Corros Rev 2019; aop
Review
Ahmed Khalid Hussain, Izman Sudin*, Uday M. Basheer and Mohd Zamri Mohd Yusop
A review on graphene-based polymer composite
coatings for the corrosion protection of metals
https://doi.org/10.1515/corrrev-2018-0097
Received November 13, 2018; accepted May 31, 2019
Abstract: Graphene-based coating is an emerging field
that focuses on developing advanced coatings by exploit-
ing new generation materials with superior properties.
Researchers are striving to develop coatings that are cost-
effective, easy to prepare and highly effective by integrat-
ing graphene with a wide range of suitable materials for
surface protection applications. In this critical review, dif-
ferent types of high performing graphene-based polymer
composite coatings have been described for anticorrosion
application. An in-depth survey on methods of prepara-
tion, coating application techniques and their influence
on the corrosion behavior of coatings is presented briefly.
Newly developed strategies to enhance the protection
efficiency of graphene-polymer matrix coatings are also
covered concisely. The authors hope that this review will
assist prospective academicians and researchers in devel-
oping novel highly efficient graphene-based anticorrosion
composite coatings for industrial applications.
Keywords: composite coatings; conductive polymers; cor-
rosion; electrodeposition; graphene; in situ polymeriza-
tion; nanoparticles.
*Corresponding author: Izman Sudin, School of Mechanical
Engineering, Faculty of Engineering, Universiti Teknologi Malaysia,
81310 Skudai, Johor, Malaysia, e-mail: izmansudin55@gmail.com
Ahmed Khalid Hussain: School of Mechanical Engineering, Faculty
of Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor,
Malaysia
Uday M. Basheer: School of Mechanical Engineering, Faculty of
Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor,
Malaysia; and UTM Centre for Low Carbon Transport in cooperation
with Imperial College London, Institute for Vehicle Systems and
Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor,
Malaysia
Mohd Zamri Mohd Yusop: School of Mechanical Engineering,
Faculty of Engineering, Universiti Teknologi Malaysia, 81310 Skudai,
Johor, Malaysia; and Advanced Membrane Technology Research
Centre (AMTEC), Universiti Teknologi Malaysia, 81310 Skudai, Johor,
Malaysia
1 Introduction
Corrosion is a serious practical problem, the effects of
which can be observed as soon as a metal is put into
service in an acidic or humid environment. To prevent
premature metals degradation due to corrosion, research-
ers are finding new ways to tackle this menacing problem.
With the considerable progress in anticorrosion techno-
logy, many modern corrosion preventive techniques are
being developed to increase the lifespan of metals. Some
of the latest improved methods used today to protect
metals from corrosive environment include metal alloy-
ing with composite materials, application of corrosion
inhibitors and protective coatings (Rezende et al., 2016).
Protective coatings can be applied in the form of metal-
based organic layers (Stratmann et al., 1994), oxide layers
(Sieber et al., 2015), polymeric films (Lu et al., 1995), sac-
rificial metallic coatings (Gonçalves et al., 2011) and var-
nishes (Merkula et  al., 1974). Diversified coatings have
been developed with better anticorrosion properties by
dispersing filler materials with special properties forming
a composite such as hybrid coatings (Hammer et al., 2013),
smart self-healing coatings (Abdullayev et  al., 2013) and
superhydrophobic coatings (El Dessouky et al., 2017). An
interesting choice of researchers nowadays for enhancing
the anticorrosion performance of anticorrosion coatings is
to include carbon-based nanofillers such as carbon nano-
tubes and graphene.
Graphene is a two-dimensional allotropic form of
carbon consisting of a single layer of bonded carbon
atoms with one atom thickness forming the hexagonal
lattice structure. It is considered as a basic structural
element of other allotropes of carbon structures, such as
graphite, carbon nanotubes, fullerenes and charcoal with
two-dimensional sp2 hybridized structure (Geim & Novo-
selov, 2007). Graphene is considered as a wonder material
exhibiting extraordinary properties of highest strength
over all materials ever tested (Shekhawat & Ritchie, 2016),
enhanced thermal conductivity (Balandin et  al., 2008),
remarkable electronic properties (Neto et al., 2009), high
optical transparency (Bonaccorso et al., 2010), large non-
linear diamagnetism (Yazyev, 2010) and impermeability
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2      A.K. Hussain et al.: Graphene-based polymer composite coatings

(Berry, 2013). Figures 1 and 2 represent the percentage
utilization of graphene in various sectors of engineer-
ing sciences and its applications in the field of films and
coatings.
Graphene also exhibits other unique properties,
making it the most promising material for useful applica-
tions such as electrochemical energy storage (Raccichini
et al., 2015), water purification (Han et al., 2013), superca-
pacitors (Tan & Lee, 2013), biomedical implants (Bitounis
et al., 2013), gas sensing (Yuan & Shi, 2013) and protective
thin films (Kirkland et al., 2012). Graphene can be synthe-
sized in a variety of forms such as single layer/bilayer gra-
phene films, graphene oxide (GO), graphene nanoplatelets
and graphene nanoribbons by latest available techniques.
Graphene nanoplatelets are increasingly used in prepa-
ration of composite materials by mixing with metals,
ceramics and polymers to suit the properties for end appli-
cations. GNPs are made of small stacks of graphene that
can be replaced with carbon nanotubes because it dif-
fuses smoothly into the matrix material and less likely to
twist and have high specific surface area, enhancing the
final properties (Jang & Zhamu, 2008). The exceptional
properties of graphene nanoribbons have wide variety
of applications and are useful in novel nanocomposites,
hi-tech batteries and supercapacitors, coatings and adhe-
sives (Shen et al., 2015). Graphene nanoflakes have prom-
ising applications in the fields of electronics, optics and
electrical engineering (Silva et al., 2010).

5% 12%
11%
Electronic devices
4%
Optoelectronic devices
Energy generation
27% Energy storage
19% Others
Composites
Biomedical devices
Synthesis and processing
8% 14%

Figure 1: Graphical distribution on percentage utilization of graphene in different fields of engineering sciences.

Anti-scratch Anti-corrosion

Hydrophobic
Tribological Graphene
Barrier
properties films and
properties
coatings

Anti-biofouling
Anti-friction

Figure 2: Schematic diagram depicting properties and applications of graphene films and coatings.

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 A.K. Hussain et al.: Graphene-based polymer composite coatings      3
Graphene is a hydrophobic material (Singh et  al.,
2013c), whereas GO possesses hydrophilic property. This
water-repellent property of graphene makes it suitable for
preparation of water resistant films and advanced hybrid
coatings (Romero Aburto et al., 2015). With the discovery
of graphene, investigators are focusing their attention
on developing pristine graphene-based ultrathin coat-
ings that are impermeable to liquids and gas molecules
without changing the properties of the base metal. Pure
graphene coatings can be utilized as conductive coating
for touch panel applications, cathode material in Li-ion
batteries, energy storage applications and dye-sensitized
solar cells for energy conversion applications (Tong et al.,
2013). Generally, graphene is treated as a chemically inert
material with dense lattice structure and have the ability to
form single and multilayer coatings that act as natural dif-
fusion barriers (Bunch et al., 2008). Prior to the isolation
of graphene in 2004, excoriated or intercalated clays (Yeh
et al., 2002) and fullerene (Jayatissa et al., 2005) materials
were applied as coatings for anticorrosion applications.
Because of their insulating and hydrophilic properties,
these materials are not suitable for impeding corrosion.
These fully insulated coatings promote accelerated corro-
sion by moisture that enters through the defects and sup-
presses the anticorrosion behavior on metals (Advincula,
2015). Large surface area and high electrical conductivity
of graphene imparts favorable effects on barrier perfor-
mance of the coatings composed. Anticorrosion mecha-
nism of pristine graphene coatings can be exemplified as
the combination of three actions: (1) by preventing elec-
trons generated at anodic sites from reaching cathodic
Figure 3: Record of graphene coatings depicting number of research papers published since year 2004 (source: Web of Science, accessed
on 09/02/2019).
sites by providing alternative paths, (2) by forming an
impermeable passive layer of graphene on the surface of
metal, (3). By making the path of corrosive elements more
tortuous to reach the graphene-metal interface (Böhm,
2014).
Many pioneering investigations have proved that gra-
phene and graphene derivatives such as functionalized
graphene, graphene oxide and reduced graphene oxide
in the form of coatings can effectively decouple the metal
surface from the surrounding environment, thus protect-
ing it from corrosion, oxidation (Kang et  al., 2012b) and
hydrogen embrittlement (Nam et  al., 2014). Defectless
graphene nanosheets are highly inert in nature and floc-
culates when mixed with other matrix materials because
of strong vander Waals forces, thus affecting the final
properties of the coatings. To eliminate this phenomenon,
graphene is often functionalized with chemicals or metal-
lic nanoparticles that increase that dispersibility and
interfacial bonding with matrix materials (Kumar et  al.,
2012). Since the discovery of graphene, the research con-
ducted on graphene coatings has gone up exponentially.
According to the Web of Science 2017 database, there were
approximately 8902 papers published alone on graphene
coatings related topics. Figure 3 shows the timeline of
publications related to graphene coatings since 2004.
While most of the reports published in the literature
confirm that graphene is a promising anticorrosion mate-
rial, most of the corrosion testing was carried in corrosive
conditions at room temperature but for a short period of
time. In real operating conditions, the graphene coatings
actually promotes corrosion in the presence of defects in
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4      A.K. Hussain et al.: Graphene-based polymer composite coatings
a long-term. The reason for this enhancement of corro-
sion is associated with the conductive nature of graphene
that consequently enhances the localized galvanic corro-
sion. In the presence of graphene coating, the free elec-
trons migrates from the metal substrate to the graphene/
air interface, resulting in galvanic corrosion (Zhou et al.,
2013). Furthermore, under the influence of low electro-
chemical potential, graphene films can also fail, leading
to enhanced local galvanic corrosion at an accelerated
rate at the graphene-metal interface (Ambrosi & Pumera,
2015). To mitigate these problems, graphene coatings must
be made crack free and durable enough to resist scratches.
Although several review articles have been published
on functional and smart composite coatings for different
applications such as semiconductor device fabrication,
wear resistance, gas sensing and antifouling (Nine et al.,
2015a,b), only a few of them are designated comprehen-
sively to corrosion-related issue particularly on coatings
composed of graphene- or GO-based composite coatings.
The objective of this review paper is to present extensive
research advances and latest trends in the field of corro-
sion prevention by utilizing graphene as the reinforce-
ment material in polymer coatings. The main highlights
of this paper include the synthesis methods for graphene
polymer composite coatings and their influence on
the corrosion behavior of different metallic substrates.
Detail discussions have been carried out on graphene-
polymer matrix composites coatings and their protection
mechanisms under different environmental conditions.
Additionally, the latest strategies used to improve the
performance of graphene-polymer matrix coatings are
elaborated in a separate section. Comparison of electro-
chemical test results for different coating types is also
presented along with the microstructure morphology for a
better understanding of corrosion mechanisms.
2 C
 oatings for anticorrosion
application
The role of the anticorrosion coating is to serve as a
barrier between the corrosive electrolyte and the metal
surface by inhibiting chemical compounds formed on the
surface that promote corrosion. Because of disparities in
the structural properties of metal and the coating layer
characteristics, failure of coatings may occur, compromis-
ing its corrosion combating affect. Anticorrosion coatings
prevent corrosion usually by one of the following mecha-
nisms: (i) barrier protection, (ii) inhibition effect and (iii)
sacrificial protection (Montemor, 2014). Barrier protection
involves the prevention of corrosion by isolating the sub-
strate from the corrosive environment by forming a thick
layer. The efficiency of the barrier is largely affected by
the thickness of the film, its composition and the pres-
ence of defects (Ates, 2016). In sacrificial protection, a
metallic coating covers the substrate and safeguards it by
depleting itself in an electrochemical cell. The ability of
the metallic coating to sacrifice depends on the electron-
egativity or the electropositivity of the metal (Shreepathi
et al., 2010). Corrosion inhibitors are metallic or nonme-
tallic materials added to the coating system that act as an
additional corrosion protection above the barrier protec-
tion of the oxide layer.
Anticorrosion coatings can be synthesized from
organic, inorganic, metallic or hybrid materials. Paints
and other organic coatings such as lacquers, varnishes
and polymer coatings are often employed to prevent
metals from the deterioration in the presence of a corro-
sive environment by forming a barrier between the metal
surface and its surrounding atmosphere. Common types
of organic and inorganic coatings include epoxy coatings,
acrylic coatings, urethane coatings and water-soluble
coatings (Sørensen et  al., 2009). Metallic coatings are
commonly applied by vapor deposition (Hampden-Smith
& Kodas, 1995), electrodeposition (Gomes & da Silva
Pereira, 2006), hot dipping (Shibli et al., 2015) and metal
cladding (Alfred, 1955) processes, but inorganic coatings
are formed by chemical conversion (Zhao et  al., 2001),
thermal spraying (Katayama & Kuroda, 2013) or diffusion
process (Vourlias et al., 2006). Porosity, flaking, cracks or
any other defects on the coatings may result in accelerated
localized galvanic corrosion on the base metal. Metallic
and ceramic coatings although offer several advantages,
some of them are extremely expensive and some are
banned because of key environmental issues and health
concerns. Furthermore, ceramic materials used in coat-
ings are highly brittle and can ultimately fail, leading to
a catastrophe (Priyantha et  al., 2003). Most of the tradi-
tionally deployed protective coatings result in substan-
tial increase in thickness and modification in electrical,
mechanical and optical properties of the base metal.
The issues mentioned above necessitated the research-
ers to develop protective coatings with ultrafine thickness
and minimal defects. During the last decade, remarkable
advancement in the field of nanotechnology research led
the investigators to fabricate novel hybrid nanocomposite
coatings with superior anticorrosion properties. Newly
fabricated hybrid coatings consisted of carbon nanoma-
terials such as carbon nanotubes, carbon nanofibers and
graphene with metals, ceramics or polymer as matrix
material (Daneshvar-Fatah & Nasirpouri, 2014). These
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 A.K. Hussain et al.: Graphene-based polymer composite coatings      5
hybrid coatings have been proved to be more effective
than coatings with a single material by combining all the
three corrosion protection mechanisms, giving extra pro-
tection to the base against metal corrosion.
3 G
 raphene polymer matrix
composite coatings (GPMCCs)
Economical sources of graphene and its outstanding
properties have led the investigators to explore novel,
high-performance and cost-effective graphene-polymer
nanocomposite coatings with improved anticorrosion
efficiency. Graphene nanosheets incorporated in polymer
matrix give extra corrosion protection to metals by making
it difficult for electrolyte molecules to penetrate through
the defects of graphene due to the surrounding polymer
phase. In addition to breaking the galvanic couple by
preventing flow of electrons from the metal to graphene,
mixing of nonconducting polymer (CP) with graphene also
improves the mechanical and thermal properties of the
metal substrate (Krishnamoorthy et al., 2014). Graphene-
reinforced polymer nanocomposite system gives enhanced
anticorrosion ability to coatings primarily because of
the following protection mechanisms: (i)  homogeneous
­distribution of polymer phase on the substrate’s surface
resulting in the formation of smooth and uniform passive
layer, (ii) limiting the penetration and providing tortuous
diffusion path to the corrosive agents along the coating
thickness and (iii) reformed mechanical strength to resist
cracks and improved adhesion ability to the metal surface
(Wang, 2018).
The resulting properties of the composite coatings
depend on the composition and properties of the polymer
matrix, coating deposition technique and how readily the
graphene sheets are dispersed into the matrix to create a
good network structure (Cui et  al., 2016). Uniformly dis-
tributed graphene nanosheets suppress the corrosion
process by restricting the flow of electrons to and from
coating interface and preventing chain mobility in the
matrix. Significant amount of research has been carried in
the fabrication of graphene-reinforced polymer nanocom-
posite coatings by adding graphene in different synthetic
polymer systems with electroactive or non-electroactive
nature to generate unique mechanical and chemical prop-
erties for a variety of applications.
To prevent agglomeration, the graphene nanosheets
are often dispersed in waterborne polymer matrices such
as waterborne epoxy resin or sodium polyacrylate in
aqueous solution (Liu et  al., 2016). Epoxy coatings are
used extensively for corrosion resistance applications due
to their exemplary superior intrinsic toughness, stability
at low and high temperatures, high adhesive ability onto
various substrates and high chemical resistivity (Kang
et al., 2012a). Nonetheless, the corrosion resistance ability
of pristine epoxy coatings is compromised after exposure
to water and oxygen molecules because of hydrolytic dete-
rioration. Published reports prove that the inclusion of gra-
phene nanosheets and its derivatives into epoxy coatings
enhances its corrosion protection property. Graphene and
GO nanosheets have been reported to be incorporated in
an epoxy matrix by in situ polymerization method to form
novel anticorrosion coatings. The addition of graphene
and its derivative (GO) as filler material showed enhance-
ment in corrosion resistance of the epoxy coatings, which
was confirmed by electrochemical impedance spectro-
scopy (EIS) spectrum results. These affirmative results
were attributed to the fact that graphene/GO nanoplate-
lets possess large specific surface area and high aspect
ratio, which makes diffusive path tortuous and difficult
to permeate for corrosive agents. However, increased per-
centage of GO in epoxy reduced the anticorrosion perfor-
mance because of agglomeration of GO nanosheets (Rajabi
et al., 2015; Alhumade et al., 2016). Recently, Chang et al.
(2014b) copied the properties of Xanthosoma sagittifolium
leaves and synthesized graphene/epoxy composite coat-
ings with hydrophobic surfaces as corrosion inhibitors on
cold rolled steel substrates. The as-prepared hydrophobic
surfaces exhibited increased water contact angle from 82°
to 127° and provided excellent corrosion protection by
forming a physical barrier and repelling moisture, which
was predicted by the increase in impedance value of the
coatings. However, this method of coating preparation is
costly and complicated and difficult to be applied in prac-
tical applications.
Waterborne epoxy coatings are increasingly used for
anticorrosion application because of its advantages of
easy cleaning and strong adhesion to different types of
metallic substrates. Monetta et al. (2017) examined exclu-
sively the anticorrosion behavior of graphene waterborne
epoxy composite coatings applied to aluminum samples.
Hydrophobic and adhesion test results revealed that the
addition of graphene nanosheets slightly enhanced the
hydrophobic property of the coatings, whereas the adhe-
sion ability was not affected much. Moreover, EIS meas-
urements indicated that graphene loading had a positive
impact on coatings and exhibited good corrosion protec-
tion of the metallic substrates. The superior anticorrosion
performance of the coatings was correlated to the forma-
tion of a passive barrier and reduced water adsorption and
transport through the filled epoxy coatings, which was
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6      A.K. Hussain et al.: Graphene-based polymer composite coatings
confirmed by the high impedance modulus and capaci-
tance values.
Embedding graphene into the polyvinyl alcohol (PVA)
polymer gives corrosion-resistant coating by lessening the
pin hole defects and forming strong bonds with the oxygen
functional groups of graphene (Amini et al., 2016). Hikku
et  al. (2017) infused graphene nanoplatelets, whereas
Zhang et  al. (2017) used reduced graphene oxide (rGO)
into the PVA matrix and formulated composite coatings
with better corrosion-resistant properties. rGO-PVA coat-
ings were synthesized by using a novel in situ reduction
process in which GO-PVA mixture was thermally treated
at a low temperature. Corrosion resistance of G/PVA and
rGO/PVA as-prepared samples was evaluated using Tafel
and Nyquist curves. EIS measurements showed that
G/PVA nanocomposite coatings exhibited high and stable
impedance value when exposed to a 3.5  wt% NaCl solu-
tion, indicating high corrosion resistance. G/PVA-coated
samples displayed better corrosion protection efficiency
than rGO/PVA-coated samples because of the introduc-
tion of defects during the reduction process. However, this
technique adopted to prepare rGO/PVA coatings is simple
and feasible as compared with conventional rGO reduc-
tion techniques that require inert atmosphere and high
temperatures.
Previous studies have shown that combining graphene
with polyurethane (PU) may yield a novel coating with
renewed anticorrosion properties. Huang et al. (2016) and
Nuraje et al. (2013) formulated graphene/PU nanocompos-
ite coatings by infusing graphene particles in PU matrix
for improved weathering, corrosion and sound absorbing
performances. The composed coatings exhibited rela-
tively high impedance values, steep acoustic adsorption
coefficient and sharp resistance against ultraviolet degra-
dation, suggesting an improvement in anticorrosion and
acoustic properties of the coating for underwater materi-
als. However, the average final coating thickness for all
samples was relatively high at approximately 100 ± 20 μm.
Cl–
O2
Graphene
sheet
Corrosion
spot
A METAL SUBSTRATE B METAL SUBSTRATE
Figure 4: Schematic representation illustrating protection mechanism of (A) graphene-epoxy coating and (B) graphene-zinc rich epoxy
coating exposed to electrolytic solution.
Similarly, (Singh et  al., 2013a,b) improvised thin, sturdy
and crack-free GO/isocyanate hybrid coatings with excep-
tional oxidation and corrosion resistance by electropho-
retic deposition process. Preliminary corrosion test results
confirmed the reduction of electrochemical degrada-
tion by three orders (25 Ω/cm2) of magnitudes compared
with the uncoated substrate (8 Ω/cm2) with outstanding
adhesion capability. To further improve the hydrophobic
property, the coating was treated with silicone fluids to
form a protective organic layer after the electrophoretic
deposition process. The credible mechanism explained by
the author for such a high corrosion resistance of GO/iso-
cyanate-coated samples was connected to the enhanced
wetting and formation of metal hydroxide during the elec-
trodeposition process.
Nowadays, zinc-rich epoxy coatings (ZREC) are a
widely studied topic among coating researchers because
of its superior corrosion protection ability for a long
period of time in harsh corrosive conditions and even
after severe damage to coating layers. The corrosion pro-
tection mechanism involved in zinc-rich coatings is sac-
rificial cathodic protection, but with the passing time,
protection efficiency decreases due to the decrease in
coating porosity (Shreepathi et al., 2010). Several efforts
have been made in the past to augment the efficiency
of zinc-rich coatings by means of incorporation of dif-
ferent kinds of additives and nanofiller materials. Liu
et  al. (2018) reported the use of single-layer graphene
nanosheets in ZREC to improve its barrier and cathodic
protection efficiency. Only 0.4  wt% of the single-layer
graphene was added to the zinc-rich epoxy resulting
in the enhancement of anticorrosion properties, which
were validated by open circuit potential and EIS meas-
urements in terms of high polarization resistance values.
Moreover, the coated samples were characterized by
localized electrochemical impedance spectroscopy
to prove the cathodic protection property. Figure  4A
and B illustrate the corrosion protection mechanisms in
Electrolyte
Epoxy
ZnO
Zn particles
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graphene-reinforced epoxy and ZREC, respectively. The
mechanism of zinc dissolution in the presence of NaCl
solution can be explained as follows (Sørensen et  al.,
2009):
O2 + 2H2O + 4e − → 4OH−
Zn − 2e − → Zn 2+
Zn + 2OH− → Zn(OH)2 + 2e −
Zinc hydroxide after absorbing CO2 from the atmos-
phere converts into Zn5(CO3)2(OH)6 and zinc oxide accord-
ing to the following reaction:
6Zn(OH)2 + 2CO2 → Zn 5 (CO3 )2 (OH)6 + ZnO + 3H2O
In a similar research work, Hayatdavoudi and
­ ahsepar (2017) lately reported a mechanistic study on
R
the impact of a few-layered graphene nanosheets on
the anticorrosion performance of a ZREC. Corrosion test
results revealed that the introduction of just 0.4 wt% of
graphene resulted in superior anticorrosion performance
as compared with pristine ZREC. The enhanced corro-
sion protection mechanism was linked with uniform
anodic protection of zinc particles and excellent infiltra-
tion activity of graphene nanosheets. Moreover, a facile
and accurate equivalent circuit model was presented to
show the influence of graphene nanosheets in terms of
galvanic reactions and seepage effects. Higher cathodic
protection efficiency was proved by the lower perco-
lation resistance of the coatings and reduced charge
transfer resistance due to sacrificial zinc particles. The
A B
Debonding
Figure 5: (A) Typical FESEM image demonstrating incomplete bonding of graphene sheets with the polymer and (B) HRTEM image
representing flocculation of graphene sheets in polymer matrix.
A.K. Hussain et al.: Graphene-based polymer composite coatings      7
primary issue in graphene-based polymer coatings is
the severe agglomeration of graphene nanosheets in
polymer matrix due to their high aspect ratio, strong
Vander Waals interactions and formation of vacuum
during vacuum filtration process. Figure 5A and B rep-
(1)
resent field emission scanning electron microscopy
(FESEM) and transmission electron microscopy (TEM)
(2) images showing debonding of graphene nanosheets
and agglomeration, respectively, dispersed in polymer
(3) resin. Besides agglomeration, the presence of porosity
formed during evaporation process, surface roughness
and adhesion ability also strongly governs the protection
efficiency of the coatings (Galpaya et  al., 2012). Thus,
to enhance the overall anticorrosion properties of the
coating, it is necessary to prevent graphene segregation
and generation of porosity to obtain a homogeneous dis-
(4)
tribution of graphene in polymer matrix.
3.1 S
 trategies to enhance anticorrosion
properties of GPMCCs
Several new approaches have been reported in the lit-
erature to increase dispersion stability, prevent agglom-
eration and promote compatibility of multilayered
graphene nanosheets with the polymer matrix. These
remedies include selection of appropriate synthesis
method, usage of hybrid nanofillers, usage of suitable
organic solvents and functionalization of graphene
sheets (Atif & Inam, 2016). Some of the newly developed
strategies to improve the barrier and corrosion perfor-
mance of GPMCCs have been discussed in detail in the
following sections.
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8      A.K. Hussain et al.: Graphene-based polymer composite coatings

3.1.1 Using conductive polymer matrix systems
CPs are widely used as anticorrosion materials because
of their superior environmental stability and exceptional
redox properties linked with the chain of nitrogen (Yao
et al., 2008). CPs can be readily deposited in the form of an
electroactive film directly on the metal surface by electropo-
lymerization technique. These CP conductive films when
formed along with suitable dopants/anions create excep-
tional redox reactions with the base metal. Electroactive
polymers when reacted with graphene nanoplatelets form
nanocomposite coating that provides double layer protec-
tion against metal corrosion. In the first stage of the protec-
tion mechanism, the conductive polymer forms a passive
oxide layer on the metal surface through redox reactions. In
the second stage, the freely dispersed graphene nanosheets
in the polymer matrix decreases O2 and H2O molecules
penetration by increasing the tortuosity of the diffusion
pathways (Jafari et  al., 2016). The commonly used con-
ductive polymers for coating applications are polyaniline
(PANI), polypyrrole (ppy), ­poly-3,4-ethylenedioxythiphene
(PEDOT) and polyimide (PI).
PANI composite coatings prevent gases/moisture
particles from reaching the substrate surface and isolate
it from the external environment by the following mecha-
nisms (i) by controlling of the electrical conductivity of
nanocomposite system (ii) by controlling redox activity
of PANI (iii) by serving PANI as a sacrificial reservoir of
inhibitor dopants/anions (Kraljić et  al., 2003). Adherent
graphene/PANI hybrid polymer coatings have been
reported to be deposited on copper substrates by elec-
tropolymerization technique using cyclic voltammetry
as shown in Figure 6. The resulted coatings showed out-
standing barrier properties preventing water and oxygen
molecules reaching coating-metal interface due to its
high surface area and better dispersion of graphene in
PANI matrix. Tafel curves indicated that in the presence
of graphene nanosheets in PANI matrix causes corro-
sion potential shifting toward anodic regions with drastic
improvement in the polarization resistance. The corrosion
current density (Icorr) values derived from the Tafel curves
were used to calculate protection efficiency with output of
98% (Jafari et al., 2016). Moreover, iterations of equivalent
circuit model revealed that the coated samples possess
high charge transfer resistance (Rct) and low double layer
capacitance (Cdl) at coating-metal interface indicating
superior corrosion performance.
An identical synthesis technique was employed
by Catt et  al. (2017) to prepare a composite coating con-
sisting of GO and an electroactive polymer (PEDOT) as
matrix material and applied as a corrosion control layer
on magnesium substrate. As-prepared coatings showed
lower hydrogen evolution and corrosion rates of samples
which were validated by hydrogen evolution test and
Tafel extrapolation measurements. Moreover, the large
radii of Nyquist curve obtained by impedance testing
showed increased Rct value indicating higher corrosion
resistance of sample coated with GO/PEDOT. After the

PPA/P2O5

Graphite 4-aminobenzoic acid (ABA) ABF-G

(NH4)2S2O8
1 M HCl
Aniline

Polyaniline/graphene composites (PAGCs)

Figure 6: Schematic diagram depicting the synthesis process of PANI/graphene composites coatings. Reproduced from Chang et al. (2012)
with permission from Elsevier.

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 A.K. Hussain et al.: Graphene-based polymer composite coatings      9
analysis of various test results, the author concluded that
the increased corrosion protection and low hydrogen gen-
eration of coated samples were attributed to the following
three factors; accumulation of negative ions in the coating
layer, formation of passive layer hindering ions diffusion
and formation of Mg-phosphate film by redox reactions.
Besides being corrosion resistant, the coated samples
also exhibited reduced toxicity when exposed to cultured
neurons indicating strong resistance to in vitro corrosion.
A recent study on electrodeposited polypyrrole films
proved that dopant mobility in the films can be minimized
significantly by employing organic anions leading to esca-
lated properties (Raudsepp et al., 2008). Li et al. (2017) fab-
ricated successfully a novel rGO/polypyrrole composite by
voltammetry reduction method as an effective protective
coating for corrosion prevention of mild steel substrates.
Analysis of potentiodynamic polarization, open circuit
potential and EIS measurements revealed that the rGO/
ppy coated samples have large polarization resistance
(54.1 kΩ cm2) and exhibited approximately 7 times higher
corrosion protection ability compared to bare samples.
Moreover, the coating protection efficiency of this nano-
composite was turn out to be 95.9% with good hydro-
phobic property. The corrosion protection mechanism in
this type of coating was explained as the combination of
formation of passive layer of rGO/ppy hybrid and forma-
tion of oxide film that retards the electron transportation
through the coating. The author also explained corrosion
and rust formation phenomenon on mild steel substrate
which consisted of the following reactions
Anodic reaction : Fe → Fe2+ + 2e− (5)
Cathodic reaction : 1 / 2O2 + 2e − + 2H2O → 2OH− (6)
Complete reaction : 2OH− + Fe2+ → Fe(OH)2
→ Fe(OH)3 → Fe2O3 (7)
A novel three-fold protection mechanism was pro-
posed by Chang et al. (2014a) in which PI formed two thin
passive oxide layers i.e. Fe2O3 and Fe3O4 (due to the pres-
ence of active redox catalyst) while graphene nanosheets
provided barrier effect. This graphene/PI composite
coating was prepared by thermal imidization process
on cold rolled steel samples. The coated samples were
inspected for corrosion resistance by cyclic voltammetry
studies and characterized by FTIR and TEM techniques.
This drastic reduction in corrosion current densities
and increase in polarization resistance (165.29  KΩ · cm2)
with corresponding increment in Rct values derived from
Nyquist plot proved that the as-prepared composite coat-
ings have superior corrosion resistance. Furthermore, gas
permeability test results disclosed that gas barrier prop-
erties were also increased due to uniform distribution of
graphene in PI matrix obstructing penetration of oxygen
and water molecules.
Although many conductive polymer matrix based
graphene composite coatings have been developed with
superior corrosion protection efficiency, most of them
have not fully emerged in practical industrial applications.
The pre-eminent reason for this issue is that the conduc-
tive polymer coatings do not adhere firmly to the metal
surface, hence cannot provide protection against large
defects for a long period of time specifically formed during
localized corrosion (Deshpande et al., 2014). In addition,
most of the conductive polymers are overpriced which
makes it impractical to employ it as main matrix materials
for the synthesis of large-scale graphene coatings.
3.1.2 Passivating graphene sheets with polymeric resins
Graphene reinforced composite coatings (GRCCs) pro-
motes galvanic corrosion similar to pristine graphene films
when graphene particles are added above electrical perco-
lation threshold in the composite due to abrupt increase
in the magnitude of bulk conductivity (Potts et al., 2011).
To phase out this corrosion furtherance effect in GRCCs,
passivation is applied to graphene nanosheets. In gra-
phene passivation process, each graphene nanosheet is
enclosed by functionalizing with an insulated or conduc-
tive polymer to reduce graphene-graphene interactions in
the matrix. Passivation by conductive polymer not only
prevents restacking of graphene nanosheets but also their
degradation by inhibiting corrosion by forming an oxide
layer on the surface. Figure 7 shows the synthesis process
of passivating polymer resin onto the surface of graphene
nanosheets by using mechanical mixing method.
To reduce the effect of galvanic corrosion, Sun et al.
(2014) synthesized low electrical conductive pernigrani-
line (PG) capped rGO composite and embedded it in poly-
vinyl-butyral (PVB) polymer matrix to modify the coating
properties. Potentiodynamic polarization and EIS analysis
indicated that the rGO/PG adapted PVB coating served as
an excellent corrosion resistant barrier compared to pris-
tine rGO or PG based PVB with reduced corrosion rate of
6.99 × 10−7 mm/year and enhanced protection efficiency of
97.3%. This amended corrosion property can be correlated
to a high surface resistance of the coating due to less inter-
action between graphene-graphene/metal interface and
by prolonging diffusion channels for corrosive species in
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10      A.K. Hussain et al.: Graphene-based polymer composite coatings
Conductive polymer
GO-polymer hybrid Suspension
Passivating
Dispersion
Graphene oxide
Air spraying
Coated sample
Figure 7: Schematic diagram illustrating passivation of graphene nanosheets by conductive polymer and subsequent coating process.
the coating matrix. Several reports have been published
that shows PANI as a promising conductive polymer to
passivate GO and rGO nanosheets to avoid direct contact
between them. Similarly, Cai et al. (2016) explicitly demon-
strated the preparation of conductive rGO/PANI compos-
ite as anticorrosive filler in waterborne PU matrix forming
a novel coating with superior anticorrosive performance.
Tafel plots and EIS spectra obtained for coated samples
immersed in 3.5% NaCl solution revealed improved cor-
rosion resistance in terms of lower Icorr values and lower
corrosion rates. Moreover, there was a drastic improve-
ment polarization resistance (3057.52 Ω · cm2) and protec-
tion efficiency of the coatings. The coatings also exhibited
good adhesion ability and high impact resistance. With an
intention to attain uniform dispersion of graphene parti-
cles and escalate adhesion capability, Zhao et  al. (2017)
used waterborne epoxy resin as matrix material instead of
PU polymer keeping the same rGO/PANI composite as an
additive. Moreover, the author employed a novel one-pot
emulsion polymerization technique resulting in escala-
tion in electrochemical properties from 1 to 3 orders of
magnitude.
In a separate investigation, Ramezanzadeh et  al.
(2017) reported the passivation strategy for the first time
to improve the corrosion protection efficiency of ZREC.
Covering GO nanosheets with PANI nanofibers not only
prevented GO-GO contact but also resulted in the increase
in electrical connections between zinc particles and base
metal. Moreover, PANI nanofibers noticeably enhanced
the sacrificial behaviour and barrier properties of zinc rich
paint. Corrosion test results revealed improved corrosion
performance with the addition of just 0.1  wt% GO/PANI
composite to ZREC. In another report by the same author,
Metal substrate
Ramezanzadeh et al. (2015) successfully grafted polyiso-
cyanate resin on graphene oxide nanosheets to enhance
its compatibility in PU resin matrix. Polyisocyanate resin
chains were adhered on GO surface because of the for-
mation of amide and carbamate ester bonds. Salt spray
tests results and EIS spectra analysis affirmed that the
PU coatings with just 0.1 wt% GO/polyisocyanate hybrid
nanosheets resulted in significant improvement in barrier
and anticorrosion properties. Moreover, pull off adhesion
test confirmed low adhesion loss in coatings even after a
long period in corrosive conditions.
Deducing the advantage of a high rate of dispers-
ibility and excellent compatibility of urea formaldehyde
(UF) resin with epoxy polymer, Zheng et al. (2017) grafted
UF resin on GO nanosheets via in-situ polycondensation
process. These modified GO/UF hybrid nanosheets were
dispersed into epoxy matrix and composed a novel GO/
UF-epoxy composite coating. Sedimentation test con-
firmed the homogenous distribution of GO/UF nanosheets
throughout the epoxy resin. Furthermore, EIS measure-
ments revealed that corrosion protection efficiency and
barrier performance of modified GO/UF-epoxy coatings
were evidently distinctive compared with pristine epoxy
coatings. The authors suggested that a plausible mecha-
nism for enhanced corrosion performance is connected
to freely dispersed GO hybrid nanosheets that blocked
the penetration of electrolyte through diffusion pathways
on the substrate, thus preventing the base metal from
corrosion.
Several selective electroactive polymers have been
exploited to refine anticorrosion properties of composite
coatings. However, because of the intense intermolecu-
lar attraction between polymer chains, agglomeration
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 A.K. Hussain et al.: Graphene-based polymer composite coatings      11
problem persists, causing high porosity and weak solubil-
ity that cripple its anticorrosion performance (Mišković-
Stanković et al., 2014). Nevertheless, this issue can be dealt
with using conductive polymer pigments as fillers in neat
organic resins such as acrylic resin or epoxy resin. Sheet
templating method for conductive polymers is relatively
a new technique in which conductive polymer pigments
when mixed with graphene transforms into sheet-like
structures because of the hybridization of graphene
particles. To extend the free distribution of graphene
nanosheets in polymer, Jiang et al. (2016) applied an inno-
vative sheet templating approach to synthesize graphene/
polypyrrole epoxy composite coatings. In this experiment,
the author used inexpensive ppy pigments with graphene
to form graphene/ppy hybrids. Composed hybrid gra-
phene/ppy epoxy coatings revealed high electric con-
duction and improved corrosion protection efficiency by
50–100 order higher compared with neat epoxy coatings.
Considerable enhancement of corrosion properties was
ascribed to their hybridized graphene nanosheets, which
causes sheet templating effect on ppy pigments. These
hybrid sheets such as graphene/ppy pigments formed a
large barrier in a parallel direction extending the path-
ways of corrosion agents to reach the coating/substrate
interface. Moreover, the author pointed out that the mass
percentage of graphene used in coatings was only about
0.05–0.15, which scales down the total cost of graphene/
ppy epoxy coatings.
From the above literature reports, it can be concluded
that passivation of graphene sheets by polymer resins
can protect the metal against corrosion attack for a longer
period as compared to pristine graphene films. However,
Nanoparticles
GO hybrid
Suspension
Anchoring
Dispersion
Air spraying
Graphene oxide
Coated sample
Figure 8: Schematic diagram illustrating anchoring of nanoparticles on graphene sheets and subsequent coating process.
the structural strength of these coatings is not sufficient
to withstand external damage and becomes susceptible
to the corrosion effect. Besides strength, another factor
that limits the use of the conductive polymer to passivate
graphene nanosheets is its high cost. Certain conductive
polymers such as PANI, ppy and PEDOT are very expen-
sive, eventually increasing the final price of the coatings
when prepared in large scale for industrial applications.
3.1.3 Anchoring nanoparticles on graphene nanosheets
Numerous research articles have been reported on prob-
lems concerning to compatibility and dispersion of gra-
phene sheets in the polymer matrix. As discussed in the
earlier section, graphene nanosheets have a tendency to
agglomerate when mixed with the polymer matrix, and to
avert this difficulty, a new strategy of tethering graphene
nanosheets with metal oxide nanoparticles is adopted
by several researchers (Zhang et al., 2014; Archana et al.,
2018). Recently, some investigators reported that the intro-
duction of inorganic nanoparticles between graphene
layers also prevents re-agglomeration. These anchored
nanoparticles increase the surface area and interplanar
spacing of graphene sheets and promote bonding with the
polymer matrix on both sides (Wang et  al., 2010). Apart
from increasing the dispersibility of graphene sheets, in
some cases, metallic nanoparticles also behave like cor-
rosion inhibitors forming an oxide layer and provide extra
protection against corrosion. Figure 8 represents the syn-
thesis process of attaching nanoparticles onto the surface
of graphene nanosheets by using simple mechanical
Metal substrate
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12      A.K. Hussain et al.: Graphene-based polymer composite coatings
mixing method. Furthermore, when these spherical
shaped nanoparticles are grafted on the surface of gra-
phene oxide, micropores generated in hybrid polymer
coatings during the solvent evaporation process are
covered inherently preventing electrolyte permeation (Ma
et al., 2016). Among various available metal oxide nano-
particles, magnetic Fe3O4 nanoparticles are considered as
ecofriendly materials with remarkable corrosion protec-
tion and adhesion properties when doped in a composite
matrix (El-Mahdy et al., 2014).
Di et  al. (2016a,b,c) synthesized a novel hybrid GO/
Fe3O4 epoxy coatings by a hydrolytic polycondensation
process in which Fe3O4 nanoparticles were decorated on GO
nanosheets. Fe3O4 nanoparticles were prepared by copre-
cipitation approach and tethered onto the GO nanosheets
with the assistance of silane coupling additives. EIS spectra
indicated an enhancement in anticorrosion efficacy with
large impedance modulus due to excellent dispersion of
GO/Fe3O4 hybrid sheets blocking the micropores to prevent
the electrolytic diffusion into the epoxy matrix. Also, the
long-term protection efficiency of the coatings was not up to
the mark because of the generation of surface defects upon
exposure to electrolyte for 20  days. This hybrid coating
developed was compact in nature and cannot be deposited
on elastic substrate surfaces such as flexible metal pipes
and plates. For stretchable surfaces, Wang et al. (2017) pio-
neered a soft flexible GO/Fe3O4-natural rubber composite
coatings using latex compounding technique. Interestingly,
the composite coatings showed up exceptional corrosion
resistance in terms of reduced corrosion current densities
and reduced corrosion rate (5.2 × 10−4 mm/year). The pro-
posed mechanism for improved anticorrosion performance
was due to the aligned structure of Fe3O4-modified GO
nanosheets that assisted to deter the diffusion pathways
for corrosion agents. Furthermore, Fe3O4 nanoparticles
attached on GO nanosheets also avoided the GO-metal
interaction, therefore raising the polarization resistance of
the coatings, which was validated by EIS calculations.
Similarly, silica nanoparticles can also be employed
as GO modifier because of its good corrosion resistance,
excellent chemical stability and high dispersion rate
(Chen et al., 2012). Ramezanzadeh et al. (2016a,b) devel-
oped a novel two-step sol-gel method of preparing silica
nanoparticles decorated GO nanohybrid and employed
it in epoxy resin to make a hybrid coating with excellent
corrosion resistance. On the contrary, Pourhashem et al.
(2017a,b) used tetraethyl orthosilicate as organosilane to
diffuse SiO2 nanoparticles on the surface of GO nanosheets.
Introduction of SiO2 nanoparticles considerably improved
dispersion and corrosion inhibition efficiency. Also, the
cathodic delamination of coating notably decreased
because of the existence of GO/SiO2 hybrid nanosheets in
the coatings. SiO2 nanoparticles functioned as a barrier
between the GO nanosheets and improved its degree of
exfoliation and dispersion in the epoxy matrix, causing a
decrease in moisture adsorption and penetration of cor-
rosive media through the nanocomposite coatings.
Recently, lanthanide nanoparticles were used as a suit-
able substitute for SiO2 and Fe3O4 nanoparticles because of
their low toxicity and good corrosion inhibition effect. Lan-
thanide-based compounds can restrain corrosion reaction
and preserve the metal surface against degradation even
under strident circumstances. Lanthanide-based coatings
have been proven as excellent corrosion inhibitors and
protector against high-temperature oxidation (Bethencourt
et al., 1998). Rahman et al. (2017) attempted to synthesize
hybrid nanocomposite coating by incorporating graphene
and ceria nanoparticles composite in water-borne PU matrix
for corrosion protection. Polarization curves of coated mild
steel samples after 15 day exposure to 3.5% NaCl showed
higher corrosion potentials for G/CeO2-PU coatings, indicat-
ing better corrosion performance compared with pristine
PU coatings. The synthesized coatings exhibited remark-
able anticorrosion properties by barrier and passivation
effects, resisting cracks formation and maintained their
integrity when exposed to extreme environment.
Titanium oxide (TiO2) nanopowder has been reported
to be successfully integrated into the neat epoxy coating to
improve its barrier and corrosion performance (Radoman
et al., 2014). Similar to graphene nanosheets, TiO2 nano-
powder also tends to segregate when mixed with other
materials because of its high polarity and large specific
surface area. To remove this limitation and enhance
the anticorrosion performance of neat epoxy coatings,
Yu et  al. (2015a,b) anchored TiO2 nanoparticles on GO
nanosheets, and this hybrid was reinforced in epoxy
coatings via solvent evaporation method. As prepared
GO/TiO2-epoxy coatings exhibited remarkable corrosion
protection behavior with maximum corrosion protection
efficiency surging up to 99.96%. Scanning electron micro-
scopy (SEM) micrographs revealed that GO/TiO2 hybrid
sheets distributed homogenously in the epoxy matrix and
formed sheet-like structures blocking the micropores in
coatings to limit the penetration of electrolytic molecules.
Experimental results also demonstrated that the anticor-
rosion performance of GO/TiO2-epoxy nanocomposite
coatings largely depends on the extent of dispersion and
exfoliation of graphene particles.
Similar to titania nanoparticles, aluminum oxide
(Al2O3) and zirconium oxide (ZrO2) nanoparticles were also
anchored on GO nanosheets by Yu et al. (2015a,b) and Di
et al. (2016a,b,c) and dispersed in epoxy resin matrix via
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 A.K. Hussain et al.: Graphene-based polymer composite coatings      13
solvent evaporation and ultrasonic mixing process using
silane coupling agents to form highly corrosion resistant
GO/Al2O3-epoxy and GO/ZrO2-epoxy coatings, respectively.
Introduction of GO/Al2O3 and GO/ZrO2 nanohybrids in
epoxy resin exhibited excellent dispersion and exfoliation
property, thereby enhancing the corrosion performance
of the coatings. However, the low weight percentage of
nanoparticles in epoxy was not able to enhance notably
the anticorrosion properties to a higher extent. Moreover,
both the composite coatings showed similar corrosion
protection mechanism. Exceptional anticorrosion behav-
ior of both the hybrid nanocoatings was associated to its
active double barrier property and free dispersion of GO
hybrid sheets in epoxy coatings.
Considering the above literature reports, it can be
noticed that the nanoparticles selected for anchoring on
GO nanosheets are metal oxide-based nanoparticles that
are expensive to synthesize. Hence, to reduce the overall
cost of graphene-epoxy coatings, low-cost calcium car-
bonate (CaCO3) nanoparticles were exploited for the
first time to modify the surface of graphene nanosheets.
Di  et  al. (2016a,b,c) fabricated GO nanosheets anchored
with CaCO3 nanoparticles by means of 3-aminopropyl-
trimethoxysilane (APTES) additive. These modified
GO/CaCO3 hybrid nanosheets were diffused in the epoxy
matrix and cured to form highly anticorrosive composite
coatings. SEM and TEM micrographs revealed homoge-
neous dispersion of CaCO3-anchored GO nanosheets in
the epoxy matrix, which in turn enhanced the anticorro-
sion performance of the coatings by providing tortuous
passage to the electrolyte.
The foremost limitation of using inorganic nano-
particles in polymer hybrid coatings is its compatibility
with graphene nanosheets and the polymer matrix (Kim
et al., 2010). Moreover, expensive coupling agents such as
APTES are needed to covalently attach nanoparticles onto
the surface of graphene sheets. Also, the thickness of the
final coated layer on the metal surface increases with the
type of polymer matrix used ranging from 40 nm to 100 μm,
which can strongly influence the structural properties of
the metal (Watcharotone et  al., 2007). Thus, the imple-
mentation of this strategy of anchoring expensive inor-
ganic nanoparticles on graphene oxide nanosheets makes
GPMCCs inappropriate for large surface area substrates.
3.1.4 Chemical functionalization of graphene nanosheets
Functionalization of graphene sheets by chemical modi-
fication is one of the convenient approaches to counter
flocculation and stabilize graphene suspension within
the polymer matrix. Chemical functionalization is an
effective way to amend the defects in graphene by altering
the electronic and crystal structure to induce specific elec-
tronic and magnetic properties (Boukhvalov & Katsnel-
son, 2008). The promising chemical methods to modify a
graphene surface are covalent functionalization and non-
covalent functionalization, which increase the interlayer
distance between graphene layers and promote steady
interfacial interactions between graphene nanosheets
and the polymer matrix (Boukhvalov & Katsnelson, 2009).
In covalent functionalization, covalent bonds are formed
between the epoxide groups and carboxylic groups of GO
and the chemical coupling agent. However, covalent graft-
ing of GO sheets involves lengthy chemical processes that
can induce irregularities changing the inherent corrosion
properties, whereas in noncovalent functionalization,
strong π-π bonds are established between GO nanosheets
and stabilizer conserving its properties (Kuila et al., 2012).
One of the most widely used chemicals for function-
alization of graphene is APTES, which is a type of silane
coupling agent and promotes strong interfacial bonding
between graphene sheets and the polymer matrix.
Pourhashem et  al. (2017a,b) evaluated the influence of
amino silane on GO nanosheets as nanofillers in epoxy
matrix coatings to increase dispersion quality. Function-
alization of GO nanosheets with APTES showed a good
interfacial interaction of GO with polymer and superior
anticorrosion performance as confirmed by FESEM and
EIS analysis. However, the addition of modified GO of more
than 0.1 wt% resulted in the agglomeration of nanosheets
in the matrix reducing the barrier properties. Another
study (Mo et  al., 2015) was carried out to investigate the
impact of modified graphene oxide by APTES in PU com-
posite coatings. The team fabricated PU composite coat-
ings by reinforcing functionalized graphene oxide (FGO)
and functionalized graphene with exceptional corrosion
and tribological properties. The graphene nanosheets
were chemically treated with APTES to enhance the dis-
persion and compatibility with PU matrix. However, cor-
rosion testing results of FGO/PU coatings exhibited lower
corrosion protection when compared with functionalized
graphene/PU coatings vowing to the presence of plentiful
oxygenated groups. These oxygenated groups of FGO pro-
moted stronger interfacial interaction but induce imperfec-
tions in graphene lattice structure. Although salinization
is a popular method to functionalize graphene, it suffers
from the limitation of hydrolytic degradation. When a
salinized composite is subjected to the aqueous atmos-
phere, the salinized interfaces absorbs moisture and gets
hydrolyzed, thereby opening additional passages for water
molecules to diffuse (Matinlinna et al., 2004).
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14      A.K. Hussain et al.: Graphene-based polymer composite coatings
Apart from silane, there are other types of coupling
agents that can be employed to functionalize graphene
such as titanate and zirconate coupling agents. Table  1
shows various chemicals used to modify graphene
nanosheets to increase dispersion and bonding with the
polymer matrix. Li et al. (2014) employed titanate coupling
agent for the first time in rGO/PU composite coatings and
found that the titanate not only improves the homogene-
ous distribution of rGO nanosheets in PU matrix but also
aligns itself parallel to the substrate surface. This auto-
alignment property of graphene nanosheets was directed
by the decrease in total excluded volume. Nevertheless,
this unique in-plane alignment property guides in utiliz-
ing the full surface area of rGO layers to confront the elec-
trolyte and provide tortuous path to limit its permeation
through the coatings. High anticorrosion performance of
the composite coatings was confirmed by Nyquist plots
even after 96  h of exposure to electrolyte. However, the
titanate-treated graphene did not display a self-alignment
behavior when added up to 0.2  wt% in the matrix and
was scattered in random three-dimensional directions. In
another research, Diouf and Asmatulu (2014) carried out
a study to determine the effect of organofunctional alkox-
ysilane modified graphene on corrosion and weathering
resistance of fiber-reinforced composite substrates. The
graphene nanoplatelets were salinized and mixed in dif-
ferent proportions in PU primer matrix via mechanical
mixing sonication process. Experimental results indicated
Table 1: Functions and synergistic effects of functionalizing agents on graphene nanosheets.
Filler + matrix   Functionalizing agent  
Graphene + epoxy   Poly-2-butylaniline (P2BA)  
GO + epoxy   3-Aminopropyl triethoxysilane  
(APTES)
GO + polystyrene   p-Phenylenediamine + 4-vinylbenzoic   Mild steel   Augments the GO particles dispersion and   Yu et al. (2014)
acid
GO + epoxy   p-Phenylenediamine (PPD)  
rGO + polyurethane  Titanate coupling agent (TCA)  
that with the addition of 2 wt% salinized graphene sheets
produced drastic improvement against corrosion and UV
degradation.
Ramezanzadeh et al. (2016a,b, 2018) and his team con-
ducted two separate experiments with ­p-phenylenediamine
(PPDA) as a functionalizing agent. In the first experi-
ment, they covalently grafted PPDA aromatic diamine
on GO nanosheets to enhance dispersion and interfa-
cial bonding of GO nanosheets with epoxy matrix. In the
second experiment, they synthesized PPDA functionalized
GO nanosheets with three different lateral sizes, i.e. small
area GO nanosheets with 0.85 μm size, medium area GO
nanosheets with 8.2 μm size and large area GO nanosheets
with 38 μm size. The covalent functionalization of GO
surface was achieved through wet transfer method and
resulted in successful intercalation leading to increased
corrosion inhibition efficiency. Addition of FGO into the
epoxy enhanced ionic resistance and hydrophobicity of the
coating while hindered the penetration of Cl− ions due to
creation of covalent bonds between amine groups of PPDA
and epoxide groups of GO. Furthermore, the GO nanosheets
with medium lateral size delivered highest barrier perfor-
mance and anticorrosion properties. A similar investiga-
tion was reported by Gu et al. (2015) in which carboxylated
aniline trimer stabilizer was used as dispersing agent with
graphene nanosheets and synthesized water-soluble gra-
phene/epoxy hybrid coatings. After functionalization,
stable high concentration of graphene nanosheets (>1 mg/
Substrates   Functions   References
Mild steel   Works as dispersing agent and helps in   Chen et al. (2017)
stabilizing the dispersion of graphene
nanosheets in organic solvents; imparts
synergistic redox catalytic effect in epoxy
coatings
Mild steel   Promotes the bonding between graphene   Pourhashem
oxide layers and epoxy matrix et al. (2017a,b)
improves the interaction of modified GO
flakes with polystyrene matrix; improves
storage modulus and mechanical strength
of the coated sample
Mild steel   Enhances interfacial interactions   Ramezanzadeh
enhancement between polymer and GO et al. (2016a,b,
sheets; increases tensile strength and 2018)
fracture toughness of the coated sample
Galvanized   Functions as adhesion promoter and   Li et al. (2014)
steel prevents agglomeration of rGO sheets;
causes self-alignment of graphene layers
parallel to the substrates surface
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 A.K. Hussain et al.: Graphene-based polymer composite coatings      15
mL) was able to disperse in epoxy system by forming strong
π-π bonds between graphene and carboxylated aniline
trimer stabilizer. A series of electrochemical measure-
ments revealed that the increased dispersion of graphene
nanosheets into waterborne epoxy drastically enhanced
corrosion resistance properties and minimized the coating
delamination.
Zhu et  al. (2017) very recently developed a novel
3-(1-(2-aminopropoxy)propan-2-ylamino)propane-1-sul-
fonate sodium functionalized water-dispersible graphene
via nucleophilic ring opening reaction. These chemi-
cally modified graphene nanosheets were dispersed in
acrylic modified alkyd resin matrix to enhance the cor-
rosion protection performance. SEM images showed the
homogeneous distribution of graphene sheets in alkyd
resin nano-emulsion forming compact and uniform coat-
ings that can improve barrier properties against moisture
and oxygen. Corrosion tests indicated that 3-(1-(2-amino-
propoxy)propan-2-ylamino)propane-1-sulfonate sodium
functionalized coatings has superior corrosion-resistant
properties compared with pristine alkyd resin coatings. EIS
measurements further revealed that the formed coatings
exhibit dual corrosion protection mechanisms, i.e. barrier
effect and anodic protection mechanism. Yu et  al. (2014)
demonstrated successfully for the first time the application
of vinyl-polystyrene/GO (V-PS/GO) hybrid coatings in anti-
corrosion system. The nanocomposite composite coating
was prepared by in situ miniemulsion polymerization
process and tested for anticorrosion properties. The as-pre-
pared hybrid coatings exhibited high corrosion resistance
properties with inhibition efficiency of 99.53% by intro-
duction of 2  wt% of functionalized GO in the polystyrene
matrix. Apart from corrosion properties, the GO-modified
coatings showed an improvement in mechanical proper-
ties, thermal stability, storage modulus and thermal decom-
position temperature. The author explained the reason for
this enhanced performance by V-PS/GO nanocomposite
coatings as the increased dispersion of GO nanosheets in
nonconjugated polystyrene matrix due to strong π-π inter-
actions between polystyrene and modified GO.
Undoubtedly, chemical modification of graphene
sheets is a beneficial approach to counter the agglom-
eration, but there are certain demerits associated with it.
First, the use of chemicals could alter graphene properties
that can subsequently affect the corrosion properties of
the coatings. Second, chemical functionalization of gra-
phene is a time-consuming and tedious process. Third,
most of the chemicals used for functionalization are
expensive and toxic in nature (Hirsch et al., 2012).
Graphene-embedded composite coatings containing
well-dispersed graphene sheets in the matrix material not
only improves barrier properties but also improves struc-
tural durability and thermal and electrical properties (Hu
et al., 2014). However, the graphene sheets used in these
coatings are synthesized employing presently available
methods generating various types of structural defects
that can affect the protection efficiency. The direct impact
of these local defects in graphene can cause accumulation
of oxygen molecules that can degrade its performance
(Rohini et  al., 2015). All the demerits described above
restrict the free usage of graphene-based coatings for
anticorrosion application in a large scale. More advanced
processes and methods with regard to the enhancements
in exfoliation, dispersion and adhesion property of gra-
phene sheets are needed so that it can be utilized effec-
tively in the preparation of anticorrosion coatings. Apart
from requiring costly equipment and tedious preparation
methods, most of the strategies described in the above
section to improve corrosion performance of GPMCCs
need expensive chemicals and materials that can harm
the surrounding environment.
Recent research reports on corrosion performance of
graphene-based composite coatings and related electro-
chemical parameters are summarized in Table 2. From the
table, it can be observed that the corrosion inhibition effi-
ciency of prepared coatings depends upon several factors
such as synthesis method, type of deposition method
and substrate material. Furthermore, the corrosive envi-
ronment to which the coatings are subjected and the
adhesion ability between the polymer and the substrate
surface could also affect the performance of the coatings.
Over the past 5 years, there is a drastic increase in research
conducted on graphene coatings with polymer as matrix
material compared with pristine graphene coatings (Bon-
avolontà et  al., 2017). Future research could be focused
on experimenting with coatings containing low-cost
inorganic fillers combined with graphene with superior
properties. Only a few innovative synthesis techniques are
reported in the recent years to improve the performance
of the coatings. Even though magnesium and titanium are
being used widely nowadays for a variety of applications,
most of the research is directed toward the deposition of
coatings on mild steel and copper substrates only.
4 Summary and future trends
In this review article, a comprehensive survey of various
synthesis techniques and strategic approaches to
prevent flocculation of graphene sheets in the different
polymer matrix has been presented. Despite impressive
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 Table 2: Summary and comparison of the electrochemical parameters of graphene-reinforced polymer composite coatings deposited on different substrate materials.

Composite coating   Coating method   Substrate   Coating with graphene   Coating without graphene  References
material   2 2
  2
Ecorr (mV)   Icorr (μA/cm )   Rcorr (mm/year)   Rp (KΩ cm ) Ecorr (mV)   Icorr (μA/cm )   Rcorr (mm/year)   Rp (KΩ cm2)

rGO/ppy   Electrodeposition   Mild steel   −544   0.85   0.0099   66.9   −691   9.34   10.85 × 10−2   6.33  Li et al. (2017)
rGO + Fe3O4/natural   Cold spraying   Mild steel   −274   1.40   0.016   0.0252   −862   110.6   1.28   271 × 10−3  Wang et al. (2017)
rubber
GO + SiO2/epoxy   Cold spraying   Mild steel   −439   0.09   0.0012   0.0417   −543   14.6   0.1705   0.00186  Pourhashem et al.
(2017a,b)
rGO/ZnAl + LDH + epoxy  Cold spraying   Mild steel   −0.635   0.0733   0.0007   3.49   −629   0.49   0.00576   3.49  Yu et al. (2017)
rGO + lanthanide   Solvent evaporation   Mild steel   −0.162   0.013   0.006   4.77 × 103   −442   3.26   1.45   2.19 × 104  Alam et al. (2016)
ions + DBSA/ppy method
GO/chitosan   Dip coating   Mild steel   −374   3.9   0.0017   1.44   −457   7.7   0.00256   0.00387  Fayyad et al. (2016)
GO/epoxy   Film applicator   Mild steel   −250   0.2015   0.0031   1.669   −0.85   0.501   5.884 × 10−3   0.756  Rajabi et al. (2015)
G/polyurethane   Film applicator   Mild steel   −27.2   2.45 × 10−5   2.88 × 10−7   –   −125   0.178 × 10−6   2.09 × 10−9   –  Huang et al. (2016)
G/epoxy   Film applicator   Q235 steel   −566   0.0551   0.0007   369.4   −637   0.121   0.00142   169.2  Liu et al. (2016)
G/polyimide   Spin coating   Cold rolled   −432   0.15   0.00176   165.29   −573   2.75   0.256   11.1  Chang et al. (2014a)
16      A.K. Hussain et al.: Graphene-based polymer composite coatings

steel
G/epoxy   Nano-casting   Cold rolled   −411   0.10   0.00009   442   −633   0.35   0.00033   37.87  Chang et al. (2014b)
steel
G/PANI   Electropolymerization   Copper   −234   0.1   0.00005   1.5 × 102   −0.3   1.8   4 × 10−3   1 × 104  Jafari et al. (2016)
GO/PMMA   Drop casting   Copper   −108   0.83 × 10−3   9.35 × 10−6   –   −237   0.157   0.001822   –  Qi et al. (2015)
rGO + DE + PDMS   Cold spray   Copper   −0.112   0.159   0.00158   –   −108.7   0.95   0.011   –  Nine et al. (2015a,b)
GO/pernigraniline   Dip coating   Copper   −23   5.98 × 10−5   6.99 × 10−7   9.86 × 105   −61   4.11 × 10−4   4.8 × 10−6   1.9 × 108  Sun et al. (2014)
rGO/isocyanate   Electrodeposition   Copper   −211   4   0.04663   –   −164   38.25   0.55   –  Singh et al. (2013a,b)
GO/isocyanate   Electrodeposition   Copper   −211   3.49   0.04068   0.025   −164   38.28   0.58   0.008  Singh et al. (2013a,b)
rGO/epoxy   Spin coating   Zinc   −957   0.18   0.00272   –   −900   0.75   1.3   –  Zhang et al. (2015)
rGO/silicon-acrylate   Spin coating   Zinc   −585   0.45   0.00682   –   −327   13.8   28.7   –  Cao et al. (2015)
resin
GO/PEDOT   Electropolymerization   Magnesium  −155   12.3   0.28233   –   −1705   49.6   1.1385   –  Catt et al. (2017)
rGO/PANI   Brush painting   Glass   −112   0.74   0.0081   –   −0.153   12.5   0.078   –  Zhao et al. (2017)
G/PANI   Nano-casting   Glass   −537   0.38   0.00044   135.22   −647   3.7   0.0043   14.43  Chang et al. (2012)

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 A.K. Hussain et al.: Graphene-based polymer composite coatings      17
results, most of the coatings described in the above sec-
tions are not fabricated in mass quantity for large surface
area application due to cost limitations. Moreover, there
are still many obscure factors influencing the corro-
sion properties that are needed to be investigated in
graphene-embedded composite coatings. The primary
challenge in fabricating effective coatings to protect the
metal surface from corrosion is to utilize economical
filler materials and develop more facile and viable ecof-
riendly synthesis techniques. Prospective future studies
will be directed on reducing the overall cost of coatings
and enhancing the dispersibility and compatibility of
graphene sheets in various polymer matrix materials
by developing innovative strategies. Further advance-
ment in this specific area could lead to the fabrication
of ultramodern nanostructure-tailored coatings with
exceptional corrosion inhibition capabilities. While this
review paper has been written with definite corrosion
application in mind, the original significance of com-
prehending graphene-based coating systems will give
far-reaching impact on a wide range of advanced emerg-
ing applications.
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