Gelling, D. Sazou, Conducting polymers for
corrosion protection: a review, J. Coat. Technol. Res. 11 (2014) 473–494, https://
doi.org/10.1007/s11998-014-9586-7.
[17] P.A. Sørensen, S. Kiil, K. Dam-Johansen, C.E. Weinell, Anticorrosive coatings: a
review, J. Coat. Technol. Res. 6 (2009) 135–176, https://doi.org/10.1007/
s11998-008-9144-2.
[18] G.S. Gonalves, A.F. Baldissera, L.F. Rodrigues, E.M.A. Martini, C.A. Ferreira,
Alkyd coatings containing polyanilines for corrosion protection of mild steel,
Synth. Met. 161 (2011) 313–323, https://doi.org/10.1016/j.
synthmet.2010.11.043.
[19] M.F. Montemor, Functional and smart coatings for corrosion protection: a review
of recent advances, Surf. Coat. Technol. 258 (2014) 17–37, https://doi.org/
10.1016/j.surfcoat.2014.06.031.
[20] Practical self-study guide to corrosion control, in: Book, [WorldCat.Org], (n.d.),
1998. https://www.worldcat.org/title/practical-self-study-guide-to-corrosion-co
ntrol/oclc/39361431 (accessed October 14, 2020).
[21] H. Wei, J. Xia, W. Zhou, L. Zhou, G. Hussain, Q. Li, K. Ostrikov, Adhesion and
cohesion of epoxy-based industrial composite coatings, Compos. Part B 193
(2020), 108035, https://doi.org/10.1016/j.compositesb.2020.108035.
[22] E. Sadeghi, N. Markocsan, S. Joshi, Advances in corrosion-resistant thermal spray
coatings for renewable energy power plants. Part I: effect of composition and
microstructure deposit, J. Therm. Spray Technol. 28 (2019) 1749–1788, https://
doi.org/10.1007/s11666-019-00938-1.
[23] J.R. Davis, Corrosion, in: Understanding the Basics, ASM International, 2000.
19
Progress in Organic Coatings 162 (2022) 106571
[24] F. Presuel-Moreno, M.A. Jakab, N. Tailleart, M. Goldman, J.R. Scully, Corrosion-
resistant metallic coatings, Mater. Today 11 (2008) 14–23, https://doi.org/
10.1016/S1369-7021(08)70203-7.
[25] N. Priyantha, P. Jayaweera, A. Sanjurjo, K. Lau, F. Lu, K. Krist, Corrosion-resistant
metallic coatings for applications in highly aggressive environments, Surf. Coat.
Technol. 163–164 (2003) 31–36, https://doi.org/10.1016/S0257-8972(02)
00590-X.
[26] P. Jayaweera, D.M. Lowe, A. Sanjurjo, K.H. Lau, L. Jiang, Corrosion-resistant
metallic coatings on low carbon steel, Surf. Coat. Technol. 87 (1996) 522–525.
[27] N. Priyantha, P. Jayaweera, A. Sanjurjo, K. Lau, F. Lu, K. Krist, Corrosion-resistant
metallic coatings for applications in highly aggressive environments, Surf. Coat.
Technol. 164 (2003) 31–36.
[28] Y. Chen, S. Shen, Q. Hou, Z. Zhang, J. Gu, Novel green manufacture of metallic
aluminum coatings on carbon steel by sol–gel method, RSC Adv. 11 (2021)
6720–6734, https://doi.org/10.1039/d0ra08175b.
[29] G. Liu, Y. An, Z. Guo, J. Chen, G. Hou, J. Chen, Structure and corrosion behavior
of iron-based metallic glass coatings prepared by LPPS, Appl. Surf. Sci. 258
(2012) 5380–5386, https://doi.org/10.1016/j.apsusc.2012.02.015.
[30] L. Bamoulid, M.T. Maurette, D. De Caro, A. Guenbour, A. Ben Bachir, L. Aries,
S. El Hajjaji, F. Benoît-Marquié, F. Ansart, An efficient protection of stainless steel
against corrosion: combination of a conversion layer and titanium dioxide
deposit, Surf. Coat. Technol. 202 (2008) 5020–5026, https://doi.org/10.1016/j.
surfcoat.2008.05.011.
[31] H. Cheraghi, M. Shahmiri, Z. Sadeghian, Corrosion behavior of TiO2–NiO
nanocomposite thin fi lms on AISI 316L stainless steel prepared by sol – gel
method, Thin Solid Films 522 (2012) 289–296, https://doi.org/10.1016/j.
tsf.2012.07.125.
[32] Q. Yu, X. Ma, M. Wang, C. Yu, T. Bai, Influence of embedded particles on
microstructure, corrosion resistance and thermal conductivity of CuO/SiO2 and
NiO/SiO2 nanocomposite coatings, Appl. Surf. Sci. 254 (2008) 5089–5094,
https://doi.org/10.1016/j.apsusc.2008.02.042.
[33] T. Xiang, S. Zheng, M. Zhang, H.R. Sadig, C. Li, Bioinspired slippery zinc
phosphate coating for sustainable corrosion protection, ACS Sustain. Chem. Eng.
6 (2018) 10960–10968, https://doi.org/10.1021/acssuschemeng.8b02345.
[34] B. Ramezanzadeh, M.M. Attar, Studying the corrosion resistance and hydrolytic
degradation of an epoxy coating containing ZnO nanoparticles, Mater. Chem.
Phys. 130 (2011) 1208–1219, https://doi.org/10.1016/j.
matchemphys.2011.08.065.
[35] K. Alaoui, Y. El Kacimi, M. Galai, R. Touir, K. Dahmani, A. Harfi, M.E. Touhami,
Anti-corrosive properties of polyvinyl-alcohol for carbon steel in hydrochloric
acid media: electrochemical and thermodynamic investigation, J. Mater. Environ.
Sci. 7 (2016) 2389–2403.
[36] F.B. Diniz, G.F. De Andrade, C.R. Martins, W.M. De Azevedo, A comparative study
of epoxy and polyurethane based coatings containing polyaniline-DBSA pigments
for corrosion protection on mild steel, Prog. Org. Coat. 76 (2013) 912–916,
https://doi.org/10.1016/j.porgcoat.2013.02.010.
[37] M. Faustini, L. Nicole, E. Ruiz-hitzky, C. Sanchez, History of organic – inorganic
hybrid materials: prehistory, art, science, and advanced applications, Adv. Funct.
Mater. 1704158 (2018) 1–30, https://doi.org/10.1002/adfm.201704158.
[38] A. Abdul, K. Yop, S. Jin, D. Hui, Epoxy clay nanocomposites – processing,
properties and applications: a review, Compos. B. Eng. 45 (2013) 308–320,
https://doi.org/10.1016/j.compositesb.2012.04.012.
[39] R. Zandi-zand, A. Ershad-langroudi, A. Rahimi, Silica based organic – inorganic
hybrid nanocomposite coatings for corrosion protection, Prog. Org. Coat. 53
(2005) 286–291, https://doi.org/10.1016/j.porgcoat.2005.03.009.
[40] M.J. Palimi, M. Rostami, M. Mahdavian, B. Ramezanzadeh, The corrosion
protection performance of the polyurethane coatings containing surface modified
Fe2O3 nanoparticles, Corrosion. 71 (2015) 1012–1026, https://doi.org/10.5006/
1365.
[41] A. Samadi, R. Amini, M. Rostami, P. Kardar, M. Fedel, Active corrosion
performance of magnesium by silane coatings reinforced with polyaniline/
praseodymium, Prog. Org. Coat. 140 (2020), 105504, https://doi.org/10.1016/j.
porgcoat.2019.105504.
[42] R. Rajkumar, C. Vedhi, A study of corrosion protection efficiency of silica
nanoparticles acrylic coated on mild steel electrode, Vacuum. 161 (2018) 1–4,
https://doi.org/10.1016/j.vacuum.2018.12.005.
[43] Y.H. Yu, Y.Y. Lin, C.H. Lin, C.C. Chan, Y.C. Huang, High-performance
polystyrene/graphene-based nanocomposites with excellent anti-corrosion
properties, Polym. Chem. 5 (2014) 535–550, https://doi.org/10.1039/
c3py00825h.
[44] E. Salehoon, S.J. Ahmadi, S.M. Razavi, N. Parvin, Thermal and corrosion
resistance properties of unsaturated polyester/clay nanocomposites and the effect
of electron beam irradiation, Polym. Bull. 74 (2017) 1629–1647, https://doi.org/
10.1007/s00289-016-1793-1.
[45] V.P.R. Remya, S. Thomas, O.S. Oluwafemi, Compatibilization of epoxidized
triblock copolymer on the generation of self-assembled nanostructured epoxies
and their surface wettability, J. Appl. Polym. Sci. (2020) 1–13, https://doi.org/
10.1002/app.49985.
[46] A.M. Atta, A.M. El-Saeed, G.M. El-Mahdy, H.A. Al-Lohedan, Application of
magnetite nano-hybrid epoxy as protective marine coatings for steel, RSC Adv. 5
(2015) 101923–101931, https://doi.org/10.1039/c5ra20730d.
[47] C. Verma, L.O. Olasunkanmi, E.D. Akpan, M.A. Quraishi, Epoxy resins as
anticorrosive polymeric materials: a review, React. Funct. Polym. 156 (2020),
104741.
[48] A. Reghunadhan, J. Datta, N. Kalarikkal, S. Thomas, Development of nanoscale
morphology and role of viscoelastic phase separation on the properties of epoxy/
J.S. George et al.
recycled polyurethane blends, Polymer. 117 (2017) 96–106, https://doi.org/
10.1016/j.polymer.2017.04.030.
[49] V. Susan, M. Christophe, S.C. George, S. Thomas, Epoxy resin/liquid natural
rubber system: secondary phase separation and its impact on mechanical
properties, J. Mater. Sci. 45 (2010) 1769–1781, https://doi.org/10.1007/s10853-
009-4154-8.
[50] J. Joy, E. George, S. Thomas, S. Anas, Effect of filler loading on polymer chain
confinement and thermo-mechanical properties of epoxy/boron nitride (h-BN)
nanocomposites, New J. Chem. 44 (2020) 4494–4503, https://doi.org/10.1039/
C9NJ05834F.
[51] R. Thomas, D. Yumei, H. Yuelong, Y. Le, P. Moldenaers, Y. Weimin, T. Czigany,
S. Thomas, Miscibility, morphology, thermal, and mechanical properties of a
DGEBA based epoxy resin toughened with a liquid rubber, Polymer. 49 (2008)
278–294, https://doi.org/10.1016/j.polymer.2007.11.030.
[52] A. Surendran, J. Pionteck, R. Vogel, N. Kalarikkal, V.G. G., S. Thomas, Effect of
organically modified clay on the morphology, rheology and viscoelasticity of
epoxy –thermoplastic nanocomposites, Polym. Test. 70 (2018) 18–29, https://
doi.org/10.1016/j.polymertesting.2018.06.023.
[53] H. Tanaka, T. Koyama, T. Araki, Network formation in viscoelastic phase
separation, J. Phys. Condens. Matter 15 (2003) 387–393.
[54] P.P. Vijayan, D. Puglia, J.M. Kenny, S. Thomas, Effect of organically modified
nanoclay on the miscibility, rheology, morphology and properties of epoxy/
carboxyl-terminated (butadiene-co- acrylonitrile) blend, Soft Matter 9 (2013)
2899–2911, https://doi.org/10.1039/c2sm27386a.
[55] Y. Xia, Y. He, C. Chen, Y. Wu, J. Chen, MoS2 nanosheets modified SiO2 to
enhance the anticorrosive and mechanical performance of epoxy coating, Prog.
Org. Coat. 132 (2019) 316–327, https://doi.org/10.1016/j.
porgcoat.2019.04.002.
[56] T. Thi Xuan Hang, T.A. Truc, T.H. Nam, V.K. Oanh, J.B. Jorcin, N. Pébère,
Corrosion protection of carbon steel by an epoxy resin containing organically
modified clay, Surf. Coat. Technol. 201 (2007) 7408–7415, https://doi.org/
10.1016/j.surfcoat.2007.02.009.
[57] W.G. Ji, J.M. Hu, J.Q. Zhang, C.N. Cao, Reducing the water absorption in epoxy
coatings by silane monomer incorporation, Corros. Sci. 48 (2006) 3731–3739,
https://doi.org/10.1016/j.corsci.2006.02.005.
[58] S. Chhetri, P. Samanta, N. Murmu, T. Kuila, Anticorrosion properties of epoxy
composite coating reinforced by molybdate-intercalated functionalized layered
double hydroxide, J. Compos. Sci. 3 (2019) 1–14, https://doi.org/10.3390/
jcs3010011.
[59] W. Choi, I. Lahiri, R. Seelaboyina, Y.S. Kang, Synthesis of graphene and its
applications: a review, Crit. Rev. Solid State Mater. Sci. 35 (2010) 52–71, https://
doi.org/10.1080/10408430903505036.
[60] X. Jin, C. Feng, D. Ponnamma, Z. Yi, J. Parameswaranpillai, S. Thomas, N.
V. Salim, Review on exploration of graphene in the design and engineering of
smart sensors, actuators and soft robotics, Chem. Eng. J. Adv. 4 (2020), 100034,
https://doi.org/10.1016/j.ceja.2020.100034.
[61] A.K. Geim, Graphene: status and prospects, Science. 324 (2009) 1530–1534,
https://doi.org/10.1126/science.1158877.
[62] D. Prasai, J.C. Tuberquia, R.R. Harl, G.K. Jennings, K.I. Bolotin, Graphene:
corrosion-inhibiting coating, ACS Nano 6 (2012) 1102–1108, https://doi.org/
10.1021/nn203507y.
[63] B. Li, X. Jin, J. Lin, Z. Chen, Green reduction of graphene oxide by sugarcane
bagasse extract and its application for the removal of cadmium in aqueous
solution, J. Clean. Prod. 189 (2018) 128–134, https://doi.org/10.1016/j.
jclepro.2018.04.018.
[64] S. Yaragalla, R. Rajendran, J. Jose, M.A. Almaadeed, N. Kalarikkal, S. Thomas,
Preparation and characterization of green graphene using grape seed extract for
bioapplications, Mater. Sci. Eng. C 65 (2016) 345–353, https://doi.org/10.1016/
j.msec.2016.04.050.
[65] J. Nine, M.A. Cole, D.N.H. Tran, D. Losic, Graphene: a multipurpose material for
protective coatings, J. Mater. Chem. A 3 (2015) 12580–12602, https://doi.org/
10.1039/C5TA01010A.
[66] M.-I. Necolau, A.-M. Pandele, Recent advances in graphene oxide-based
anticorrosive coatings: an overview, Coatings. 10 (2020) 1–15, https://doi.org/
10.3390/coatings10121149.
[67] R.K.S. Raman, A. Tiwari, Graphene: the thinnest known coating for corrosion
protection, JOM. 66 (2014) 637–642, https://doi.org/10.1007/s11837-014-
0921-3.
[68] G. Synthesis, M. Saeed, Y. Alshammari, S.A. Majeed, E. Al-Nasrallah, Chemical
vapour deposition of graphene—synthesis, Characterisation, and applications: a
review, molecules. 25 (2020) 1–62, https://doi.org/10.3390/
molecules25173856.
[69] M. Diba, D.W.H. Fam, A.R. Boccaccini, M.S.P. Shaffer, Electrophoretic deposition
of graphene-related materials: a review of the fundamentals, Prog. Mater. Sci. 82
(2016) 83–117, https://doi.org/10.1016/j.pmatsci.2016.03.002.
[70] X. Liu, J. Mao, P. Liu, X. Wei, Fabrication of metal-graphene hybrid materials by
electroless deposition, Carbon. 49 (2010) 477–483, https://doi.org/10.1016/j.
carbon.2010.09.044.
[71] P.K. Nayak, C. Hsu, S. Wang, J.C. Sung, J. Huang, Graphene coated Ni films: a
protective coating, Thin Solid Films 529 (2012) 312–316, https://doi.org/
10.1016/j.tsf.2012.03.067.
[72] Vesna Mišković-Stanković, I. Jung Jevremovic, K. Rhee, Electrochemical study of
corrosion behavior of graphene coatings on copper and aluminum in a chloride
solution, Carbon. 75 (2014) 335–344, https://doi.org/10.1016/j.
carbon.2014.04.012.
20
Progress in Organic Coatings 162 (2022) 106571
[73] S. Chen, L. Brown, M. Levendorf, W. Cai, S. Ju, J. Edgeworth, X. Li, C.
W. Magnuson, A. Velamakanni, R. Junyong KangPiner, J. Park, R.S. Ruoff,
Oxidation resistance of graphene-coated Cu and Cu/Ni alloy, ACS Nano 5 (2011)
1321–1327, https://doi.org/10.1021/nn103028d.
[74] Y.J. Yuda Zhao, Yizhu Xie, Yeung Yu Hui, Libin Tang, S.P.L.Y.C. Ling Xu Wenjing
Jie, Highly impermeable and transparent graphene as an ultra-thin protection
barrier for Ag thin films, J. Mater. Chem. C 1 (2013) 4956–4961, https://doi.org/
10.1039/c3tc30743c.
[75] D.G. Papageorgiou, I.A. Kinloch, R.J. Young, Mechanical properties of graphene
and graphene-based nanocomposites, Prog. Mater. Sci. 90 (2017) 75–127,
https://doi.org/10.1016/j.pmatsci.2017.07.004.
[76] L. Zhang, H. Wu, M. Wei, Z. Zheng, D.D. Vu, T. Tuyet, X. Bui, X. Huang,
Preparation, characterization, and properties of graphene oxide/urushiol-
formaldehyde polymer composite coating, J. Coat. Technol. Res. 15 (2018)
1343–1356, https://doi.org/10.1007/s11998-018-0084-1.
[77] F. Jiang, W. Zhao, Y. Wu, J. Dong, K. Zhou, G. Lu, J. Pu, Anti-corrosion behaviors
of epoxy composite coatings enhanced via graphene oxide with different aspect
ratios, Prog. Org. Coat. 127 (2019) 70–79, https://doi.org/10.1016/j.
porgcoat.2018.11.008.
[78] S. Pourhashem, M.R. Vaezi, A. Rashidi, M.R. Bagherzadeh, Exploring corrosion
protection properties of solvent based epoxy-graphene oxide nanocomposite
coatings on mild steel, Corros. Sci. 115 (2016) 78–92, https://doi.org/10.1016/j.
corsci.2016.11.008.
[79] S. Manchala, V.S.R.K. Tandava, D. Jampaiah, S.K. Bhargava, V. Shanker, Novel
and highly efficient strategy for the green synthesis of soluble graphene by
aqueous polyphenol extracts of Eucalyptus bark and its applications in high-
performance supercapacitors, ACS Sustain. Chem. Eng. 7 (2019) 11612–11620,
https://doi.org/10.1021/acssuschemeng.9b01506.
[80] J.S. George, K.P. Jibin, V. Prajitha, S. Thomas, Spectroscopic characterizations of
graphitic structures, Emerging Trends in Spectroscopy (2019) 1–16.
[81] J. Li, H. Zheng, L. Liu, F. Meng, Y. Cui, F. Wang, Modification of graphene and
graphene oxide and their applications in anticorrosive coatings, J. Coat. Technol.
Res. 18 (2021) 311–331, https://doi.org/10.1007/s11998-020-00435-z.
[82] N. Pu, C. Wang, Y. Liu, Y. Sung, D. Wang, M. Ger, Dispersion of graphene in
aqueous solutions with different types of surfactants and the production of
graphene films by spray or drop coating, J. Taiwan Inst. Chem. Eng. 43 (2012)
140–146, https://doi.org/10.1016/j.jtice.2011.06.012.
[83] A. Uthaman, H.M. Lal, C. Li, G. Xian, S. Thomas, Mechanical and water uptake
properties of epoxy nanocomposites with surfactant-modified functionalized
multiwalled carbon nanotubes, Nanomaterials. 11 (2021) 1–15, https://doi.org/
10.3390/nano11051234.
[84] Z.G. Mohammadsalih, B.J. Inkson, B. Chen, The effect of dispersion condition on
the structure and properties of polystyrene/graphene oxide nanocomposites,
Polym. Compos. (2020) 320–328, https://doi.org/10.1002/pc.25827.
[85] D. Konios, M.M. Stylianakis, E. Stratakis, E. Kymakis, Dispersion behaviour of
graphene oxide and reduced graphene oxide, J. Colloid Interface Sci. 430 (2014)
108–112, https://doi.org/10.1016/j.jcis.2014.05.033.
[86] Z. Qin, M. Taylor, M. Hwang, K. Bertoldi, M.J. Buehler, Effect of wrinkles on the
surface area of graphene: toward the design of nanoelectronics, Nano Lett. 14
(2014) 6520–6525, https://doi.org/10.1021/nl503097u.
[87] C. Salom, M.G. Prolongo, A. Toribio, A.J. Martínez-Martínez, I.A. de Cárcer, S.
G. Prolongo, Mechanical properties and adhesive behavior of epoxy-graphene
nanocomposites, Int. J. Adhes. Adhes. 84 (2018) 119–125, https://doi.org/
10.1016/j.ijadhadh.2017.12.004.
[88] U. Kilic, M.M. Sherif, O.E. Ozbulut, Tensile properties of graphene nanoplatelets/
epoxy composites fabricated by various dispersion techniques, Polym. Test. 76
(2019) 181–191, https://doi.org/10.1016/j.polymertesting.2019.03.028.
[89] L.C. Tang, Y.J. Wan, D. Yan, Y.B. Pei, L. Zhao, Y.B. Li, L. Bin Wu, J.X. Jiang, G.
Q. Lai, The effect of graphene dispersion on the mechanical properties of
graphene/epoxy composites, Carbon. 60 (2013) 16–27, https://doi.org/10.1016/
j.carbon.2013.03.050.
[90] L. Amirova, A. Surnova, D. Balkaev, D. Musin, R. Amirov, A.M. Dimiev,
Homogeneous liquid phase transfer of Graphene oxide into epoxy resins, Appl.
Mater. Interfaces 9 (2017) 11909–11917, https://doi.org/10.1021/
acsami.7b02243.
[91] J.M. Chem, J. Liu, J.J. Gooding, Strategies for chemical modification of graphene
and applications of chemically modified graphene, J. Mater. Chem. 22 (2012)
12435–12452, https://doi.org/10.1039/c2jm31218b.
[92] X. Wang, X. Qi, Z. Lin, D. Battocchi, Graphene reinforced composites as protective
coatings for oil and gas pipelines, Nanomaterials. 8 (2018) 1–14, https://doi.org/
10.3390/nano8121005.
[93] Y.J. Wan, L.C. Tang, L.X. Gong, D. Yan, Y.B. Li, L. Bin Wu, J.X. Jiang, G.Q. Lai,
Grafting of epoxy chains onto graphene oxide for epoxy composites with
improved mechanical and thermal properties, Carbon. 69 (2014) 467–480,
https://doi.org/10.1016/j.carbon.2013.12.050.
[94] Y. Xie, C. Liu, W. Liu, L. Liang, S. Wang, F. Zhang, H. Shi, M. Yang, A novel
approach to fabricate polyacrylate modified graphene oxide for improving the
corrosion resistance of epoxy coatings, Colloids Surfaces A Physicochem. Eng.
Asp. 593 (2020), 124627, https://doi.org/10.1016/j.colsurfa.2020.124627.
[95] S. Pourhashem, A. Rashidi, M.R. Vaezi, M.R. Bagherzadeh, Excellent corrosion
protection performance of epoxy composite coatings filled with amino-silane
functionalized graphene oxide, Surf. Coat. Technol. 317 (2017) 1–9, https://doi.
org/10.1016/j.surfcoat.2017.03.050.
[96] S. Hou, S. Su, M.L. Kasner, P. Shah, K. Patel, C. John, Formation of highly stable
dispersions of silane-functionalized reduced graphene oxide, Chem. Phys. Lett.
501 (2010) 68–74, https://doi.org/10.1016/j.cplett.2010.10.051.
J.S. George et al.
[97] K. Rajitha, K. Narasimha, S. Mohana, A. Mohanan, A.M. Madhusudhana,
Evaluation of anti-corrosion performance of modi fi ed gelatin-graphene oxide
nanocomposite dispersed in epoxy coating on mild steel in saline media, Colloids
Surf. A Physicochem. Eng. Asp. 587 (2020), 124341, https://doi.org/10.1016/j.
colsurfa.2019.124341.
[98] M.G. Sari, B. Ramezanzadeh, Epoxy composite coating corrosion protection
properties reinforcement through the addition of hydroxyl-terminated
hyperbranched polyamide non-covalently assembled graphene oxide platforms,
Constr. Build. Mater. 234 (2020), 117421, https://doi.org/10.1016/j.
conbuildmat.2019.117421.
[99] Y. Hayatgheib, B. Ramezanzadeh, P. Kardar, M. Mahdavian, A comparative study
on fabrication of a highly effective corrosion protective system based on graphene
oxide-polyaniline nano fibers/epoxy composite, Corros. Sci. 133 (2018) 358–373,
https://doi.org/10.1016/j.corsci.2018.01.046.
[100] M. Ramezanzadeh, B. Ramezanzadeh, M.G. Sari, M.R. Saeb, Corrosion resistance
of epoxy coating on mild steel through polyamidoamine dendrimer-covalently
functionalized graphene oxide nanosheets, J. Ind. Eng. Chem. 82 (2020) 290–302,
https://doi.org/10.1016/j.jiec.2019.10.025.
[101] S. Pourhashem, M. Reza, A. Rashidi, M.R. Bagherzadeh, Distinctive roles of silane
coupling agents on the corrosion inhibition performance of graphene oxide in
epoxy coatings, Prog. Org. Coat. 111 (2017) 47–56, https://doi.org/10.1016/j.
porgcoat.2017.05.008.
[102] J. Cui, Z. Xiong, H. Qiu, J. Li, J. Yang, Functionalized graphene oxide: carrier for
corrosion inhibitor and barrier in waterborne epoxy coating, Compos. Part A
Appl. Sci. 144 (2021), 106354, https://doi.org/10.1016/j.
compositesa.2021.106354.
[103] S. Zhao, B. Dou, S. Duan, X. Lin, Y. Zhang, W. Emori, X. Gao, Z. Fang, Influence of
fluorinated graphene-modified epoxy coatings on the corrosion behaviour of 2024
aluminium alloy, RSC Adv. 11 (2021) 17558–17573, https://doi.org/10.1039/
d1ra01870a.
[104] Y. Wu, W. Zhao, Y. Qiang, Z. Chen, L. Wang, X. Gao, Z. Fang, π-π interaction
between fluorinated reduced graphene oxide and acridizinium ionic liquid:
synthesis and anti-corrosion application, Carbon. 159 (2020) 292–302, https://
doi.org/10.1016/j.carbon.2019.12.047.
[105] Z. Yang, W. Sun, L. Wang, Z. Wan, J. Wang, S. Wang, G. Liu, Tuning the oxygen
reduction reaction activity of graphene through fluorination modification to
inhibit its corrosion-promotion activity, Corros. Sci. 175 (2020), 108860, https://
doi.org/10.1016/j.corsci.2020.108860.
[106] Z. Yang, L. Wang, W. Sun, S. Li, T. Zhu, W. Liu, G. Liu, Superhydrophobic epoxy
coating modified by fluorographene used for anti-corrosion and self-cleaning,
Appl. Surf. Sci. 401 (2017) 146–155, https://doi.org/10.1016/j.
apsusc.2017.01.009.
[107] F. Lei, B. Wu, H. Sun, F. Jiang, J. Yang, D. Sun, Simultaneously improving the
anticorrosion and antiscratch performance of epoxy coatings with graphite
fluoride via large-scale preparation, Ind. Eng. Chem. Res. 57 (2018)
16709–16717, https://doi.org/10.1021/acs.iecr.8b04405.
[108] Y. Wu, W. Zhao, Z. Lu, L. Wang, Fluorinated graphene film for corrosion control
on copper: experimental and theoretical studies, Carbon. 179 (2021) 445–457,
https://doi.org/10.1016/j.carbon.2021.04.040.
[109] Z. Yu, H. Di, Y. Ma, Y. He, L. Liang, L. Lv, X. Ran, Y. Pan, Z. Luo, Preparation of
graphene oxide modified by titanium dioxide to enhance the anti-corrosion
performance of epoxy coatings, Surf. Coat. Technol. 276 (2015) 471–478, https://
doi.org/10.1016/j.surfcoat.2015.06.027.
[110] Y. Li, Y. Cao, J. Xie, D. Jia, H. Qin, Z. Liang, Facile solid-state synthesis of Ag/
graphene oxide nanocomposites as highly active and stable catalyst for the
reduction of 4-nitrophenol, Catal. Commun. 58 (2015) 21–25, https://doi.org/
10.1016/j.catcom.2014.08.022.
[111] L. Chen, S. Chai, K. Liu, N. Ning, J. Gao, Q. Liu, F. Chen, Q. Fu, Enhanced epoxy/
silica composites mechanical properties by introducing graphene oxide to the
interface, ACS Appl. Mater. Interfaces 4 (2012) 4398–4404, https://doi.org/
10.1021/am3010576.
[112] A. Kumar, R. Anant, K. Kumar, S.S. Chauhan, S. Kumar, R. Kumar, Anticorrosive
and electromagnetic shielding response of a graphene/TiO2–epoxy
nanocomposite with enhanced mechanical properties, RSC Adv. 6 (2016)
113405–113414, https://doi.org/10.1039/C6RA15273B.
[113] J. Liu, Q. Yu, M. Yu, S. Li, K. Zhao, B. Xue, H. Zu, Silane modification of titanium
dioxide-decorated graphene oxide nanocomposite for enhancing anticorrosion
performance of epoxy coatings on AA-2024, J. Alloys Compd. 744 (2018)
728–739, https://doi.org/10.1016/j.jallcom.2018.01.267.
[114] H. Di, Z. Yu, Y. Ma, C. Zhang, F. Li, L. Lv, Y. Pan, H. Shi, Y. He, Corrosion-resistant
hybrid coatings based on graphene oxide–zirconia dioxide/epoxy system,
J. Taiwan Inst. Chem. Eng. 67 (2016) 511–520, https://doi.org/10.1016/j.
jtice.2016.08.008.
[115] S. Ding, T. Xiang, C. Li, S. Zheng, J. Wang, M. Zhang, C. Dong, W. Chan,
Fabrication of self-cleaning super-hydrophobic nickel/graphene hybrid film with
improved corrosion resistance on mild steel, Mater. Des. 117 (2017) 280–288,
https://doi.org/10.1016/j.matdes.2016.12.084.
[116] M. Merisalu, T. Kahro, J. Kozlova, A. Niilisk, A. Nikolajev, M. Marandi, A. Floren,
H. Alles, V. Sammelselg, Graphene-polypyrrole thin hybrid corrosion resistant
coatings for copper, Synth. Met. 200 (2015) 16–23, https://doi.org/10.1016/j.
synthmet.2014.12.024.
[117] M.S. Selim, S.A. El-safty, M.A. Abbas, M.A. Shenashen, Facile design of graphene
oxide-ZnO nanorod-based ternary nanocomposite as a superhydrophobic and
corrosion-barrier coating, Colloids Surf. A Physicochem. Eng. Asp. 611 (2021),
125793, https://doi.org/10.1016/j.colsurfa.2020.125793.
21
Progress in Organic Coatings 162 (2022) 106571
[118] Y. Jafari, S.M. Ghoreishi, Polyaniline/Graphene nanocomposite coatings on
copper: electropolymerization, characterization, and evaluation of corrosion
protection performance, Synth. Met. 217 (2016) 220–230, https://doi.org/
10.1016/j.synthmet.2016.04.001.
[119] S. Wang, W. Liu, H. Shi, F. Zhang, Co-modification of nano-silica and lysine on
graphene oxide nanosheets to enhance the corrosion resistance of waterborne
epoxy coatings in 3.5% NaCl solution, Polymer 222 (2021), 123665, https://doi.
org/10.1016/j.polymer.2021.123665.
[120] H. Yan, L. Zhang, H. Li, X. Fan, M. Zhu, Towards high-performance additive of
Ti3C2/graphene hybrid with a novel wrapping structure in epoxy coating,
Carbon. 157 (2020) 217–233, https://doi.org/10.1016/j.carbon.2019.10.034.
[121] E. Bakhshandeh, A. Jannesari, Z. Ranjbar, S. Sobhani, M.R. Saeb, Anti-corrosion
hybrid coatings based on epoxy-silica nano-composites: toward relationship
between the morphology and EIS data, Prog. Org. Coat. 77 (2014) 1169–1183,
https://doi.org/10.1016/j.porgcoat.2014.04.005.
[122] Z. Yu, H. Di, Y. Ma, L. Lv, Y. Pan, C. Zhang, Y. He, Fabrication of graphene oxide-
alumina hybrids to reinforce the anti-corrosion performance of composite epoxy
coatings, Appl. Surf. Sci. 351 (2015) 986–996, https://doi.org/10.1016/j.
apsusc.2015.06.026.
[123] Y. Ma, H. Di, Z. Yu, L. Liang, L. Lv, Y. Pan, Y. Zhang, D. Yin, Fabrication of silica-
decorated graphene oxide nanohybrids and the properties of composite epoxy
coatings research, Appl. Surf. Sci. 360 (2016) 936–945, https://doi.org/10.1016/
j.apsusc.2015.11.088.
[124] Y. Wu, F. Jiang, Y. Qiang, W. Zhao, Synthesizing a novel fluorinated reduced
graphene oxide-CeO2 hybrid nanofiller to achieve highly corrosion protection for
waterborne epoxy coatings, Carbon. 176 (2021) 39–51, https://doi.org/10.1016/
j.carbon.2021.01.135.
[125] B. Ramezanzadeh, Z. Haeri, M. Ramezanzadeh, A facile route of making silica
nanoparticles-covered graphene oxide nanohybrids (SiO2-GO); fabrication of
SiO2-GO/epoxy composite coating with superior barrier and corrosion protection
performance, Chem. Eng. J. 303 (2016) 511–528, https://doi.org/10.1016/j.
cej.2016.06.028.
[126] R. Mohammadkhani, M. Ramezanzadeh, S. Saadatmandi, B. Ramezanzadeh,
Designing a dual-functional epoxy composite system with self-healing/barrier
using graphene oxide nano-scale platforms decorated with zinc doped-conductive
polypyrrole nanoparticles with great environmental stability and non-toxicity,
Chem. Eng. J. 382 (2019), 122819, https://doi.org/10.1016/j.cej.2019.122819.
[127] Y. Zhan, J. Zhang, X. Wan, Z. Long, S. He, Y. He, Epoxy composites coating with
Fe3O4 decorated graphene oxide: modified bio-inspired surface chemistry,
synergistic effect and improved anti-corrosion performance, Appl. Surf. Sci. 436
(2018) 756–767, https://doi.org/10.1016/j.apsusc.2017.12.095.
[128] H. Yuan, F. Qi, N. Zhao, P. Wan, B. Zhang, H. Xiong, Graphene oxide decorated
with titanium nanoparticles to reinforce the anti-corrosion, Coatings. 10 (2020),
https://doi.org/10.3390/coatings10020129.
[129] S. Wang, J. Zhu, Y. Rao, B. Li, S. Zhao, H. Bai, J. Cui, Polydopamine modified
graphene oxide-TiO 2 nanofiller for reinforcing physical properties and
anticorrosion performance of waterborne epoxy coatings, Appl. Sci. 3 (2019)
1–18, https://doi.org/10.3390/app9183760.
[130] K. Amirazodi, M. Sharif, M. Bahrani, Polypyrrole doped graphene oxide
reinforced epoxy nanocomposite with advanced properties for coatings of mild
steel, J. Polym. Res. 26 (2019) 1–12.
[131] S. Wang, Z. Hu, J. Shi, G. Chen, Q. Zhang, Z. Weng, K. Wu, M. Lu, Green synthesis
of graphene with the assistance of modi fi ed lignin and its application in
anticorrosive waterborne epoxy coatings, Appl. Surf. Sci. 484 (2019) 759–770,
https://doi.org/10.1016/j.apsusc.2019.03.229.
[132] K. Rajitha, K.N. Mohana, Application of modified graphene oxide –
Polycaprolactone nanocomposite coating for corrosion control of mild steel in
saline medium, Mater. Chem. Phys. 241 (2020), 122050.
[133] S. Wang, J. Zhu, Y. Rao, B. Li, S. Zhao, H. Bai, J. Cui, Polydopamine modified
graphene oxide-TiO2 nanofiller for reinforcing physical properties and
anticorrosion performance of waterborne epoxy coatings, Appl. Sci. 9 (2019),
https://doi.org/10.3390/app9183760. Switzerland.
[134] S. Pourhashem, M. Reza, A. Rashidi, Investigating the effect of SiO 2-graphene
oxide hybrid as inorganic nano filler on corrosion protection properties of epoxy
coatings, Surface & Coatings Technology 311 (2017) 282–294.
[135] Q. Zhu, E. Li, X. Liu, W. Song, Y. Li, X. Wang, C. Liu, Epoxy coating with in-situ
synthesis of polypyrrole functionalized graphene oxide for enhanced
anticorrosive performance, Prog. Org. Coat. 140 (2020), 105488, https://doi.org/
10.1016/j.porgcoat.2019.105488.
[136] C. Chen, Y. He, G. Xiao, Y. Xia, H. Li, Z. He, Y. He, G. Xiao, Y. Xia, H. Li, Z. He,
Two-dimensional hybrid materials: MoS2 -RGO nanocomposites enhanced the
barrier properties of epoxy coating, Appl. Surf. Sci. 444 (2018) 511–521, https://
doi.org/10.1016/j.apsusc.2018.03.013.
[137] V. A.B.A., P.V. Pasas, S. Thomas, J. Parameswaranpillai, D. Puglia, S. Siengchin,
L. Aryakrishna, A. Manohar, Fabrication of water-resistant epoxy nanocomposite
with improved dynamic mechanical properties and balanced thermal and
dimensional stability: study on dual role of graphene oxide nanosheets and
barium oxide microparticles, Colloids Surfaces A Physicochem. Eng. Asp. 617
(2021), 126405, https://doi.org/10.1016/j.colsurfa.2021.126405.
[138] G. Grundmeier, W. Schmidt, M. Stratmann, Corrosion Protection by Organic
Coatings: Electrochemical Mechanism and Novel Methods of Investigation 45,
2000, pp. 2515–2533.
[139] Y. Ye, H. Chen, Y. Zou, Y. Ye, H. Zhao, Corrosion protective mechanism of smart
graphene-based self-healing coating on carbon steel, Corros. Sci. 174 (2020),
108825, https://doi.org/10.1016/j.corsci.2020.108825.
J.S. George et al.
[140] J.G.C. Du Hongxia Wan, Dongdong Song, Xiaogang Li, Dawei Zhang, Failure
mechanisms of the coating/metal interface inwaterborne coatings: the effect of
bonding, Materials. 10 (2017) 1–15.
[141] A. Uthaman, G. Xian, S. Thomas, Y. Wang, Q. Zheng, X. Liu, Durability of an
epoxy resin and its carbon Fiber- reinforced polymer composite upon immersion,
Polymers. 12 (2020) 1–23, https://doi.org/10.3390/polym12030614.
[142] S. Zhou, Y. Wu, W. Zhao, J. Yu, F. Jiang, Y. Wu, L. Ma, Designing reduced
graphene oxide/zinc rich epoxy composite coatings for improving the
anticorrosion performance of carbon steel substrate, Mater. Des. 169 (2019),
107694, https://doi.org/10.1016/j.matdes.2019.107694.
[143] P.P. Vijayan, D. Puglia, Biomimetic multifunctional materials: a review
biomimetic multifunctional materials: a review, Emerging Materials. 2 (2019)
391–415, https://doi.org/10.1007/s42247-019-00051-7.
[144] P. P.V., Y.M.H. El-Gawady, M.A.S.A. Al-Maadeed, Halloysite nanotube as
multifunctional component in epoxy protective coating, Ind. Eng. Chem. Res. 55
(2016) 11186–11192, https://doi.org/10.1021/acs.iecr.6b02736.
[145] H. Gu, C. Ma, J. Gu, J. Guo, X. Yan, An overview of multifunctional epoxy
nanocomposites, J. Mater. Chem. C 4 (2016) 5890–5906, https://doi.org/
10.1039/c6tc01210h.
[146] H. Kim, A.L. Yarin, M. Wook, Self-healing corrosion protection film for marine
environment, Compos. B. Eng. 182 (2020), 107598, https://doi.org/10.1016/j.
compositesb.2019.107598.
[147] P. Najmi, N. Keshmiri, M. Ramezanzadeh, B. Ramezanzadeh, Synthesis and
application of Zn-doped polyaniline modified multi-walled carbon nanotubes as
stimuli-responsive nanocarrier in the epoxy matrix for achieving excellent
barrier-self-healing corrosion protection potency, Chem. Eng. J. 412 (2021),
128637, https://doi.org/10.1016/j.cej.2021.128637.
[148] R. Najjar, S. Adib, M. Ghasem, Self-healing and corrosion protection performance
of organic polysulfide@urea-formaldehyde resin core-shell nanoparticles in
epoxy/PANI/ZnO nanocomposite coatings on anodized aluminum alloy, Prog.
Org. Coat. 124 (2018) 110–121, https://doi.org/10.1016/j.
porgcoat.2018.08.015.
[149] S.A. Kumar, T. Balakrishnan, M. Alagar, Z. Denchev, Development and
characterization of silicone/phosphorus modified epoxy materials and their
application as anticorrosion and antifouling coatings, Prog. Org. Coat. 55 (2006)
207–217, https://doi.org/10.1016/j.msea.2005.09.097.
[150] X. Quan, J. Wang, S. Zhao, W. Cai, Z. Wang, S. Wang, X. Cui, Improved
antibacterial, antifouling and corrosion protective performance ofepoxy coatings
with poly(m-aminophenol), Prog. Org. Coat. 5 (2018) 9–17, https://doi.org/
10.1016/j.porgcoat.2017.11.005.
[151] P. Saravanan, K. Jayamoorthy, S.A. Kumar, Design and characterization of non-
toxic nano-hybrid coatings for corrosion and fouling resistance, J. Sci. Adv. Mater.
Dev. 1 (2016) 367–378, https://doi.org/10.1016/j.jsamd.2016.07.001.
[152] S. Ananda Kumar, A. Sasikumar, Studies on novel silicone/phosphorus/Sulphur
containing nano-hybrid epoxy anticorrosive and antifouling coatings, Prog. Org.
Coat. 68 (2010) 189–200, https://doi.org/10.1016/j.porgcoat.2010.02.005.
[153] X. Liu, T.C. Zhang, H. He, L. Ouyang, S. Yuan, A stearic acid/CeO2 bilayer coating
on AZ31B magnesium alloy with superhydrophobic and self-cleaning properties
for corrosion inhibition, J. Alloys Compd. 834 (2020), 155210, https://doi.org/
10.1016/j.jallcom.2020.155210.
22
Progress in Organic Coatings 162 (2022) 106571
[154] K. Chang, M. Hsu, H. Lu, M. Lai, P. Liu, Room-temperature cured hydrophobic
epoxy/graphene composites as corrosion inhibitor for cold-rolled steel, Carbon.
66 (2013) 144–153, https://doi.org/10.1016/j.carbon.2013.08.052.
[155] P. Vijayan p, M.A. Almaadeed, ‘Containers’ for self-healing epoxy composites and
coating: trends and advances, Express Polym Lett 10 (2016) 506–524, https://doi.
org/10.3144/expresspolymlett.2016.48.
[156] S. Javadian, Z. Ahmadpour, A. Youse, Polypyrrole nanocapsules bearing
quaternized alkyl pyridine in a green self- healing coating for corrosion protection
of zinc, Prog. Org. Coat. 147 (2020), 105678, https://doi.org/10.1016/j.
porgcoat.2020.105678.
[157] P. P.V., M. Al-Maadeed, Self-repairing composites for corrosion protection: a
review on recent strategies and evaluation methods, Materials. 12 (2019) 1–17,
https://doi.org/10.3390/ma12172754.
[158] M. Ramezanzadeh, B. Ramezanzadeh, M. Mahdavian, G. Bahlakeh, Development
of metal-organic framework (MOF) decorated graphene oxide nanoplatforms for
anti-corrosion epoxy coatings, Carbon. 161 (2020) 231–251, https://doi.org/
10.1016/j.carbon.2020.01.082.
[159] H. Pulikkalparambil, P. Siengchin, Jyotishkumar Suchart, Corrosion protective
self-healing epoxy resin coatings based on inhibitor and polymeric healing agents
encapsulated in organic and inorganic micro and nanocontainers, Nano-Struct.
Nano-Objects. 16 (2018) 381–395, https://doi.org/10.1016/j.
nanoso.2018.09.010.
[160] P. P.V., A. Tanvir, Y.H. El-gawady, M. Al-maadeed, Cellulose nano fibers to assist
the release of healing agents in epoxy coatings, Prog. Org. Coat. 112 (2017)
127–132, https://doi.org/10.1016/j.porgcoat.2017.07.008.
[161] P. P.V., M.A.S.A. Al-maadeed, TiO2 nanotubes and mesoporous silica as
containers in self-healing epoxy coatings, Sci. Rep. 6 (2016) 1–9, https://doi.org/
10.1038/srep38812.
[162] C. Chen, G. Xiao, Y. He, F. Zhong, H. Li, Y. Wu, J. Chen, Bio-inspired superior
barrier self-healing coating: self-assemble of graphene oxide and polydopamine-
coated halloysite nanotubes for enhancing corrosion resistance of waterborne
epoxy coating, Prog. Org. Coat. 139 (2020), 105402, https://doi.org/10.1016/j.
porgcoat.2019.105402.
[163] C. Guo, H. Ding, M. Xie, H. Zhang, X. Hong, L. Sun, Multifunctional
superamphiphobic fluorinated silica with a core-shell structure for anti-fouling
and anti-corrosion applications, Colloids Surf. A Physicochem. Eng. Asp. 615
(2021), 126155, https://doi.org/10.1016/j.colsurfa.2021.126155.
[164] C. Wu, J. Wang, S. Song, Z. Wang, Antifouling and anticorrosion performance of
the composite coating made of tetrabromobisphenol-A epoxy and polyaniline
nanowires, Prog. Org. Coat. 148 (2020), 105888, https://doi.org/10.1016/j.
porgcoat.2020.105888.
[165] Y. Chen, G. Zhang, G. Zhang, C. Ma, Rapid curing and self-stratifying lacquer
coating with antifouling and anticorrosive properties, Chem. Eng. J. 421 (2021),
129755, https://doi.org/10.1016/j.cej.2021.129755.
[166] S. Fazli-shokouhi, F. Nasirpouri, M. Khatamian, Epoxy-matrix polyaniline/p-
phenylenediamine-functionalised graphene oxide coatings with dual anti-
corrosion and anti-fouling performance, RSC Adv. 11 (2021) 11627–11641,
https://doi.org/10.1039/d0ra10665h.
[167] S. Verma, S. Mohanty, S.K. Nayak, Preparation of hydrophobic epoxy
polydimethylsiloxane graphene oxide nanocomposite coatings for antifouling
application, Soft Matter 16 (2020) 1211–1226, https://doi.org/10.1039/
C9SM01952A.