J. Coat. Technol. Res.
, 17 (1) 19–55, 2020
https://doi.org/10.1007/s11998-019-00275-6
REVIEW ARTICLE
A review on application of carbon nanostructures as nanofiller
in corrosion-resistant organic coatings
Sepideh Pourhashem, Ebrahim Ghasemy, Alimorad Rashidi, Mohammad Reza Vaezi
 American Coatings Association 2019
Abstract Since corrosion has tremendous economic
effects, academics and industries have sought to
develop more effective coatings. These efforts have
led to profound importance of nanocomposite coatings
based on polymers and carbon nanostructures. It is
shown that good reinforcement, advanced mechanical
properties, and high corrosion resistance are only
found at relatively low levels of nanocarbon (i.e.,
fullerene, carbon black, carbon nanotubes, graphene,
graphene oxide, and carbon dots) loadings in coating
compositions. Herein, a survey of breakthrough scien-
tific studies on application of carbon nanostructures in
corrosion-resistant organic coatings is carried out to
pave the way for future developments in novel
nanocoatings.
Keywords Carbon nanostructures, Polymer
composites, Coatings, Corrosion
Introduction
Corrosion is one of the main challenges of countries
because of its notable economical, mechanical, chem-
ical, and health side effects on the development of
S. Pourhashem, A. Rashidi (&)
Nanotechnology Research Center, Research Institute of
Petroleum Industry (RIPI), West Entrance Blvd., Olympic
Village, P.O. Box 14857-33111, Tehran, Iran
e-mail: rashidiam@ripi.ir
E. Ghasemy
Nanotechnology Department, School of New Technologies,
Iran University of Science and Technology, Tehran, Iran
M. R. Vaezi
Department of Nanotechnology and Advanced Materials,
Materials and Energy Research Center, P.O. Box 31787-316,
Karaj, Iran
industries.1–4 Unfortunately, corrosion cannot be fully
prevented, and thus, corrosion control strategies focus
on slowing the kinetics and/or altering its mechanism.5
Meanwhile, protective coatings are the most common
and cost-effective means of corrosion and biofouling
control for materials susceptible to environmental
interactions,6,7 and they are the first option for
protecting metallic structures against corrosive envi-
ronments.8
Long lifetime of metallic structures and their finan-
cial benefits can be achieved by selecting an appropri-
ate coating material.9 In order to develop coating
systems possessing enhanced performance, various
factors such as longer protective lifetime, lower price,
lower weight, and sustainability should be considered.
The common coatings which are considered for indus-
trial applications include metallic coatings (e.g., Zn and
Cr) and polymeric coatings and paints.10,11 In this
respect, it is reported that the Zn- and Cr-based
coatings are mostly used in industry.11 However, the
application of the Cr-based coatings is restricted due to
environmental issues.12,13 Furthermore, considering
the high cost and the need for higher weight of the
Zn-based coatings, they are not regarded as practical
candidates anymore.10 Finally, the polymeric coatings
and paints containing porosity need to be modified to
become an interesting alternative.14 To tackle these
shortcomings, researchers have mainly focused on
using nanocomposite coatings to provide novel and
optimum corrosion-inhibiting systems.15–20 The wide
range of studies devoted to this field have shown that
incorporating carbon nanostructures into polymers to
prepare polymer-based nanocomposites can lead to the
development of novel, low-cost, environmental-
friendly, and lightweight corrosion-inhibiting
nanocoatings with longer lifetime.
Paints based on resins including urethanes, latexes,
epoxies, and silicon alkyds are a class of organic or
polymeric coatings mainly used for decoration and
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J. Coat. Technol. Res., 17 (1) 19–55, 2020
protection of surfaces against corrosive environ-
ments.21–23 Organic coatings provide an effective bar-
rier between the metallic substrate and its environment
and/or inhibit corrosion.7,24
However, the most important issue in the field of
paints is developing a new generation of coatings with
enhanced corrosion resistance in order to increase the
lifetime and reduce the environmental impacts, main-
tenance, and replacement cost.21,25 Moreover, extend-
ing service life has positive environmental and
economic effects on waste reduction and energy and
raw material consumption.26
One technique that has recently been used to
achieve the desired mentioned properties is addition
of nanoscale additives into various polymer matrices to
generate corrosion resistance nanocomposite coat-
ings,7,21,22 because nanocomposite coatings combine
the outstanding performance of both nanoscale fillers
and polymer matrix in material design.27 Nanocom-
posite coatings can significantly increase the cost-to-
benefit ratio, provide cost-effective solutions, and
improve the performances.28
Engineered nanoparticles have been used in organic
coatings as hardener (silica dioxide), UV-light absor-
ber (titanium dioxide or zinc oxide), or biocide
(nanometals) in addition to the conventionally applied
pigments.29,30 However, within the past decades, the
discovery of nanostructure carbon materials, namely
zero-dimensional (0D) fullerene, 1D carbon nan-
otubes, and 2D graphene nanosheets, has boosted a
revolution in the field of the science and technology of
materials due to their remarkable physical and
mechanical properties. They are widely used as
nanofillers to improve electrical, thermal, optical, and
anticorrosion properties of polymer composites.31–36
The schematic of different carbon nanostructures used
in coating industry is shown in Fig. 1. Furthermore,
(c)
(b)
(a)
Carbon
Oxygen
Hydrogen
Fig. 1: Schematic of different carbon nanostructures: (a) fullerene; (b) carbon nanotube; (c) graphene; (d) graphene oxide;
(e) carbon dots
20
nanocarbons show the ability to achieve enhancements
in properties at significantly low-weight fractions of
additives (i.e. 0.1–1 wt%); by contrast, the optimal
loading fraction of other fillers lies in the 5–10% weight
fraction range which can result in significant weight
penalty.37
Therefore, the mentioned properties make nanocar-
bon the best current and future solution for a wide
range of applications. Although a significant amount of
review studies exist on polymer composites containing
carbon nanostructures,38–41 to the best of our knowl-
edge, there is no review published on the corrosion-
and degradation-resistant properties gained via the
incorporation of carbon nanostructures in organic
coatings and paints. Therefore, this review presents
the current research trends in application of carbon
nanostructures in corrosion-resistant organic coatings.
Fullerene
The discovery of soccer-ball-shaped Buckminster-full-
erene in 1985 was an exciting and unexpected discov-
ery that established an entirely new branch of
chemistry.42 In defect-free form, C60 fullerenes are
enclosed cage-like structures comprised of 12 five-
member rings and an unspecified number of six-
member rings.39,43,44 Fullerene has attracted the atten-
tion of theoretical and experimental scientists, and its
physical and chemical properties are investigated in
detail.45 Typical properties of fullerene are briefly
described in Table 1. Consequently, their specific
properties in terms of electrochemistry, gas absorption,
chemical, optical, mechanics, and others have been
revealed.46
(e)
(d)
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

Table 1: Typical properties of fullerene C60

Diameter (nm) BET surface area (m2/g) Density (g/cm3) Thermal conductivity (W/m K) Electrical conductivity (Sm1)

0.5–1.247 1.1–17648 1.6544 0.449 10–1250

C60 fullerene carbon allotropes have been incorpo-

rated in polymer materials to combine the interesting
electronic and optical properties of C60 with mechan-
ical and processing advantages of polymers.51 For
example, fullerene additives show potential to signif- o
icantly enhance the mechanical properties (i.e., NH o
Young’s modulus, ultimate tensile strength, fracture Si

toughness, fracture energy, and the material’s resis- o

tance to fatigue crack propagation) of epoxy compos-
ites at relatively low ( 1%) nanofiller loading
fractions. This will have a beneficial impact on struc-
tural applications of epoxies such as protective paints,
coatings, and composites.37 It should be mentioned Fig. 2: Schematic of C60 functionalization with silane
that Badamshina and Gafurova52 published a review
article about the mechanical, tribological, high-tem-
matrix, improving the adhesion between polymer and
perature stability, gas permeability, electrical and
nanofiller, reducing the coating porosity, and enhanc-
optical properties of polymeric nanocomposites con-
ing the adhesion of coating to metallic substrate.
taining C60.
However, the tribological and corrosion resistance
Moreover, a study on corrosion behavior of paint
properties of epoxy composite coatings significantly
containing 1 wt% of fullerene was done in 3.5 wt% of
weaken when the content of FC60 and FG is more than
NaCl, 2 wt% HCl, and 2 wt% NaOH solutions. It was
0.5 wt% due to aggregation of FC60 and FG, leading
found that the corrosion penetration rate of fullerene
to growth of cracks across the whole epoxy composite
paints decreased by 1 order of magnitude in solutions
coatings. Besides, epoxy/FC60 shows better tribologi-
of NaCl and NaOH, while it was normal effective in
cal and scratch resistance properties but worse anti-
HCl solutions by the addition of only 1 wt% of
corrosion performance compared to epoxy/FG
fullerene nanofiller.53
coatings, which can be assigned to different shape
Further, Liu et al.54 considered the effect of func-
and inherent properties (including hardness, shear
tionalized fullerene C60 (FC60) and functionalized
stress, and surface area) of fillers.
graphene (FG) on corrosion protection performance
However, it should be mentioned that fullerenes
and tribological properties of solvent-based epoxy
exist in a variety of forms with different carbon
coatings. As Fig. 2 shows, 3-aminopropyltriethoxysi-
numbers; therefore, it is problematic to make gener-
lane (KH550) was used as silane-coupling agent for
alizations about their applications.55
chemical modification of C60 and graphene. The epoxy
composite coatings containing different mass fractions
of nanofiller including 0, 0.25, 0.5, 0.75, and 1 wt%
were prepared. The electrochemical impedance spec- Carbon black
troscopy (EIS) results of epoxy/FG and epoxy/FC60
nanocomposite coatings are presented in Fig. 3. The Carbon black (CB), a conductive and low-cost spher-
results show that the tribological and anticorrosion ical nanoparticle,56 is widely used as a pigment in
performance of epoxy coatings enhances via adding the coating industry.57 The intrinsic properties of CB
FC60 or FG. Higher tribological properties of are listed in Table 2.
nanocomposite samples are due to lubrication effects Wei et al.59 prepared a series of fusion-bonded
of nanofillers in epoxy matrices. Also, the enhance- epoxy coatings containing 0.5–4 wt% CB on mild steel
ment of corrosion resistance is due to barrier perfor- substrates. The EIS results (Fig. 4) in 3% NaCl
mance of nanofillers (FC60 and FG) in epoxy coatings solution show that the impedance modulus values of
and zigzagging the diffusion path of corrosive agents. epoxy coatings containing less than 3 wt% CB de-
Besides, chemical functionalization of nanofillers is crease by increasing immersion time because of coating
another important parameter for improving the corro- delamination. On the other hand, epoxy coatings
sion protection performance of nanocomposite coat- containing CB above the percolation concentration
ings. Indeed, silane functional groups on nanofillers act (3 wt%) show conducting or semiconducting behavior
as chemical bridging between nanofillers and epoxy with lower resistance and higher capacitance, indicat-

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J. Coat. Technol. Res., 17 (1) 19–55, 2020

(a) (b)
4.8 4.8
0.75 wt%FG
0.5 wt%FC60 0.5 wt%FG
4.6 0.75 wt%FC60 4.6
log(⎪Z⎪/Ω cm2)

log(⎪Z⎪/Ω cm2)
4.4 4.4

1.0 wt%FG
0.25 wt%FG
4.2 0 wt%FC60 4.2 0 wt%FG
0.25 wt%FC60 1.0 wt%FC60

4.0 4.0

–2 –1 0 1 2 3 4 5 –2 –1 0 1 2 3 4 5
Log(f/Hz) Log(f/Hz)

3.0 x 104 (c) 3.0 x 104 (d)

2.5 x 104 2.5 x 104

0.5 wt%FG
Z ꞌꞌ(Ω cm2)

2.0 x 104 2.0 x 104

Z ꞌꞌ(Ω cm2)
0.25 wt%FG

1.5 x 104 0.25 wt%FC60 1.5 x 104

1.0 wt%FC60 1.0 wt%FG
0 wt%FC60
1.0 x 104 0.75 wt%FC60 1.0 x 104
0.75 wt%FG
0.5 wt%FC60 0 wt%FG
5.0 x 103 5.0 x 103

0.0 0.0

10,000 20,000 30,000 40,000 50,000 60,000 70,000 10,000 20,000 30,000 40,000 50,000 60,000 70,000
Z ꞌ(Ω cm2) Z ꞌ(Ω cm2)

Fig. 3: (a) Bode and (c) Nyquist plots of epoxy/FC60 nanocomposite coatings; (b) Bode and (d) Nyquist plots of epoxy/FG
nanocomposite coatings. The thickness of prepared coatings is 30 lm and the EIS results are derived after 24 h of
immersion in 3.5 wt% NaCl solution.54

Table 2: Intrinsic properties of carbon black

Diameter (nm) BET Surface Area Density Thermal conductivity Electrical conductivity Tensile strength
(m2/g) (g/cm3) (W/m K) (Sm1) (GPa)

3–10056 15–100056 1.7–1.958 0.2–0.356 1–200056 20–5056

ing that the corrosion reactions can easily initiate on coating matrix due to their high surface area; therefore,
coating/metal interface due to conductive properties of grafting CB nanoparticles is a way for preventing their
CB. However, the impedance modulus of conducting agglomeration in coating matrix and improving the
or semiconducting epoxy coatings containing 3 and compatibility of nanoparticles with coating, leading to
4 wt% CB has not changed remarkably for long-time enhanced corrosion resistance.
immersion, which can be attributed to the formation of Foyet et al.61 considered the barrier properties of
continuous CB network within polymer coating and epoxy nanocomposite coatings containing 1 or
barrier performance of CB nanoparticles in coating, 1.25 vol% of CB on AA2024-T3 substrates. Their
and therefore, reducing the diffusion of corrosive results showed that the corrosion rate of nanocompos-
agents in the polymer. Accordingly, corrosion resis- ite coating is by a factor of 10 slower than pure epoxy
tance of nanocomposite coating significantly improves coating. CB nanoparticles provide conductive path-
by increasing the wt% of CB above the percolation ways within polymer coating and prevent the localiza-
concentration for long exposure time. tion of electrons at defective regions of coating/metal
Zhang et al.60 have prepared composite lacquer interface. The distribution of electrons within polymer
coatings containing different loadings of CB nanopar- coatings can decrease the rate of oxygen reduction at
ticles grafted with polyvinyl alcohol by mechanical coating/metal interface, and therefore, the coating
agitation method. The results showed that the corro- delamination will be reduced.
sion resistance of nanocomposite coating containing Ghasemi-Kahrizsangi et al.62 have improved the
1 wt% CB in 3.5 wt% NaCl solution has improved. CB dispersion quality of CB nanoparticles in epoxy coating
nanoparticles have high tendency for agglomeration in via assisting sodium dodecyl sulfate (SDS) surfactant.

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 J. Coat. Technol. Res., 17 (1) 19–55, 2020

–100 12 –100
(b) 10
13
(a) 10
1012 1011
–80
1011 –80
1010 0.5 h
1010 0.5 h

Phase angle (°)

18 d
⎪Z⎪ (Ω cm2)

18 d –60

Phase angle (°)

109 101 d

⎪Z⎪ (Ω cm2)
109 101 d –60
200 d 200 d
108 360 d –40 108 391 d
508 d 508 d
107 –40
107
–20
106
E0.5 106
E1 –20
105
0
105
104
10–3 10–2 10–1 100 101 102 103 104 105 106
104 0
f (Hz) 10–3 10–2 10–1 100 101 102 103 104 105 106
f (Hz)

12 –100 12 –100
(c) 10 (d) 10
1011 1011
–80 –80
1010 1010 0.5 h
0.5 h –60 22 d

Phase angle (°)

Phase angle (°)
109 109 –60
⎪Z⎪ (Ω cm2)

22 d 49 d

⎪Z⎪ (Ω cm2)
105 d 114 d
108 186 d –40 108 265 d
–40
256 d
107 306 d 107
–20
106 –20
106
E1.5 E2
105 0 105
0

104 104
10–3 10–2 10–1 100 101 102 103 104 105 106 10–3 10–2 10–1 100 101 102 103 104 105 106
f (Hz) f (Hz)

(e) (f) –70

–80
108
–60
107
0.5 h
20 d –60 –50

Phase angle (°)

Phase angle (°)

107 0.5 h
⎪Z⎪ (Ω cm2)

47 d
⎪Z⎪ (Ω cm2)

111 d 18 d
106
161 d 122 d –40
–40 220 d
106 192 d
391 d
508 d –30
105

105 –20
E3 E4 –20

104
104 0 –10
10–3 10–2 10–1 100 101 102 103 104 105 106 10–3 10–2 10–1 100 101 102 103 104 105 106
f (Hz) f (Hz)

Fig. 4: Impedance spectra of fusion-bonded epoxy coatings containing (a) 0.5, (b) 1, (c) 1.5, (d) 2, (e) 3, and (f) 4 wt% CB,
after exposure to 3% NaCl solution for different immersion times59

The surfactant prevents the agglomeration of nanopar- is ascribed to the excellent barrier performance of well-
ticles via providing steric hindrance. The EIS results of distributed CB nanoparticles against diffusion of cor-
coatings during immersion in 3.5 wt% NaCl solution rosive ions into metal–coating interface. Further, the
are shown in Fig. 5. Accordingly, nanocomposite wet adhesion strength of epoxy coatings to metallic
coatings containing 0.75 wt% CB nanoparticles indi- substrate increased by adding CB up to 0.75%;
cated better corrosion protection than other epoxy however, the adhesion strength decreased by increas-
coatings (containing 0.25, 0.5, and 2.5 wt% CB), which ing the amount of nanoparticles up to 2.5% due to

23
J. Coat. Technol. Res., 17 (1) 19–55, 2020

(a) 1.00E+09 EP tures, providing unique properties.66,67 Depending on

1.00E+08
E25 CNT fabrication process, there are two types of CNTs:
E75 single-walled CNTs (SWCNTs) and multi-walled
E250
1.00E+07 CNTs (MWCNTs); SWCNTs consist of a single
graphene layer rolled up into a seamless cylinder,
⎪Z⎪/Ω cm2

1.00E+06 whereas MWCNTs consist of two or more concentric

1.00E+05
cylindrical shells of graphene sheets coaxially arranged
around a central hollow core with van der Waals forces
1.00E+04 between adjacent layers.68,69
CNTs have special thermal, mechanical, chemical,
1.00E+03
and electrical properties that make them an interesting
1.00E+02
option for developing new polymer nanocomposite
0.01 0.1 1 10 100 1,000 10,000 100,000 materials.70–77 CNT/polymer nanocomposites are fab-
F / (Hz) ricated by various methods including solution mixing,
melt blending, in situ polymerization, latex technology,
(b) 1.00E+09 and methods like densification, spinning of coagulant,
EP
E25
and layer-by-layer process.68,78 Although numerous
1.00E+08
E75
scientific papers review the application of CNTs in
1.00E+07 E250
polymers with the main goals of improving mechanical,
thermal, and electrical properties of the polymer
⎪Z⎪/Ω cm2

1.00E+06 composites,66,68,79–82 this section reviews the corro-

1.00E+05
1.00E+04
1.00E+03
1.00E+02
0.01 0.1 1 10 100 1,000
F / (Hz)
Fig. 5: Bode plots of epoxy coatings containing 0 (EP),
0.25 (E25), 0.75 (E75), and 2.5 (E250) wt% CB after
immersion in 3.5 wt% NaCl solution at 65°C for (a) 8 h
and (b) 145 h62
agglomeration and hydrophobic nature of CB nanopar-
ticles.
Moreover, Marchebois et al.63,64 studied the effect
of conductive carbon black on corrosion protection
performance of zinc-rich epoxy coatings. In zinc-rich
epoxy coatings, zinc particles provide cathodic protec-
tion in initial stage of immersion, and then, the
corrosion products of zinc can enhance the barrier
performance of coatings. The results showed that
carbon black can improve the electrical conduction
and cathodic protection of zinc-rich coatings.
Corrosion protection performance of polymer coat-
ings containing CB developed by researchers is sum-
marized in Table 3.
Carbon nanotubes
A carbon nanotube (CNT) is a hexagonal network of
carbon atoms rolled up into a seamless, hollow
cylinder, with each end capped with half of a fullerene
molecule. CNTs have similar chemical composition
with graphite. They are highly isotropic, and their
topology distinguishes them from other carbon struc-
sion-resistant properties obtained via incorporation of
CNTs in organic coating systems. Table 4 summarizes
the intrinsic properties of CNTs.
Gopakumar et al.51 studied the effect of different
nanofillers including pristine montmorillonite (MMT-
Na) and hydrotalcite (HT) lamellar clays, nonpurified
10,000 100,000
single-walled carbon nanotubes (SWCNT), and fullere-
nes (Ful) at 5 and 10 wt% based on the paint solid
contents in a waterborne flexible acrylic coating
(PACR). By assuming no correction for film thickness
differences, MMT-Na, SWNT, and FUL reduce some-
what water vapor transmission rate (WVTR), whereas
HT has practically no effect. However, after normal-
izing for thickness, HT is increasing WVTR, whereas
all three MMT-Na, SWNT, and FUL may cause
reductions from 15% to about 40% depending on the
filler type. Hence, the barrier properties of the com-
posites depend not only on the polymer structure but
also on the structure and properties of the nanofiller. In
this case, coatings containing SWNT and FUL show
higher hydrophobicity and coatings loaded with HT
and MMT-Na show more hydrophilicity compared
with bare coating, which is expected to play an
important role in the water vapor transport through
the polymeric films. In general, the results of this work
indicate that it is possible to improve certain properties
of acrylic protective coatings through addition of low-
cost, unmodified nanoclays or by using nonpurified
carbon allotropes, without a significant compromise of
the strength and ductility of the polymeric matrix.51
Aglan et al.22 prepared MWCNT-incorporated
epoxy and vinyl chloride/vinyl acetate copolymer
coatings in order to protect the steel substrates. The
epoxy resin is quite brittle and the neat vinyl chloride/
vinyl acetate copolymer is very ductile. The results of
this study revealed that the toughness of epoxy and the
stiffness of vinyl chloride/vinyl acetate have increased
by adding MWCNTs. Also, thin nanocomposite films
showed enhanced strength and cohesive strength, both

24
 Table 3: A summary of polymer/CB composite coatings for corrosion protection of metallic substrates
Reference Polymer Carbon black Dispersion Metallic Coating Corrosion protection
matrix method substrate thickness performance
Size BET Loading Surface Optimum (lm)
(nm) (m2/g) treatment loading

65 Fusion- 56 45 0.5–4 wt% – 4 wt% High-intensity Mild steel 100–200 Formation of percolation
bonded mixer and regime; sharp drop in
epoxy ball mill electrical resistance;
barrier performance
60 Lacquer 60 – 0.6–1.3 wt% Grafting 1 wt% Ultrasonic Cold-rolled 30 Strong interface
with dispersion steel between CB and
polyvinyl and polymer; enhanced
alcohol mechanical dispersion; barrier
mixing performance
61 Epoxy – – 1, 1.25 vol% – 1.25 vol% High-speed AA2024-T3 60 Electrical conducting
shear mixer coatings; barrier
and performance
ultrasonic
treatment
62 Epoxy 26–30 – 0.25–2.5 wt% – 0.75 wt% Surfactant Steel 70 Enhance barrier
(SDS)- performance;
assisted corrosion efficiency
dispersion 92.5% (vs 62.5% for
and pure coating)
ultrasonic
treatment
63,64 Zinc-rich – – 2.1, 5 wt% – 5 wt% Mechanical Steel 80 Increase in cathodic
epoxy mixing protection and barrier
performance of zinc-
rich coating
J. Coat. Technol. Res., 17 (1) 19–55, 2020

25
J. Coat. Technol. Res., 17 (1) 19–55, 2020

before and after immersion in 5% NaCl solution. EIS
results confirmed that the charge transfer resistance of
epoxy and vinyl chloride/vinyl acetate copolymer
coatings in salt water has increased with addition of
0.1 wt% MWCNTs. Therefore, appropriate dispersion
of MWCNTs in resins enhances the cohesive and
adhesive properties of nanostructure coatings, leading
to enhancement of their corrosion resistance.
Wei et al.17 prepared conductive polyurethane/
MWCNT nanocomposite coatings via in situ surface-
initiated polymerization method for corrosion protec-
tion of stainless-steel substrate. The potentiodynamic
polarization curves for bare substrate and composite
coatings are shown in Fig. 6. The electrochemical
corrosion tests in 3.0 wt% NaCl solution revealed that
the corrosion protection efficiency of the prepared
nanocomposite coating is about 97.70%. The enhanced
corrosion resistance is due to physical barrier perfor-
mance of composite coatings against corrosive agents
that corrosive agents cannot penetrate through the
coating to induce the corrosion of steel substrate. The
MWCNTs with high aspect ratio and good dispersion
in the polymer matrix act as solid barrier in the path of
gas molecules which pass through the coating; there-
fore, the path of corrosive agents through coating
becomes more tortuous and the corrosion procedure
retards significantly.
Khun et al.90 studied the effect of MWCNT content
(0.1 and 0.5 wt%) on the properties of epoxy coatings
on aluminum alloy substrates. The EIS results during
short immersion time (less than 50 h) showed that the
total impedance at 0.01 Hz (|Z|0.01Hz) in 0.5 M NaCl
solution for epoxy/0.1 wt% MWCNT coating was not
significantly different than that for pure epoxy coating.
However, epoxy coatings containing 0.5 wt%
MWCNT show remarkably higher |Z|0.01Hz which can
be attributed to the improvement in corrosion protec-
tion performance of epoxy coating via increasing the
MWCNT content. Moreover, the tribological proper-
ties of epoxy/MWCNT composite coatings were stud-
ied by ball-on-disk microtribological tests. The carbon
particles dispersed in polymer matrix can be released
during sliding and transferred into the interface of steel
balls and coatings. These particles serve as lubricant,
and also, they can increase the rolling effect; therefore,
MWCNTs can reduce the friction of epoxy coatings.
According to this study, load-bearing capacity,
Young’s modulus, and wear and corrosion resistance
of epoxy coatings improved by incorporating
MWCNTs.
Kumar et al.91 reported a systematic approach based
on applying simultaneously ultrasonic waves and shear
forces generated by an axial flow impeller for prepar-
ing epoxy nanocomposites containing different load-
ings (0.25, 0.5, 0.75, and 1 wt%) of MWCNT. As
derived from Tafel curves (Fig. 7), the corrosion rate
of mild steel substrate coated with epoxy/0.75 wt%
MWCNT in 3.5 wt% NaCl solution decreases up to
2.5 9 103 MPY, and protection efficiency has in-
creased up to 99.99%.
Zhdanok et al.93 have shown that the introduction of
carbon nanomaterials (carbon nanofibers and carbon

Table 4: Typical properties of CNTs

CNT Diameter BET surface Density Thermal conductivity Tensile strength
(nm) area (m2/g) (g/cm3) (W/m K) (GPa)

SW–CNT 0.4–283 131584 1.86–1.9485 80–950086 13–5287

MW–CNT 3–3088 50–85084 1.58–1.9085 300–10,00086 11–6389

–0.4 (a) 10 h
(b)
46 h 0.2
–0.5
120 h
10 h
–0.6 312 h
46 h
0.1
Potential (V)

120 h
Potential (V)

–0.7
312 h
–0.8 0.0

–0.9

–0.1
–1.0

–1.1
–0.2
1E–8 1E–7 1E–6 1E–5 1E–4 1E–12 1E–11 1E–10 1E–9 1E–8 1E–7

Current (A) Current (A)

Fig. 6: Potentiodynamic polarization curves of (a) stainless steel and (b) polyurethane/MWCNT nanocomposite coatings at
different immersion times in 3.0 wt% NaCl solution17

26

–4
–6
–8
–10
–12
logl (Acm–2)
–14
–16
–18
–20 Mild Steel
Neat Epoxy
–22
CNT/Epoxy 0.25 wt%
–24 CNT/Epoxy 0.50 wt%
–26 CNT/Epoxy 0.75 wt%
–28
CNT/Epoxy 1.00 wt%
–1.0 –0.9 –0.8 –0.7 –0.6 –0.5
Potential (V)
Fig. 7: Tafel plots for mild steel substrate, pure epoxy, and
epoxy/MWCNT nanocomposite coatings92
nanotubes) into a paint coating positively influences its
adhesion, impact and bending strengths, hardness, and
protective characteristics, which makes it possible to
increase the longevity of the surface protected by this
coating. Paint coatings modified with carbon nanoma-
terials can be successfully used in machine building as
well as in the civil and industrial construction engi-
neering.
In another study, some bolts and nuts were coated
with the cup-stacked CNT (CSCNT) polymer paint.
CSCNT is another type of CNT and its morphology is
like the stack of truncated cone shape graphene layers,
which has the edge of a graphene sheet exposed at the
tube sidewall. It was shown that by applying the
CSCNT coating, mechanical properties enhanced94,95
and the CSCNT–polymer paint can enhance the
durability of components used in ships and bridges;
as a consequence it can reduce the maintenance
costs.74
In an invention, the paint formulation of a poly-
urethane paint system or an epoxy system was modified
by the percentage loading of carbon nanotubes
between 1% and 20% weight. The paint layer can be
applied by spraying, and it may be the top coat of the
paint system or it may be a primer or undercoat of the
paint system which has numerous applications.96
In another study, a coating system consisting of
epoxy/polyamide primer formulated with SWCNT and
zinc dust and a compatible epoxy/polyamide interme-
diate coating and polyurethane top coat was devel-
oped. The primer utilizes pure zinc dust at a
concentration of about 50% by weight compared with
a traditional zinc-rich epoxy. The results showed that
CNT utilized in the primer is very efficient; CNT can
be used in a relatively small amount and provides both
a strengthening and stiffening reinforcement and elec-
trically conductive path through the resin system. This
approach is expected to be compatible with a wide
J. Coat. Technol. Res., 17 (1) 19–55, 2020
variety of binder systems and is a way to overcome
challenges like poor physical and mechanical proper-
ties in paint systems and lowers the levels of toxic
heavy metals that are always used with zinc.26
On the other hand, Beigbeder et al.97,98 considered
silicone-based coatings filled with low levels of
MWCNTs. It was shown that, independent of the bulk
properties, the presence of 0.05% of MWCNTs within
a silicone elastomer results in a significant enhance-
ment of the fouling resistance properties, and after
water exposure, surface wettability was modified.97
Furthermore, the influence of dispersion quality (mas-
ter-batch process and direct blending) and quantity of
MWCNTs in a polydimethylsiloxane resin on the
marine fouling release performance was investigated.
–0.4 –0.3 –0.2 The results showed that the fouling resistance enhance-
ment is clearly related to the quality of nanotubes
dispersion within the material, and the best results
were obtained by master-batch process. Besides, this
improvement is dependent on the amount of filler and
maximum removal of Ulva sporeling biomass from
silicon-based surfaces was obtained with incorporation
of 0.1 wt% MWCNTs in coatings.98
Moreover, Il’darkhanova et al.99 modified the epoxy
silicone resins with carbon nanotubes and nanofibers
which afford nanostructuring of the paint coating
surface layer. Their results showed that the contact
wetting angle of paint without modification and after
modification with 2 wt% of CNT and CNF is 72, 88,
and 90. These results have application potential for
development of anticorrosion–antifouling biocide-free
paints with high level of hydrophobicity and slippery
properties for corrosion- and fouling-resistant items.
In recent studies, new approaches have been con-
sidered for dispersion of CNTs in polymer matrices to
avoid their agglomeration and enhance their dispersion
quality in coating matrix. Indeed, the dispersion of
CNTs in polymer matrix is a challenge due to high
specific surface area of CNTs and strong van der Waals
and p–p interactions of CNTs.100
In this regard, covalent and noncovalent methods
have been utilized for modifying the surface of CNTs.
In covalent approaches, chemical functional groups
will be developed on the sidewalls of CNTs. For
example, Subramanian et al.101 used polydopamine
(PDA) coated on acid treated MWCNTs as nanofiller
in epoxy coatings. Moreover, Cai et al.102 prepared
polyurethane coatings loaded with polydopamine-
wrapped CNTs. The results showed that higher
amounts of CNTs could be dispersed within polymer
matrix via modifying the surface of nanofillers, leading
to nanocomposites with superior corrosion resistance
and mechanical performance.
In the case of noncovalent methods, functional
molecules are adsorbed on the sidewalls of CNTs
through van der Waals forces and p–p stacking
between CNTs and polymer chains without destroying
the structure of the CNTs.100 As an example, Cui
et al.100 used poly(2-butylaniline) (PBA) as dispersant
for dispersion of MWCNTs in epoxy coatings. As
27
J. Coat. Technol. Res., 17 (1) 19–55, 2020
Fig. 8 shows, the water absorption of epoxy coatings
(which is in close relation with corrosion protection
performance of the coatings) decreases with loading
modified CNTs, and the curves indicate that the
loading amount of CNTs and, therefore, the dispersion
quality have great effect on the performance of
nanocomposite coatings.
Therefore, polymer coatings containing CNT have
application as anticorrosion coatings with enhanced
stiffness and strength, and these nanocomposite coat-
ings can provide electric pathways for cathodic protec-
tion. Moreover, these nanopaints can reduce biofouling
and are an alternative to environmentally hazardous
biocides.82 However, the use of CNTs in nanocompos-
ites to date has been limited due to challenges in their
processing and dispersion, environmental concerns and
their prohibitively high cost.103–106 Besides, the toxicity
of carbon nanomaterials also depends on their geo-
metric structure. CNTs have been shown to cause
necrosis, cell degeneration, and apoptosis in macro-
phage cell lines and recent studies point to the
similarity of the toxicity of asbestos and CNTs;
therefore, it is required to comprehensively consider
the cautions before introducing nanoproducts to the
market.107
Accordingly, Table 5 presents the summary of
research in the field of anticorrosion coatings contain-
ing CNTs.
Graphene
Graphene is the basic building block of all graphitic
forms of carbon and consists of a single atomic layer of
sp2 hybridized carbon atoms arranged in a honeycomb
structure41,43,110–113 and is the thinnest 2D material114
which has revolutionized the nanotechnology platform
since its discovery.115
Graphene, as a new class of nanofiller, may be
preferred over other carbon nanofillers (such as CNT,
CNF, and exfoliated graphite) due to its exceptional
1.2
(a)
1.0 Blank EP
0.5% MWCNTs/EP
Water absorption (%)
1.0% MWCNTs/EP
0.8 2.0% MWCNTs/EP
0.6
0.4
0.2
0.0
0 10 20 30 40 50
Immersion time (h)
Fig. 8: Water absorption (a) and OCP (b) curves of different coating/steel systems after different immersion time in 3.5%
NaCl solution100
28
properties (Table 6) such as high surface area and
aspect ratio, superior mechanical properties, thermal
and electrical conductivity, electromagnetic interfer-
ence-shielding ability, flexibility, transparency, thermal
stability, low coefficient of thermal expansion, and low
viscosity when compounded with polymers.27,38,116–125
It is also reported that the improvement in mechan-
ical and electrical properties of graphene-based poly-
mer composites are much better in comparison with
that of clay or other carbon filler-based polymer
composites. Although CNTs show comparable
mechanical properties to graphene, still graphene is
better nanofiller than CNT in certain aspects such as
thermal and electrical conductivity.126 Besides, gra-
phene-based polymer composites exhibit superior
mechanical properties and higher electrical conductiv-
ity than the neat polymer or conventional graphite-
based composites.127 Also, graphene is highly inert and
can also act as corrosion barrier against water and
oxygen diffusion.128–130 Moreover, recent studies sug-
gest that the production costs for graphene in large
quantities are much lower than for CNTs.123,131 Hence,
graphene as fillers have been used in polymer
nanocomposites and hold potential of enhanced prop-
erties for a variety of applications such as aerospace,
electronics, energy, structural and mechanical, envi-
ronmental, and medicine.111,115,122,132–139
It should be mentioned that most graphene/polymer
composites have been developed using both reduced
and unreduced graphene oxide (GO) using three
strategies: solvent processing, in situ polymerization,
and melt processing.119
In this regard, several papers on graphene and
graphene-based nanocomposites have recently been
published, and many companies involved in the carbon
business have already established programs on gra-
phene and graphene oxide production, and it is
possible to expect graphene-based composites to
appear on the market within a few years.128
Sun et al.146 discussed an important question:
whether graphene nanosheets are corrosion inhibitors
0.10
(b)
0.05
Blank EP
0.00 0.5% MWCNTs/EP
OCP (V) vs SCE
1.0% MWCNTs/EP
2.0% MWCNTs/EP
–0.05
–0.10
–0.15
–0.20
–0.25
60 70 80 0 10 20 30 40 50
Immersion time (day)
 Table 5: A summary of polymer/CNT composite coatings for corrosion protection of metallic substrates
Reference Polymer CNT Dispersion Substrate Coating Corrosion protection
matrix method thickness performance
Type Loading Surface Optimum wt% (lm)
(wt%) treatment

22 Epoxy and MWCNT 0.1 – 0.1 Centrifugal Steel 200 Epoxy/CNT provides 27%
vinyl (5–20 layers) mixing more corrosion
chloride/ protection than neat
vinyl coating.
acetate
copolymer
90 Epoxy MWCNT 0.1, 0.5 – 0.5 Sonication AA2024-T3 50 Enhanced adhesion;
(3–15 layers) decreasing pores in
coating; improved
barrier performance
91 Epoxy MWCNT (diameter 0.25, – 0.75 Ultrasonic Mild steel 20 99% drop in corrosion
30 nm) 0.5, waves and rate (compared to 63%
0.75, axial flow of pure epoxy) due to
1 impeller homogeneous
dispersion CNT in
coating
26 Epoxy/ SWCNT – – – – – – 50% decrease in the zinc
polyamide dust concentration
with zinc compared to
dust conventional zinc-rich
epoxy.
108 Polyurethane MWCNT (diameter 0.4, – 0.4 Phosphated Enhanced corrosion
20 nm and 0.7, 1 steel resistance and
length 10 lm) adhesion strength
99 Epoxy MWCNT (diameter 0.25, Fluorosilane <1 Bead mill Steel 320–350 Hydrophobicity via adding
silicone 15–20 nm); CNF 0.5, 2 CNF; anticorrosion,
(diameter antifouling.
20–60 nm)
109 Epoxy MWCNT (diameter 3 Fe3O4 3 Ball mill Carbon steel 20 Improved barrier
15–90 nm) performance and
adhesion strength
polymer coating
102 Polyurethane MWCNT (diameter 0.5, 1, 2 Polydopamine 1 Ultrasonication Aluminum 100 ± 5 Improving corrosion
20–30 nm and alloy resistance and
length adhesion strength
10–30 lm)
100 Epoxy MWCNT 0.5, 1, 2 Poly(2- 1 Ultrasonication Mild steel 20 Enhanced mechanical
butylaniline) and tribological
performance
J. Coat. Technol. Res., 17 (1) 19–55, 2020

29
J. Coat. Technol. Res., 17 (1) 19–55, 2020
Table 6: Typical properties of graphene
Theoretical Density Thermal conductivity
surface (g/cm3) (in plane) (W/m k)
area (m2/g)
2630140 2.2141 2000–4000142 and 5300143
or promoters in graphene/polymer nanocomposite
coating. They prepared graphene nanosheets via par-
tially reducing graphite oxide by Fe powder-induced
hydrogen bubbling and then by rapid microwave-
assisted thermal reduction. After that, epoxy/graphene
nanocomposites were prepared by dispersing graphene
into epoxy matrix by using ball milling. Their exper-
iments revealed that when the amount of graphene is
less than 0.1 vol%, graphene nanosheets act as corro-
sion inhibitor. However, by increasing the loading
more than 0.1 vol%, graphene nanosheets significantly
promote the corrosion when the coating is mechani-
cally damaged. Indeed, the percolation threshold for
graphene/epoxy sample is 0.1 vol%. Increasing electri-
cal conductivity and dispersion of graphene materials
will decrease the percolation threshold.
In this section, the effectiveness of graphene
nanofillers on paints is discussed with emphasis on
corrosion- and degradation-resistant applications of
these nanocomposite coatings.
Dennis et al.105 studied two coating systems: an
unfunctionalized graphene (UFG)/polyetherimide
(PEI) composite with high loading of nanomaterial
filler and a combined graphene/MWCNT/PEI system
with a much lower loading of filler in order to consider
synergetic effects between two types of carbon nano-
materials. Also, MWCNT/PEI system was tested, but it
showed no enhanced corrosion-resistant properties.
Meanwhile, 2 wt% UFG/MWCNT/PEI coating system
showed the least corrosion rate. Also, the results of
immersion in 3.5% NaCl solution after 3144 h showed
extensive corrosion across the test substrates for all
samples, except for the two coated with 20 wt% UFG/
PEI and 2 wt% UFG/MWCNT/PEI.
In a study by Christopher et al.,147 the corrosion
protection performance of GO/ZnO and CB/ZnO as
nanofiller in waterborne polyurethane coating was
compared. The electrochemical measurements re-
vealed that the corrosion rate of polyurethane coating
decreased from 0.120 mm/year to 0.011 and 0.002 mm/
year by incorporating 0.3 wt% CB/ZnO and GO/ZnO,
respectively. The superior corrosion resistance of
polyurethane/GO–ZnO coatings is due to sheet-like
morphology of GO and its high surface-to-volume
ratio which can more effectively reduce the porosity of
coating and restrict the diffusion path, leading to
enhanced barrier performance of polymer coatings.
Monetta et al.148 studied the properties of water-
based epoxy coatings containing 1 wt% graphene
nanosheets on Al 2024-T3 substrates. The EIS results
are shown in Fig. 9. The Bode plots show that the
corrosion resistance of epoxy coating improves due to
30
Thermal conductivity Electrical Intrinsic
(along c axis) conductivity strength
(W/m K) (Sm1) (GPa)
6142 700,000144 and 100,000143 130145
barrier performance of graphene sheets in epoxy
matrix. Also, they reported that the adhesion strength
has not changed via incorporating graphene nano-
flakes.
Liu et al.149 used graphene dispersed in water (in the
presence of sodium polyacrylate and fumed silica
antisediment) as nanofiller in waterborne epoxy coat-
ings. Figure 10 presents the potentiodynamic polariza-
tion curves of composite samples. The protection
efficiency calculated for pure epoxy, epoxy/0.5 wt%
graphene, and epoxy/1.0 wt% graphene is 99.2, 99.7,
and 99.4%, respectively. Besides, EIS results confirmed
that the corrosion resistance of epoxy coatings con-
taining 0.5 wt% graphene is one order of magnitude
lower than neat epoxy coating. The enhanced corro-
sion resistance of nanocomposite coatings is due to
barrier performance of graphene nanosheets against
diffusion of H2O molecule through coating.
Zhang et al.150 prepared epoxy coatings containing
polyvinylpyrrolidone/reduced GO (0.1, 0.4, and
0.7 wt%). A significant improvement in thermal,
mechanical, and corrosion resistance of epoxy coating
was obtained by loading 0.7 wt% modified graphene
sheets. In this regard, the corrosion rate of epoxy
coating decreased from 1.3 to 0.3 mm/year.
Moreover, Chang et al.151 prepared polyani-
line/graphene composites (PAGCs) with different
amounts of 4-aminobenzoyl group-functionalized gra-
phene-like (ABF-G) sheets for corrosion protection of
steel. Figure 11 shows O2 and H2O permeability
through nanocomposite coating, revealing outstanding
barrier properties of PAGC samples against O2 and
H2O compared with neat polyaniline (PANI) and
polyaniline/clay composites (PACC). Moreover,
polyaniline/graphene composites containing 0.5 wt%
ABF-G (PAGCs05) showed superior corrosion resis-
tance and barrier protection than PACCs05 at the
same graphene loading, because the aspect ratio of
graphene ( 500) is higher than that of clay ( 220)
and ABF-G disperses well in PANI and maximizes the
interfacial area. Therefore, gas molecules pass through
more tortuous path in the polymeric matrix by inclu-
sion of ABF-G and effectively enhance the corrosion
protection. Further, the conductivity of PANI,
PACCs05, and PAGCs05 is 1.09 9 103, 0.7 9 102,
1.4 9 102 S/cm, respectively; revealing graphene is
conductive nanofiller which can form conducting net-
work in polymer matrix, while clay is nonconductive
nanofiller.
On the other hand, Chang et al.5 developed
epoxy/graphene composites as corrosion inhibitors
with hydrophobic surfaces. They used nanocasting
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

(a) 108 108

0 (b) 0
1d 1d
2d 2d
107 5d 107 5d
7d 7d
Impedance modulus, Ω*cm2
10d

Impedance modulus, Ω*cm2

10d
106 106

105 105

104 104

103 103

102 102
10–2 10–1 100 101 102 103 104 105 10–2 10–1 100 101 102 103 104 105
F / Hz F / Hz

Fig. 9: Bode plots for (a) pure epoxy and (b) epoxy/graphene coatings148

–0.2 0.9
240
0.8 220

Vapor permeability rate (g/h m2)

–0.3 (c)
200
0.7
Permeability (barrer) O2

(d) 180
Potential (V vs. SCE)

–0.4 0.6
160
0.5 140
–0.5
(a) 120
0.4
100
–0.6
0.3 80

–0.7 0.2 60
40
0.1
–0.8 20
(b) 0.0 0
PANI PAGCs01 PAGCs025 PAGCs05 PACCs05
–0.9
–10 –9 –8 –7 –6 –5 –4 –3 –2 Sample

logi (A cm–2)
Fig. 11: Permeability and vapor permeability rates of PANI,
PAGCs (PAGCs01, PAGCs025, PAGCs05), and PACCs05151
Fig. 10: Potentiodynamic polarization curves for (a) bare
steel, (b) epoxy coating, (c) epoxy/0.5 wt% graphene, and
(d) epoxy/1.0 wt% graphene after 48 h immersion in of epoxy coating increases from 88.45% to 99.33% via
3.5 wt% NaCl solution149 using hydrophobic epoxy/graphene composites.
Chen et al.152 have used poly(2-butylaniline)
(P2BA) for noncovalent modification of graphene
sheets to decrease the tendency of graphene sheets in
technique to directly duplicate the surface features of polymer matrix. For comparing the effect of weight
fresh plant leaves (superhydrophobic Xanthosoma content of P2BA and G, two different nanocomposite
sagittifolium) onto the composite surface. The results coatings named as P2BA0.5%–G0.5% and
showed that the contact angle of water droplets on P2BA0.5%–G1% were prepared. Water absorption
surfaces can be increased from  82 (epoxy surface) curves of pure epoxy and nanocomposite coatings are
to  127 (hydrophobic epoxy and epoxy/graphene shown in Fig. 13, indicating water penetration in
composites) and no decrease in the water contact angle organic coating has two stages: In the first stage, water
of nanocoatings was observed during 1 month in the rapidly penetrates into pores of coating, and in the
ambient atmosphere at room temperature, indicating second stage, water absorption smoothly reaches a
the hydrophobic property is stable enough. In addition, stable saturation level. Figure 13 obviously shows that
Fig. 12 indicates that epoxy/graphene composites the water uptake of epoxy coatings dramatically
provide an excellent corrosion protection effect on decreases via incorporating graphene nanosheets due
cold-rolled steel electrode. According to electrochem- to excellent barrier performance of graphene sheets.
ical corrosion measurements, the protection efficiency However, the water uptake of P2BA0.5%–G0.5% is

31
J. Coat. Technol. Res., 17 (1) 19–55, 2020

28M
3
1000

800
24M
2

Z ꞌꞌ (Ω)
600

400
20M
200
1 (a)
log I (mA/cm2)

Z ꞌꞌ (Ω cm2)
0
16M 0 500 1k 2k 2k
Z ꞌ (Ω)
0
12M
–1 (a)
8M
bare
–2 (b)
(c) 4M
epoxy
HE (d)
–3 HEGC 0 (c) (d)
(b)

–1000 –900 –800 –700 –600 –500 –400 –300 0 4M 8M 12M 16M 20M 24M 28M 32M
Potential (mV) Z ꞌ (Ω)

Fig. 12: (Left) Potentiodynamic polarization curves and (right) Nyquist plots for: (a) bare, (b) epoxy-coated, (c)
hydrophobic epoxy (HE)-coated, and (d) hydrophobic epoxy/graphene composite (HEGC)-coated samples5

from different aspects: (1) improving the hardness of

1.0
Neat epoxy coating and reducing the penetration depth; (2)
P2BA0.5%–G1% formation of graphene transfer layer during friction
P2BA0.5%–G0.5% test; (3) increasing the thermal conductivity of coatings
0.8
and easily transferring the generated heat during
friction test at interface and reducing the interfacial
Water absorption (%)

0.6
0.4
0.2
0.0
0 1
Fig. 13: Water absorption curves for pure epoxy and
epoxy/P2BA-G nanocomposite samples as function of
immersion time in water at 25°C152
less than P2BA0.5%–G1.0% sample, assigned to
agglomeration of graphene sheets and producing
porosity. Also, according to electrochemical parame-
ters calculated from potentiodynamic polarization
curves, the corrosion rate of neat epoxy, epoxy/
P2BA0.5, epoxy/P2BA0.5–G0.5, and epoxy/P2BA0.5–
G1.0 is 1.64 9 1011, 3.31 9 1013, 9.34 9 1015, and
5.70 9 1014, respectively. Therefore, results show that
by embedding small percentage of well-dispersed
graphene nanosheets (P2BA0.5%–G0.5%) in epoxy
coating, corrosion resistance of epoxy coatings have
improved, which can be attributed to redox catalytic
capability of poly(2-butylaniline) and barrier proper-
ties of graphene sheets. Moreover, epoxy/P2BA0.5-
G0.5 coatings showed relatively stable frictional behav-
ior due to lubricating effect of well-distributed gra-
phene sheets. Indeed, well-distributed rigid graphene
can improve the wear resistance of epoxy coatings
temperature.
Stage I
On the other hand, since incorporation of graphene
Stage II
in polymer matrix can increase the bulk conductivity of
insulating polymer which may lead to enhanced
corrosion phenomenon, Sun et al.153 have used encap-
sulated graphene sheets derived from reduced gra-
phene oxide with (3-aminopropyl)-triethoxysilane
(rGO@APTES) in polyvinyl butyral coating. The
synthesized rGO@APTES showed two-dimensional
structure, high aspect ratio, impermeability, and insu-
2 3 4 5 6 7 8 9 10 lating properties which can enhance the barrier prop-
Immersion time (day) erties of the coating. Figure 14 shows the coating
resistance of pure epoxy and epoxy/rGO@APTES
coatings. The coating resistance of epoxy coating
increases by adding appropriate amount of
rGO@APTES due to reducing the defects of coating
and enhancing the diffusion resistance of aggressive
species in coating matrix. Further, APTES acts as
spacer which can impede the graphene–metal–gra-
phene connections and prevent galvanic corrosion of
graphene–metal couple. However, when the amount of
rGO@APTES is more than optimum (0.1 wt%), the
structure of coating destroys as a result of nanosheets
agglomeration.
Zhu et al.154 proposed a new method for application
of water-dispersible graphene in waterborne acrylic-
modified alkyd resin (AMAR). In this regard, the
primary amine groups of 3-(1-(2-aminopropoxy) pro-
pane-2-ylamino) propane-1-sulfonate sodium (PPS)
were reacted by epoxy groups of graphene oxide via
nucleophilic ring-opening reaction and then reduced
by hydrazine hydrate to produce PPS-functionalized
graphene (PG). The potentiodynamic polarization
curves and Nyquist plots of these coatings are shown
in Fig. 15. According to electrochemical parameters

32
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

derived from Tafel curves, the corrosion rate of Ding et al.155 studied the effect of graphene in zinc-
AMAR coating is 0.263 mm/year, and its corrosion rich epoxy coatings. They prepared epoxy coatings
rate decreases to 3.31 9 104 mm/year by adding containing different loadings of graphene (0, 0.1, 0.3,
2 wt% PG nanosheets. Indeed, the corrosion protec- and 0.5 wt%). The protection steps for nongraphene
tion mechanism of PG/AMAR coatings is through coating are cathodic protection, shielding, and failure.
barrier performance and anodic protection: (I) the However, the activation of zinc becomes slow by using
electrochemical measurements reveal that the well- graphene in zinc-coating due to barrier performance of
distributed graphene sheets with relatively high aspect graphene layers; indeed, graphene sheets provide
ratio are able to improve the corrosion resistance of initial shielding stage and the stable cathodic protec-
organic coatings by providing more compact coatings tion and failure steps happen with delay. Moreover,
with lower defects and enhancing the barrier perfor- graphene sheets can prolong the time of cathodic
mance of coatings against diffusion of electrolyte and protection, due to increase in electrical contact
oxygen. (II) Further, GO is nonconducting, whereas between zinc particles as well as zinc and iron via
PG is conducting, and passive metal oxides can be utilizing conductive graphene sheets. Therefore, en-
formed due to redox capability of electroconductive hanced corrosion resistance of zinc coatings containing
PG/AMAR coatings. Therefore, the electrons pro- graphene can be attributed to both barrier perfor-
duced during oxidation reaction of iron are able to mance and electrical conductivity of graphene sheets.
migrate through conductive coating and inhibit the Also, Zhou et al.156 used reduced graphene oxide as
redox reactions of corrosion spots. nanofiller in zinc-rich epoxy coatings. They concluded
that reduced graphene oxide can also improve the
electrical conductivity of zinc-rich epoxy coatings,
9 because reduced graphene oxide nanosheets can
increase the electrical connection between zinc parti-
8
Coating resistance Rc / Ω cm2

GAP0.1 cles and steel substrate. Further, these nanosheets act

7
as impermeable barrier in polymer matrix. Therefore,
reduced graphene oxide nanosheets are an appropriate
6 GAP0.2 candidate for increasing the corrosion resistance of
zinc-rich epoxy coatings. Also, as summarized in
GAP0.3
5 Table 7, graphene possesses exceptional properties
GAP0.05
which seem to be an ideal material to enhance
4 mechanical and anticorrosion properties of coatings.
These nanomaterials are nontoxic and have minimal
GAP0
3
environmental impacts.21
0 20 40 60 80 100 120 140 160 180 200
Time t/ h

Fig. 14: The coating resistance of epoxy and epoxy/

rGO@APTES coatings derived from fitting EIS results153

0.1 120000
10000
(a) (b)
8000
0.01
100000 6000
Log[Current density (Α/cm2)]

1E-3
o

4000

80000 2000
1E-4
0
Zim (Ω)

0 2000 4000 6000 8000 10000

1E-5 60000 A

1E-6
40000
1E-7 Uncoated
Uncoated
AMAR
AMAR
1E-8 20000 GO/AMAR
GO/AMAR
PG/AMAR1 PG/AMAR1
1E-9
PG/AMAR2 PG/AMAR2
0
PG/AMAR3 PG/AMAR3
1E-10
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0 20000 40000 60000 80000 100000 120000 140000

Potential vs. SCE(V) Zre (Ω)

Fig. 15: (a) Tafel plots and (b) Nyquist plots for uncoated steel, AMAR-coated, GO/AMAR-coated, PG/AMAR1-coated, PG/
AMAR2-coated, and PG/AMAR3-coated samples after immersion in 3.5 wt% NaCl solution154

33
J. Coat. Technol. Res., 17 (1) 19–55, 2020
Graphene oxide
Graphene oxide (GO) nanosheets with quasi-two-
dimensional honeycomb lattice structure are derived
from chemical exfoliation of graphite and have
attracted the attention of researchers along with
graphene due to their outstanding inherent proper-
ties.143,165,166 Important features of GO are mentioned
in Table 8.
In this regard, since GO nanosheets show high
aspect ratio, low density, unique electrical, thermal,
mechanical, and barrier properties, the potential appli-
cation of GO in polymer composites has been consid-
ered.171
In this regard, Jiang et al.172 synthesized GO with
different aspect ratios by controlling the parameters of
chemical exfoliation method, and then, GO with
different aspect ratios were used as nanofiller in
waterborne epoxy coating. They showed that GO
nanosheets with higher aspect ratio can provide higher
corrosion resistance in polymer matrix. Indeed, GO
nanosheets with higher aspect ratio exhibit more
tortuous permeation path in polymer matrix against
diffusion of corrosive agents, and therefore, superior
corrosion resistance can be achieved.
For example, Krishnamoorthy et al.21 developed
multifunctional GO nanopaints by incorporating GO
sheets in alkyd resin with suitable nontoxic additives
using ball milling. The prepared GO nanopaint exhib-
ited good corrosion-resistant behavior in both acidic
and high salt content solutions and showed a corrosion
protection efficiency of about 76% in salt water
estimated from the linear polarization tests. Besides,
the GO nanopaint inhibited the bacterial growth on its
surface and demonstrated the inhabitation of fouling
on the GO nanopaint surface.
Rajabi et al.173 prepared epoxy/GO nanocomposite
coatings by incorporating different amounts of GO
nanosheets (0.125, 0.25, and 0.5 wt%) into epoxy
matrix by mechanical agitation and sonication pro-
cess. Their study proved that the sonication process is
an appropriate method for achieving good GO
dispersion in polymer coating. The electrochemical
studies of the prepared nanocomposite coatings show
that the best corrosion protection can be achieved via
incorporation of 0.25 wt% GO, which is attributed to
efficient dispersion of GO nanosheets in epoxy and
creation of tortuous path against diffusion of aggres-
sive agents.
Pourhashem et al.174 studied the effect of GO
dispersion on corrosion protection performance of
solvent-based epoxy coatings, revealing that the vis-
cosity of polymer matrix and GO wt% are two
important parameters for controlling the GO disper-
sion in coating matrix. Among epoxy coatings loaded
with different amounts of GO (0.05, 0.1, 0.3, and
0.5 wt%), nanocomposite coatings prepared via direct
addition of 0.1 wt% GO nanosheets to polymer matrix
with lower viscosity (the viscosity of hardener was
34
lower than epoxy resin) showed maximum corrosion
protection performance.
However, GO sheets are hydrophilic due to the
presence of various oxygen functional groups including
hydroxyl, epoxide, carboxyl, and carbonyl groups on
the basal plane and edges of GO,104 leading readily to
their dispersion in water and their poor dispersion in
weakly polar organic solvents.104,175 Organic solvents
are hard to penetrate into the interlayer spaces of GO,
which in turn prevents their agglomeration.117 The
functional groups of GO are reactive sites for modi-
fication of GO sheets to alter the van der Waals
interactions among the nanofiller aggregates, making
them easily dispersed in polymer matrix.135,176 Differ-
ent approaches including covalent and noncovalent
modification besides decorating the surface of GO
sheets with nanoparticles are utilized to modify GO
which are discussed in detail in a review article by
Georgakilas et al.177 Herein, we describe the applica-
tion of modified GO nanosheets for enhancing the
corrosion resistance of polymer coatings.
Functionalizing GO sheets
In this section, various studies for utilizing functionalized
GO sheets in organic coatings are reviewed. Ramezan-
zadeh et al.178 used p-phenylenediamine (PPDA) as
aromatic diamine for modifying the surface of GO sheets
to increase the interaction of GO with epoxy matrix. The
EIS results for pure epoxy, epoxy/GO, and epoxy/FGO
samples after 40 days of immersion in NaCl solution are
shown in Fig. 16, indicating superior corrosion resistance
of epoxy/FGO nanocomposite coatings. Indeed, diamine
imparted hydrophobic properties to GO sheets, leading
to enhancement of GO distribution in epoxy matrix.
Further, functionalized GO (FGO) nanosheets act as
barrier against diffusion of corrosive agents through
coating, improving the corrosion resistance of epoxy
coating. The other corrosion protection mechanism of
FGO is enhancing the ionic resistance of epoxy coatings
which is derived from creation of negative charges on GO
and FGO sheets during exposure to neutral and alkaline
condition. Accordingly, Cl anions cannot penetrate
through coating due to cation selectivity of nanocompos-
ite coatings, leading to decrease in Cl at coating–metal
interface. Besides, OH diffusion into the coating from
cathodic sites decreases and hydrolytic degradation of
organic coating declines.
Ramezanzadeh et al.179 covalently modified the GO
nanosheets with polyisocyanate (PI) resin for incorpo-
ration in polyurethane matrix. The chains of PI resin
were chemically reacted with oxygen groups on GO
nanosheets and have formed amide and carbamate
ester bonds. Figure 17 shows the impedance modulus
of samples during exposure in NaCl solution, revealing
the corrosion protection performance of polyurethane
coatings containing 0.1 wt% PI-modified GO na-
nosheets is significantly higher than polyurethane
 Table 7: A summary of polymer/graphene composite coatings for corrosion protection of metallic substrates
Reference Polymer matrix Graphene
Type Loading (wt%) Surface treatment Optimum wt%

105 Polyetherimide Ultrasonic exfoliation graphite 2, 20 – 2 wt% + adding

in N-methylpyrrolidone MWCNT
148 Epoxy Average surface area = 500 m2/g 1 – –
149 Waterborne epoxy length: 5–20 lm; layer number: 3– 0.5, 1 – 0.5
10
150 Waterborne Epoxy Reduced graphene oxide 0.1, 0.4, 0.7 Polyvinylpyrrolidone
151 Polyaniline Graphite exfoliation 0.1, 0.25, 0.5 4-aminobenzoyl 0.5
groups
5 Epoxy Thermally reduced graphene oxide 1 duplicate the surface features of 1
fresh
plant leaves
152 Epoxy Graphene P2BA0.5%–G0.5%, Noncovalent functionalized P2BA0.5%-G0.5%
P2BA0.5%–G1% by poly(2-butylaniline) (P2BA)
153 Polyvinyl butyral Reduced graphene oxide 0.05, 0.1, 0.2, 0.3 APTES 0.1
154 Waterborne Chemically reduced graphene 1, 2, 3 3-[1-(2-Aminopropoxy)propan- 1
acrylic- oxide 2-ylamino]propane-
modified alkyd 1-sulfonate sodium (PPS)
157 Polyether imide Exfoliating graphite in NMP 5 – 5
using ultrasonic treatment
158 Polyvinylbutyral Average surface area  17 m2/g 0.02, 0.04, 0.06, 0.08, – 0.124
0.10,0.124 volume
fractions
159 Low-zinc Graphene 0.04, 0.08, 0.11, 0.33 –
waterborne
epoxy
155 Zinc-rich epoxy Graphene 0.1, 0.3, 0.5 – 0.3
156 Zinc-rich epoxy Reduced graphene oxide 0.5 – 0.5
16 Polyvinylbutyral Graphene 0.028, 0.056 – 0.056 (volume fraction)
160 Epoxy Cationic reduced 0.5, 0.8 – 0.8
graphene oxide (GO-ID+)
18 Epoxy Carboxylic functional graphite 5 1,8-diaminooctane 5
161 Epoxy Reduced graphene oxide 0.1, 0.5, 1 Poly(styrenesulfonate)-polyaniline 0.5
162 Epoxy Graphene – 3, 4, 9, 10-perylene –
tetracarboxilic acide
163 Polyurethane Reduced graphene oxide 0.15 – 0.15
164 Epoxy Reduced graphene oxide 0.25 – 0.25
J. Coat. Technol. Res., 17 (1) 19–55, 2020

35
36
Table 7: continued
Reference Dispersion method Substrate Coating thickness (lm) Corrosion protection performance

105 Ultrasonic treatment; in situ
polymerization
148 Ultrasonic treatment
149 Ultrasonic treatment
150 Magnetic stirring
151 Magnetic stirrer assisted with
ultrasonic treatment
5 Three-roll mill
Low alloy steel 15–20 More than three orders of enhancement in corrosion
protection efficiency compared with bare steel.
AA 2024-T3 28 Improving corrosion resistance; Increasing contact
angle; no effect on adhesion
Carbon steel 50 Protection efficiency of 99.7%
Zn plate – Reducing corrosion rate from 1.3 to 0.3 mm/year.
Steel 30 Increasing protection efficiency from 4.82% (for pure)
to 53.49% (for nanocomposite sample)
Cold-rolled steel 110–115 Increasing water contact angle; decreasing O2 permeability;
increasing protection efficiency from 88.45% to 99.33%.
J. Coat. Technol. Res., 17 (1) 19–55, 2020

152 Stirring Steel 20 Decreasing corrosion rate from 1.64 9 1011 to 9.34
9 1015 mm/year due to formation of passive oxide
layer catalyzed by electroactive P2BA
153 Ultrasonic treatment Copper 97 Prohibiting galvanic corrosion of graphene/metal couple
via APTES
154 Emulsion Steel 30 Increasing corrosion protection efficiency from 2.97%
(for pure coating) to 94.70% (for nanocomposite coating)
157 Mixing Steel 20 An alternative for solving the short service life of hot-dip
galvanized coatings.
158 Mixing Iron – Reducing the delamination rate by 98.6%
159 Mechanical mixing Q235 steel 30 Graphene as a good electron conductor, enabled zinc
to continue to constitute a galvanic couple with the iron
substrate, prolonging the protective effect
155 Mechanical mixing Q235 steel – Graphene increases the barrier performance and cathodic
protection of zinc-coating
156 Stirring Steel 30 Enhanced cathodic protection; superior electrical
conductivity and higher barrier performance
16 Mechanical mixing Hot-dip-galvanized 16 Decreasing O2 permeability of polymer coating
steel
160 Ultrasonic treatment Mild steel 29 Self-aligned GO-ID+ sheets in epoxy matrix; corrosion
protection; self-antibacterial coatings
18 Mixing Copper 1500 Higher corrosion resistance
161 Tri-roller mill Carbon steel 300 39% and 127% increase in tensile strength and tensile
toughness; decrease in corrosion rate from 0.865 to
1.21 9 104 mm/year
162 Mechanically mixing Steel – Enhance barrier and corrosion resistance
163 Ultrasonication Mild steel 70 Reduction of graphene oxide by Urtica dioica leaves;
enhanced corrosion resistance
164 Ultrasonication Steel 60 Antimicrobial and anticorrosion performance
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

Table 8: Typical features of graphene oxide

Theoretical surface area (m2/g) Thermal conductivity (W/m K) Electrical conductivity (Sm1) Intrinsic strength (GPa)

890167 8.8–28.8168 Insulating169 100170

40 10
10
FGO/EP

GO/EP 8
9.5
2
EP
30
6 1.5
–Z ꞌꞌ (Mohm cm 2)

(a) 1 9
4

log (Z/Ω cm2)

0.5
20
2 0 8.5
0 0.5 1 1.5 2

3.16 Hz
0
0 2 4 6 8 10 8
10
10 kHz
0.01 kHz
PI–GO/PU
7.5
GO/PU
0
0 5 10 15 20 25 30 35 40 PU
Z ꞌ (Mohm cm 2) 7
6 12 18 24 30
10 Immersion time (day)
FGO/EP (b)
80
GO/EP Fig. 17: The variation of impedance modulus (log |Z|) at
9
EP 10 mHz for polyurethane (PU), polyurethane/GO (GO/PU),
and polyurethane/PI-GO (PI-GO/PU) coatings as a function
60 of immersion time in 3.5 wt% NaCl solution at pH = 7179
–Phase angle (°)

8
log (Z/Ω cm 2)

7
6
5 phenylenediamine and p-phenylenediamine/4-vinyl-
4 0
–2 –1 0 1
log (f/Hz)
Fig. 16: (a) Nyquist and (b) Bode plots derived from EIS
results for pure epoxy, epoxy/GO, and epoxy/FGO samples
after immersion in 3.5 wt% NaCl solution for 40 days178
coating loaded with 0.1 wt% unmodified GO. En-
hanced corrosion protection performance of nanocom-
posite coatings can be discussed from different aspects.
First, covalent functionalization of GO sheets with PI
chains improves the GO dispersion in polyurethane
matrix and provides good chemical bonding between
PI-GO and polyurethane. The well-distributed PI-GO
nanosheets can block the diffusion path of corrosive
agents through coating and act as impermeable barrier.
Second, GO and PI-GO nanosheets have negative
charges due to presence of hydroxyl and carboxyl
groups and provide ionic resistance against diffusion of
OH and Cl anions through the coating.
40 Yu et al.180 showed that polystyrene (PS) coatings
containing well-dispersed modified GO nanosheets can
be successfully applied as corrosion-resistant coating.
20 In this research, GO nanosheets were modified by p-
benzoic acid (pv-GO) using two-step method. The
gas permeability and the Nyquist plots of pure PS and
2 3 4 PS/pv-GO nanocomposite samples are presented in
Fig. 18. The best barrier performance is obtained by
adding 2 wt% pv-GO nanosheets to PS matrix, and in
the case of PS/pv-GO2, the oxygen and nitrogen
transmittance reduced about 25% and 60%, respec-
tively. Moreover, the corrosion protection efficiency of
pure polystyrene coating increases from 37.90 to
99.53% via adding 2 wt% modified GO nanosheets.
The pv-GO nanosheets with high aspect ratio and
flexible structure which are uniformly dispersed in PS
matrix can increase the diffusion path of O2 and H2O
in coating, and therefore, they can inhibit corrosion
reactions at coating/metal interface.
Sheng et al.65 used p-phenylenediamine functional-
ized graphene oxide (PG)/polyaniline (PANI)
nanocomposite as anticorrosion coating. P-phenylene-
diamine improves the dispersion stability in acidic
condition and compatibility of GO with polymer
matrix. The corrosion protection efficiency of PANI
coatings increased from 85.16% to 99.9% by adding

37
J. Coat. Technol. Res., 17 (1) 19–55, 2020

3.5 250
(A) Cc
(B)
0.5

–Zimaginary (kΩ cm2)

O2 0.4 (a)
3.0 N2 0.3
Gas permeability (Barrier) 200
Cdl
0.2
2.5 Rs

–Zimaginary (kΩ cm2)

0.1
Rcp W
0.0
2.0 150 Rp 0.0 0.2 0.4 0.6 0.8 1.0

Zreal (kΩ cm2)

1.5 (f)
100
1.0
(e)
0.5 50 (d)
(c)
0.0
(b)
PS PS/pv–GO0.5 PS/pv–GO1 PS/pv–GO1.5 PS/pv–GO2 0
Compound code 0 100 200 300 400 500
Zreal (kΩ cm2)

Fig. 18: (A) The results of the gas barrier properties of PS/pv-GO nanocomposites. (B) Nyquist plots of (a) steel, (b) PS, (c)
PS/pv-GO0.5, (d) PS/pv-GO1, (e) PS/pv-GO1.5, and (f) PS/pv-GO2 samples after immersion in 3.5 wt% NaCl solution180

(APTES)-functionalized graphene (FG) and function-

1012 EP
alized graphene oxide (FGO). The Bode plots are
GO/EP
shown in Fig. 20. The enhanced corrosion protection is
GUF/EP
1011 obtained by incorporating 0.25–0.5 wt% of modified
nanosheets which is due to their lubricating effect and
⎪Z⎪0.01Hz (Ω cm2)

barrier performance. However, the cracks are grown in

1010
109
108
0 500
Fig. 19: |Z|0.01 Hz as a function of immersion time for
epoxy (EP), GO/EP, and GUF/EP samples in 3.5 wt% NaCl
solution; the scatter band reveals the data variation range
over the average of three replicates181
PG sheets which can retard the diffusion of corrosive
agents from the environment through the coating.
Zheng et al.181 used urea–formaldehyde (UF) resin
for surface modification of GO sheets (GUF) via in situ
polycondensation method. As Fig. 19 indicates, epoxy
coatings containing GUF show higher corrosion resis-
tance than epoxy and epoxy/GO coatings. The UF
chemically bonds to GO surface and forms micro-
spheres and also changes the hydrophilic nature of GO
to lipophilicity. The modification of GO with UF
increases the compatibility between GO sheets with
epoxy matrix and improves GO dispersion in epoxy
resin and, therefore, provides corrosion protection.
Mo et al.182 fabricated polyurethane composite
coatings reinforced with different loadings (0.25, 0.5,
0.75, and 1 wt%) of 3-aminopropyltriethoxysilane
polyurethane matrix by adding excess amount of FG
and FGO, weakening the properties of the nanocom-
posites. Meanwhile, polyurethane coatings containing
FGO showed higher tribological property and worse
corrosion resistance which can be assigned to the
abundant oxygen functionalized groups of GO; these
groups of GO are active sites for silane modification of
GO, besides destroying the lattice structure and barrier
1000 1500 2000 2500 3000 3500 performance of graphene sheets.
Dong et al.183 used c-methacryloxypropy-
Time (h)
ltrimethoxysilane (KH-570) for surface modification
of GO sheets in order to improve the dispersion and
the strength at filler–matrix interface in acrylic resin.
The GO sheets agglomerate within acrylic matrix due
to van der Waals forces between GO sheets; however,
the aggregation and restacking decrease in the case of
acrylic/FGO coating. The nanocomposite samples
containing 0.087 wt% of FGO showed maximum
coating adhesion and corrosion resistance.
Pourhashem et al.184 investigated the effect of silane
type on corrosion resistance of epoxy/GO nanocom-
posite coatings. In this regard, 3-aminopropyl tri-
ethoxysilane (APTES) and 3-glysidyloxypropyl
trimethoxysilane (GPTMS) are used as silane agents
with amine and epoxy end-groups, respectively. EIS
results (Fig. 21) showed that both epoxy/APTES-GO
and epoxy/GPTMS-GO nanocomposite coatings (con-
taining 0.1 wt% nanofiller) show superior corrosion
resistance compared to epoxy/GO and pure epoxy
coating which is due to the positive effect of silane
agent on enhancing the interfacial interaction between
modified GO sheets with polymer matrix. Besides, the
adhesion strength of epoxy coatings to metallic sub-

38
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

(a) (b)
5.5 5.5

5.0 5.0

4.5 4.5

log(⎪Z⎪/Ω cm2)
log(⎪Z⎪/Ω cm2)

4.0 4.0

3.5 3.5

3.0 substrate 3.0 substrate

0wt%FG 0wt%FGO
2.5 0.25wt%FG 2.5 0.25wt%FGO
0.5wt%FG 0.5wt%FGO
2.0 0.75wt%FG 2.0 0.75wt%FGO
1wt%FG 1wt%FGO
1.5 1.5
–2 –1 0 1 2 3 4 5 –2 –1 0 1 2 3 4 5
log(f/Hz) log(f/Hz)

Fig. 20: Bode plots of (a) polyurethane/functionalized graphene (PU/FG) and (b) polyurethane/functionalized graphene
oxide (PU/FGO) composite coatings182

have structural compatibility with amine groups of the

9
hardener, providing strong chemical bonds.
Further, Pourhashem et al.185 considered the effect
8 of APTES-GO amount (0.05, 0.1, 0.3, and 0.5 wt%) on
corrosion resistance of epoxy coatings. The EIS results
7 (Fig. 22) showed that epoxy coatings containing
log (⎪Z⎪Ω cm2)

0.1 wt% APTES-GO can provide superior corrosion

6
Pure Epoxy resistance and the resistance of coatings decreases by
Epoxy/GO
embedding higher amounts of APTES-GO due to
Epoxy/A–GO
agglomeration of nanosheets in epoxy matrix and
5 Epoxy/G–GO
hindering barrier performance.
4

Decorating nanoparticles on GO sheets

3
0 5
Fig. 21: The variation of |Z| value as a function of
immersion time for pure epoxy, epoxy/GO, epoxy/APTES-
GO (epoxy/A-GO), and epoxy/GPTMS-GO (epoxy/G-GO)
samples184
strates and the water contact angle on epoxy coatings
increase by incorporating silane-modified GO na-
nosheets. The improved adhesion strength is due to
the formation of covalent Si–O–metal bonds between
the silane and the surface metal-hydroxyls, increasing
the density of linkage between coating and the
substrate. The decrease in hydrophilicity is because
of reaction between OH groups of GO with silane
agent and formation of Si–O–Si bonds accompanying
with aliphatic chains of organosilane on GO sheets,
decreasing the hydrophilicity of GO nanosheets.
Meanwhile, the corrosion resistance of epoxy/
APTES-GO sample is remarkably higher than epoxy/
GPTMS-GO sample which can be considered from
different aspects: (1) Amine functional groups of
APTES are more active than epoxy groups of GPTMS;
(2) since FGO is directly added to low-viscosity
polyamide hardener, amine groups of APTES-GO
10 15 20 25 30 Decorating the surface of GO sheets with inorganic
immersion time (day) nanoparticles is another method for improving the
dispersion of GO within polymer matrix.186,187 The
decorated nanoparticles can increase the spacing
between GO sheets and separate the GO sheets.188
Since Al2O3 nanoparticles are widely used in coating
industry due to their superior hardness, chemical
stability, low cost, and good corrosion resistance, Yu
et al.188 anchored Al2O3 nanoparticles on GO sheets
via using 3-aminopropyltriethoxysilane. Among
nanocomposite epoxy coatings containing 2 wt% GO,
Al2O3, and GO–Al2O3, the synthesized GO–Al2O3
hybrid showed better dispersion quality in epoxy
matrix and provided higher corrosion resistance.
Yu et al.189 prepared TiO2–GO hybrid via using 3-
aminopropyltriethoxysilane as coupling agent for load-
ing titanium dioxide on GO sheets. Their results
showed that the water contact angle and the corrosion
resistance (Fig. 23) of epoxy coatings have increased
by incorporating 2 wt% TiO2–GO hybrid, attributing
to thin sheet-like structure and high efficiency of the
prepared hybrid in plugging the inherent micropores of
epoxy coating.
Ma et al.190 prepared epoxy coatings containing
2 wt% SiO2–GO hybrids, which is synthesized through
decorating SiO2 on GO sheets with the help of 3-

39
J. Coat. Technol. Res., 17 (1) 19–55, 2020

8 9
(a) 0 wt.% Go (b) 0 wt.% A-Go
0.05 wt.% Go 0.05 wt.% A-Go
7 0.1 wt.% Go 8 0.1 wt.% A-Go
0.3 wt.% Go 0.3 wt.% A-Go
0.5 wt.% Go

log (|Z|\Ω cm2)

0.5 wt.% A-Go
log (|Z|\Ω cm2)
7
6
6
5
5
4
4

3 3
-2 -1 0 1 2 3 4 5 -1 0 1 2 3 4 5
log F\Hz log F\Hz

Fig. 22: Bode plots for (a) epoxy/GO and (b) epoxy/APTES-GO nanocomposite coatings after 7 days of immersion in
3.5 wt% NaCl solution185

pure epoxy
2wt.% Tio2/epoxy

2wt.% GO/epoxy
2wt.% Tio2–GO/epoxy
40,0000
fitted
35,0000

30,0000
Zim (Ω cm2)

25,0000

20,0000
CPEf
15,0000
Rs
10,0000
Rct
50,000

0
Equivalent circuit models for the initial soaking
–50,000
0 200,000 400,000 600,000 800,000

Zre (Ω cm2)

Fig. 23: Nyquist plots of pure epoxy, epoxy/TiO2, epoxy/GO, and epoxy/TiO2-GO coatings after 2 h immersion in 3.5 wt%
NaCl solution; the amount of nanofiller in epoxy matrix is 2 wt%189

aminopropyltriethoxysilane and 3-glycidoxypropy-
ltrimethoxysilane. In this research, the effect of SiO2-
to-GO weight ratio including 1:6, 1:5, 1:4, 1:3, and 1:2
on the properties of nanocomposite epoxy coatings was
considered. In the case of SiO2–GO (1:5), SiO2 covers
GO in quantity; however, the SiO2 aggregates by
increasing the weight ratio to 1:6. Therefore, SiO2–GO
(1:5) are selected as nanofiller in epoxy matrix, which
leads to increase in water contact angle from 84 ± 1
to 104.8 ± 1 and enhancement in the corrosion
protection performance (Fig. 24). Indeed, the hydro-
philic surface of epoxy coating turns to hydrophobic
surface, and therefore, the wettability and the contact
between electrolyte and coating can be reduced to
protect the metallic substrate. Moreover, the SiO2–GO
nanofiller, which benefits from both advantages of GO
(i.e., sheet-like structure with high specific surface
area) and SiO2 (high chemical stability), can decrease
the defects of polymer matrix and improve the barrier
performance of epoxy coatings.
Ramezanzadeh et al.191 used 0.2 wt% of SiO2–GO
nanohybrid synthesized via a two-step in situ sol–gel
process using a mixture of 3-aminopropyltriethoxysi-
lane and tetraethyl orthosilicate for increasing the

40
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

30,000 pure epoxy that simultaneous hydrolysis of silane and GO provides

2wt.% GO/epoxy higher amount of silane grafting on GO nanosheets via
25,000 2wt.% nano–SiO2/epoxy reacting with hydroxyl and carboxyl groups of GO.
2wt.% SiO2–GO(1:5)/epoxy They studied the potential application of SiO2–GO
20,000 fitted nanohybrids prepared via both methods on corrosion
Zim (Ω cm2)

protection performance of epoxy coatings. The Z

15,000 modulus values derived from EIS results for nanocom-
posite coatings during immersion in NaCl solution are
10,000 presented in Fig. 25. The results indicate that nanohy-
brids synthesized from both methods can enhance the
5000 corrosion resistance of epoxy coatings. The NH2
groups on the surface of SiO2–GO sheets are active
0 sites for nucleophilic substitution ring-opening reaction
with epoxide groups of epoxy resin, leading to increase
0 10,000 20,000 30,000 40,000 50,000 in crosslink density in coating matrix and improving
Zre (Ω cm2) the barrier performance of nanocomposite coatings.
Further, the NH2 groups are available to increase the
Fig. 24: Nyquist plots for pure epoxy, 2 wt% GO/epoxy, bonding strength of epoxy coating to metallic substrate
2 wt% nanoSiO2/epoxy, and 2 wt% SiO2–GO (1:5)/epoxy via developing hydrogen bonds with hydroxyl groups
coatings after soaking in 3.5 wt% NaCl solution for 72, 120, on the steel substrate. Moreover, results show that
156, and 312 h, respectively190
nanohybrids synthesized via method I provide higher
corrosion resistance; indeed, the silane film on GO
nanohybrids synthesized from procedure I can more
12
(a1) SiO2-GO 24 h effectively increase the distance between GO sheets
11
SiO2-GO 48 h
and prevent the agglomeration of GO sheets in
SiO2-GO 72 h

Blank sample
polymer matrix.
Pourhashem et al.192 used tetraethyl orthosilicate
log (Z/ Ω cm 2)

10
(TEOS) as organosilane to decorate the surface of GO
9 nanosheets by SiO2 nanospheres via a facile in situ
method and studied the effect of incorporating
8
0.1 wt% SiO2–GO nanohybrids on properties of epoxy
7
coatings. The impedance modulus at low frequencies
and the amount of water uptake derived from EIS
6 results are presented in Figs. 26a and 26b, respectively.
0 10 20 30 40 50 60 70
Immersion time (days) The results clearly show that epoxy/SiO2–GO
nanocomposite coating has higher corrosion resistance
12
SiO2-GO 24 h and lower water uptake. Further, pull-off adhesion
(a2) SiO2-GO 48 h
strength and water contact angle of epoxy/SiO2–GO
11 SiO2-GO 72 h

Blank sample
coatings were significantly higher than neat epoxy and
epoxy/GO samples. These results could be assigned to
log (Z/ Ω cm 2)

10
9
8
7 coatings declines with immersion time due to degra-
6
0 10 20 30 40
Immersion time (days)
Fig. 25: Variation of |Z| at 10 mHz (extracted from Bode
plots) vs immersion time in 3.5 wt% NaCl solution: (a1)
SiO2–GO nanohybrid obtained through method I; (a2) SiO2–
GO nanohybrids obtained through method II191
corrosion resistance of epoxy coatings. They prepared
SiO2–GO nanohybrid via two different procedures: (I)
adding GO nanosheets to silane mixture and contin-
uing hydrolysis reactions for 24, 48, and 72 h; (II)
adding GO nanosheets to silane mixtures which were
prehydrolyzed for 24, 48, and 72 h. Their results show
strong Si–O–metal bonding, hydrophobic nature of
SiO2–GO nanosheets and barrier effect of SiO2–GO
nanofiller. Moreover, as Fig. 26a shows, although the
corrosion resistance of pure epoxy and epoxy/GO
dation of coatings, the corrosion resistance of epoxy/
50 60 70 SiO2–GO nanocomposite sample enhances with pro-
longing immersion time. This behavior of epoxy/SiO2–
GO is due to the presence of active silane groups which
undergo the hydrolysis reaction by consuming the
diffused water; the hydrolysis product can repel water
and also the hydrolysis reactions could lead to the
formation of Si–O–Si bonds in the coatings, improving
the compactness of matrix.
Zhan et al.20 used co-modification of GO/Fe3O4
hybrid with polydopamine and KH550 for improving
the corrosion resistance of epoxy coatings. For this
purpose, GO/Fe3O4 hybrid was synthesized by
hydrothermal method, and then, it was bio-modified
by self-polymerization between dopamine (DA) and

41
J. Coat. Technol. Res., 17 (1) 19–55, 2020

9 0.16
(a) (b)
0.14
8
log (|Z|0.01HZ/Ω cm 2 )

Water uptake (ϕ w)
0.12
7
0.10 Epoxy/GO
Epoxy/SiO2 –GO
6 Pure epoxy 0.08
Epoxy/GO
Epoxy/SiO 2 –GO 0.06
5
0.04
4
0.02
3 0.00
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Immersion time (day) t (h )
1/2 1/2

Fig. 26: The variation of (a) |Z|0.01 Hz and (b) water uptake as function of immersion time in 3.5 wt% NaCl solution for pure
epoxy, epoxy/GO and epoxy/SiO2–GO coatings192

–14,000 EP
144h
GO/EP
–12,000
107 TiO2+GO/EP

–10,000 ⎪Z⎪ (Ω cm2) TiO2–GO/EP

Z ꞌꞌ(Ω cm2)

–8000 106 TiO2–GO–f–EP

fitting
–6000
2.0 wt%
105
–4000 1.5 wt%
1.0 wt%
–2000 0.5 wt%
0 wt% 104
0
0 10,000 20,000 30,000 40,000 50,000 60,000 10–2 10–1 100 101 102 103 104 105
Z ꞌ(Ω cm2) F (Hz)

Fig. 27: Impedance spectra of coatings containing Fig. 28: The Bode plot after 96-h immersion in 3.5 wt%
different amounts of GO-Fe3O4@poly (KH550 and DA) NaCl solution193
hybrid after soaking for 144 h20
resistance of epoxy coatings compared to GO and
TiO2–GO nanofillers.
Table 9 shows the summary of research in the field
secondary functional monomer (KH550). The abun- of polymer coatings reinforced with GO. Accordingly,
dant amino-groups developed on GO/Fe3O4 hybrid GO is an interesting nanofiller for enhancing the
facilitated the dispersion of nanohybrid in epoxy corrosion protection performance of organic coatings
coating and enhanced the interfacial interaction due to its low cost, chemical stability, barrier proper-
between nanofiller and polymer matrix. The prepared ties, and environmentally friendly properties.194
nanocomposite coatings show higher corrosion resis-
tance (Fig. 27) and higher microhardness compared to
pure epoxy sample. Carbon dots
In another study, Liu et al.193 synthesized titanium
dioxide-decorated GO nanocomposites using 3-amino- Carbon dots are quasi-spherical carbon nanoparticles
propyltriethoxysilane (APS). Then, the TiO2–GO with size below 100 nm which show quantum confine-
nanocomposite was chemically modified with GPTMS ment and edge effects.204 Carbon dots, including
(TiO2–GO–f) before introducing into epoxy resin. carbon nanodots, graphene quantum dots, and polymer
GPTMS modification improved the TiO2–GO dots, are a new generation of 0D carbon-based
nanocomposite dispersion in epoxy resin and enhanced nanomaterials, and they have attracted the attention
the crosslinking density and adhesion strength by of researchers in recent years due to their strong
covalent bonds. As Fig. 28 shows, TiO2–GO–f is an photoluminescence, high chemical stability, environ-
appropriate nanofiller for increasing the corrosion

42
 Table 9: A summary of polymer/GO composite coatings for corrosion protection of metallic substrates
Reference Polymer matrix Graphene Oxide Dispersion method Substrate Coating Corrosion protection performance
thickness
Loading Surface treatment Optimum wt% (lm)
(wt%)

172 Epoxy 0.1 – 0.1 Ultrasonication Carbon steel 20 ± 5 GO sheets with higher aspect ratio can provide
more tortuous path in polymer matrix
21 Alkyd resin 16 – 16 Ball milling Galvanized iron 150 Increasing corrosion protection efficiency to 76%;
antifouling
173 Epoxy 0.125, – 0.25 Mechanical stirring Carbon steel 40 Increasing corrosion protection efficiency to 79.7%
0.25, 0.5
174 Epoxy 0.05, – 0.1 Ultrasonic treatment Mild steel 150 Enhancing GO dispersion in coating via dispersion
0.1, 0.3, GO in low-viscosity polymer matrix (i.e.,
0.5 hardener)
195 Polybenzoxazine 0.5, 1, – 3 Ultrasonication Carbon steel 50 Barrier performance against oxygen and water
(Rubber) 1.5, 2, 3
178 Epoxy 0.1 P-phenylenediamine 0.1 Ultrasonic treatment Mild steel – Increasing hydrophobicity and ionic resistance
(PPDA)
179 Polyurethane 0.1 Polyisocyanate 0.1 High shear mixer Steel 60 Increasing corrosion resistance and adhesion
180 Polystyrene 0.5, 1, p-phenylenediamine/ 2 Ultrasonic treatment Steel 15.7 Corrosion protection efficiency increased from
1.5, 2 4-vinylbenzoic acid 37.90–99.53%
65 Polyaniline 3, 5, 10 p-phenylenediamine 10 Ultrasonic treatment Carbon steel – Anticorrosion efficiency increases from 85.16–
99.9%
181 Epoxy 0.3 Poly (urea–formaldehyde) 0.3 Agate grinding ball Steel 120 Enhancing corrosion performance via using
lipophilic-modified GO
196 Waterborne epoxy – Polydopamine – Ultrasonic treatment Mild steel 20 Enhanced corrosion resistance
196 Waterborne epoxy – Polydopamine Ultrasonication Carbon steel 20 Enhanced corrosion resistance
197 Maleic anhydride 15, 30, Octadecylamine (ODA) 60 Mixing Steel – Enhanced corrosion resistance and gas barrier
grafted 45, 60 modified graphene performance
polypropylene oxide
198 Epoxy – Polyaniline (PANI) – Ultrasonic treatment Steel 50 Improving the compatibility between epoxy and
GO via PANI fibers on GO sheets; decreasing
the storage modulus and crosslink density and
increasing Tg of epoxy; improving thermal
stability; enhancing barrier performance and
corrosion resistance
199 Waterborne acrylic – Polyhedral oligomeric – Stirring Galvanized steel 3 Enhanced corrosion resistance
acid silsesquioxane (POSS)
182 Polyurethane 0.25, 0.5, APTES 0.5 Ultrasonic treatment Cast iron 25 Increasing protection efficiency from 59.84% to
0.75, 1 99% and 91.84% via adding functionalized
graphene and functionalized GO, respectively
183 Acrylic 0.06, 0.08, KH570 0.08 In situ polymerization – – Increasing water resistance, acid and alkali
0.10, resistance of coating
0.12
184 Epoxy 0.1 APTES &GPTMS 0.1 Ultrasonic treatment Mild steel 150 Increasing corrosion resistance, water contact
angle and adhesion strength of coatings;
improving GO dispersion in coating via altering
the end-group of silane agent
185 Epoxy 0.05, 0.1, APTES 0.1 Ultrasonic treatment Mild steel 150 Enhancing corrosion resistance via improving GO
0.3, 0.5 dispersion in coating; increasing pull-off
adhesion strength by two times
200 Polyurethane – GPTMS – Mixing Steel 70 Improving mechanical properties and corrosion
resistance
188 Epoxy 2 Al2O3 2 Ultrasonic treatment Steel 60 Increasing the corrosion resistance due to higher
aspect ratio of GO sheets via adding Al2O3
J. Coat. Technol. Res., 17 (1) 19–55, 2020

43
44
Table 9: continued
Reference Polymer matrice Graphene Oxide Dispersion method Substrate Coating Corrosion protection performance
thickness
Loading Surface treatment Optimum wt% (lm)
(wt%)

189 Epoxy 2 APTES-modified TiO2 2 Ultrasonic treatment Steel 40 Increasing corrosion resistance due to good
exfoliation and dispersion and blocking
micropores; increasing water contact angle
from 87.5 ± 1 to 96.2 ± 1
193 Epoxy – GPTMS-modified TiO2 – Stirring Aluminum alloy – AntiUV aging; enhanced corrosion resistance
2024
190 Epoxy 2 Modification of GO with 2 Ultrasonic treatment Steel 60 Increasing corrosion resistance; increasing
GPTS-& APTES- water contact angle from 84 ± 1 to
modified SiO2 104.8 ± 1
191 Epoxy 0.2 SiO2 synthesis on GO via 0.2 Ultrasonic treatment Mild steel 50 Increasing corrosion resistance; increasing
in situ hydrolysis of crosslink density due to NH2 groups of SiO2
J. Coat. Technol. Res., 17 (1) 19–55, 2020

TEOS-APTES
192 Epoxy 0.1 SiO2 decoration on GO via 0.1 Ultrasonic treatment Mild steel 150 Decreasing corrosion rate from 0.1705 to
in situ hydrolysis of 0.0012 mm/year; increasing water contact
TEOS (tetraethyl angle from 73.1 ± 2 to 84.3 ± 1;
orthosilicate) increasing pull-off adhesion strength from
8.5 ± 0.5 MPa to 17.7 ± 1.5 MPa
20 Epoxy 0.5, GO-Fe3O4 modification by 0.5 Mechanical stirring Steel – Enhanced corrosion protection; improving
1, self-polymerization microhardness by 71.8% compared to pure
1.5, 2 between dopamine and epoxy sample
KH550
193 Epoxy – GPTMS-modified TiO2-GO – Ultrasonication Aluminum alloy – Enhanced UV resistance and corrosion
resistance
201 Epoxy 0.15 Polyaniline nanofiber- 0.15 Ultrasonication Steel 75 Enhanced corrosion resistance
CeO2-grafted GO
nanosheets
202 Epoxy 0.2 GO grafted by zinc doped 0.2 Wet transfer migration Steel 65, 85, Active corrosion inhibition and barrier
polyaniline 115 performance
203 Zinc-rich epoxy 1 Zinc-reduced graphene 1 Ultrasonication Steel – Enhanced corrosion resistance
oxide
 J. Coat. Technol. Res., 17 (1) 19–55, 2020

8 4 x 106
(a) 80 (b)
7
3 x 106

–Phase angle (°)

log (Z/Ω cm2)
60

–Zꞌꞌ (Ω cm2)
6

2 x 106
40
5

20 106
4

3 0 0
–2 –1 0 1 2 3 4 5 0 2 x 106 4 x 106 6 x 106 8 x 106 10 x 106
log (f/Hz) Zꞌ (Ω cm2)
pure epoxy
epoxy/0.1f–GQDs
epoxy/0.5f–GQDs

Fig. 29: (a) Bode and (b) Nyquist plots for pure epoxy, epoxy/GO and epoxy/f-GQDs after 28 days of immersion in 3.5 wt%
NaCl solution15

mental-friendly behavior, low toxicity, and excellent filler to polymers such as polymethacrylate (PMMA),
biocompatibility.205,206 The chemical structure of car- polyethyl methacrylate (PEMA), and mixtures of
bon dots depends on the synthesis method. Indeed, PMMA with PEMA, PMMA with polybutyl methacry-
graphene quantum dots have graphene structure inside late (PBMA), and PMMA with polystyrene (PS),
the dots and show the properties of graphene.207 revealing 22–36% restoration of the initial tensile
Carbon nanodots are spherical nanoparticles with or strength. Also, polyurethane/carbon dots nanocompos-
without obvious crystal lattice. Polymer dots are ite coatings with 600 lm thickness on stainless steel
aggregation or crosslinked polymers from linear non- showed higher corrosion resistance than pure polyur-
conjugated polymers.208 ethane sample. Further, the self-healing and corrosion
Cui et al.209 proved that carbon dots with high water protection performance of other polymer coatings
solubility and low cytotoxicity are an appropriate eco- including poly acrylic acid, epoxy, and fluorocarbon
friendly corrosion inhibitor for carbon steel in aggres- paint have improved by adding carbon dots. The
sive solutions. The corrosion protection performance obtained properties in polymer/carbon dots nanocom-
of carbon dots is attributed to absorption of carbon posite coatings are the result of strong interaction of
dots on the surface of steel substrate and forming a carbon dots with polymers.
protective layer during immersion in 1 M HCl solution. Further, Pourhashem et al.15 investigated the effect
Also, their results showed that the corrosion inhibition of APTES-modified graphene quantum dots (f-GQDs)
of carbon dots is controlled by the concentration of on corrosion protection performance of solvent-based
carbon dots in corrosive electrolyte. epoxy coatings. They used a simple and low-cost
Konwar et al.210 investigated the effect of carbon method with gram-scale production capability for
dots derived from tea as a green source on the synthesizing graphene quantum dots which is compet-
properties of chitosan hydrogel films. The prepared itive with other carbon-based nanomaterials. The
nanofilms showed excellent thermal stability, mechan- compatibility between polymer matrix and graphene
ical strength, and UV–visible blocking due to electro- quantum dots improved via functionalizing the
static interactions between chitosan with positive nanoparticles with aminosilane. The electrochemical
charge and carbon dots with negative charge. The analysis (Fig. 29) proved that the corrosion resistance
water contact angle on chitosan film increased by and barrier performance of coatings have enhanced by
adding carbon dots, which is ascribed to the increase in adding 0.5 wt% f-GQDs.
the density of hydrophobic aromatic groups on the Also, Ramezanzadeh et al.212 used graphene oxide
surface of film via incorporating carbon dots. quantum dots synthesized by pyrolyzing citric acid and
In the specific field of corrosion protection functionalized by polyaniline as corrosion-resistant
nanocomposite coatings, Zhu et al.211 proposed a nanofiller in epoxy coatings. In another study, Ren
simple and cost-effective method for preparing self- et al.213 synthesized nitrogen-doped carbon dots via
healing and corrosion-resistant coatings via incorpo- solvothermal method using o-phenylenediamine as
rating carbon dots into polymer matrix. In this precursor and then used it as nanofiller in waterborne
research, carbon dots, synthesized initially via electro- epoxy coatings. Both of these studies revealed that
chemical etching of graphite rods, were introduced as

45
J. Coat. Technol. Res., 17 (1) 19–55, 2020
carbon quantum dots have potential application for
increasing the corrosion resistance of polymer coatings.
Application of multicarbon nanostructures
In order to benefit from the advantages of different
carbon-based nanomaterials, researchers have used
multicarbon nanomaterials in polymer coatings. In this
regard, Yao et al.19 used carboxylic-functionalized
CNT and GO for modifying the surface of carbon
fibers to improve the interfacial properties of carbon
fiber/epoxy composites. The results confirmed that
both CNTs and GO can be appropriate candidates for
improving the interfacial properties of carbon fiber–
polymer composites. Composites containing CNT–
carbon fiber showed higher shear strength and com-
posites containing GO/carbon fiber provided higher
humidity resistance. The enhancement of mechanical
properties is because of increasing the interaction and
decreasing the stress concentration at fiber–matrix
interface. The decrease in moisture absorption is due
to increase in the surface free energy and surface
wettability of fibers, providing close molecular contact
between fibers and matrix. Also, functional groups of
CNTs and GO nanosheets can improve the chemical
bonding between epoxy matrix and carbon fibers.
Further, the different behavior of CNT/fiber and
GO/fiber nanofillers can be assigned to different
structure of CNTs and GO; indeed, CNTs have porous
network and GO nanosheets have layered structure,
leading to lower moisture absorption of epoxy/GO-
fiber composites.
Also, Hu et al.214 considered the synergetic effect of
3-aminophenoxyphthalonitrile-functionalized carbon
nanotubes (CNTs–CN) and graphene oxide (GO–
CN) on corrosion protection performance of epoxy
coatings. Epoxy coatings containing 2 wt% of nano-
fillers including GO–CN, GO–CN: CNTs–CN = 1:3,
and CNTs–CN were prepared via sonication and
mechanical stirring. Meanwhile, epoxy coatings con-
taining GO–CN and CNTs–CN show superior corro-
sion protection. Further, the corrosion resistance
gradually increases via increasing the GO–CN and
CNT–CN loading from 1 to 2 wt%; however, the
corrosion resistance slightly decreases by loading
2.5 wt% GO–CN and CNT–CN, due to the serious
aggregation of the nanofillers.
Almajid et al.215 prepared vinyl ester nanocompos-
ites containing both graphene (0.01–0.3 wt%) and
CNTs (0.5–5 wt%). The main challenge for preparing
this composite is achieving good dispersion of nano-
fillers with different geometry and aspect ratio. The
results indicated that conductive hybrid composite
provided higher corrosion resistance than neat vinyl
ester. In the case of electrically conductive corrosion-
resistant coatings, a physical barrier against diffusion of
corrosive agents is obtained by combination of
46
graphene with layered morphology and CNT without
losing electrical conductivity.
In another research directed by Asthana et al.,216
electrically conductive superhydrophobic polymer-
based coatings were prepared. Carbon black, CNT,
graphene, and their combination were loaded in
fluoropolymers to prepare electrically conductive coat-
ings. Although all prepared nanocomposite coatings
showed superhydrophobic and oleophilic behavior,
best performance was obtained by combining carbon
nanofillers in polymer matrix; indeed, coatings con-
taining carbon black: graphene nanosheets: poly-
mer = 1:1:2 showed both excellent impalement
resistance and electrical conductivity.
Corrosion protection mechanism
Corrosion of metals involves the oxidation of metals
and reduction of oxygen, protons (H+), and water217:
Fe ! Fe2þ þ 2e
Fe2þ ! Fe3þ þ e
O2ðgÞ þ 2H2 O þ 4e ! 4OH
2Fe2þ þ O2 ðgÞ þ 2H2 O ! 2FeOOH þ 2Hþ
Meanwhile, organic coatings can protect metallic
structures from corrosion via different aspects includ-
ing: (1) organic coatings provide a physical barrier
against the diffusion of corrosive agents (i.e., water and
oxygen) through coating, (2) organic coatings have
strong adhesion to the metallic substrate under chem-
ical and electrochemical conditions imposed by the
corrosive environment, and (3) organic coatings can
block the local anodes and cathodes at metal/coating
interface.218 However, defects of coatings such as
cracks, air bubbles, microvoids, and contaminants,
beside the poor resistance of organic coatings to crack
propagation and inherent internal stresses, have great
influence on the lifetime of organic coatings.219 In fact,
O2 and H2O can easily diffuse into pure polymer
coatings and reach at metal–coating interface to react
with metal substrate.
Corrosion protection, barrier performance, and
mechanical properties of organic coatings can be
improved via adding carbon nanofiller. As Fig. 30
shows, carbon-based nanomaterials increase the tortu-
osity of diffusion path of corrosive agents through
coating, leading to high corrosion-resistant nanocom-
posite coatings.
The higher corrosion resistance of nanocomposite
coatings can be considered from different aspects
which are discussed below:

Cathodic reaction: O2 + 2H2O + 4e–
(a) (b) (c)
M M M M
Anodic reaction : M
Fig. 30: Schematic of corrosion protection for (a) pure polymer coating and polymer coatings containing carbon-based
nanomaterials including (b) fullerene, (c) carbon black, (d) carbon nanotubes, (e) graphene and graphene oxide, and (f)
carbon dots
1. Carbon-based nanomaterials act as second phase
in the polymer matrix and enhance the barrier
performance of coating by decreasing the porosity,
improving the integrity of coating and tortuousing
the diffusion path for deleterious species.220 There-
fore, O2 and H2O are forced to diffuse into coating
via a tortuous path and the permeation rate of
corrosive agents through nanocomposite coatings
decreases. Meanwhile, graphene and graphene
oxide may be preferred over other carbon-based
nanomaterials due to their layered two-dimen-
sional structure, high surface area and aspect ratio,
low density, and low production cost.38,221,222
Indeed, graphene-based materials are regarded as
ultrahigh barrier materials with outstanding
mechanical properties,223 and these nanomaterials
act as physical barriers for corrosion protection.224
These nanomaterials can effectively prevent cor-
rosive agents from the steel substrate.20 Hence, the
corrosion rate decreases via limiting the accessi-
bility of aggressive specie to metal surface.
2. Since carbon-based nanomaterials tend to agglom-
erate in organic coatings due to their high specific
surface area and van der Waals interactions, the
dispersion quality of carbon-based nanomaterials
within polymer matrix is an important factor for
achieving high corrosion resistance nanocomposite
coatings.221 The nanofiller loading in coating
matrix, the surface treatment of carbon-based
materials, and using surfactants are considered as
different approaches for improving the dispersion
quality of nanofillers in polymer matrix. Surface
modification of carbon-based nanofillers is a way
for preventing the agglomeration of nanofillers in
polymer matrix, and therefore, the surface-to-
volume ratio of nanofillers would not be reduced,
leading to restriction of coating porosity and
enhancement in barrier performance.147
J. Coat. Technol. Res., 17 (1) 19–55, 2020
4OH–
(d) (e) (f)
M M
M n+ + ne –
3. Modification of carbon-based nanomaterials is an
appropriate method for improving the efficiency of
nanofiller loading in polymer matrix and enhancing
the interfacial interactions between nanofiller and
matrix,135,225,226 leading to enhanced corrosion
resistance properties. The functional groups devel-
oped on the surface of carbon-based materials can
participate in curing reactions of polymer matrix,
and therefore, the interfacial interactions between
polymer and nanofillers enhance.20 The functional
groups on the surface of carbon nanofillers provide
chemical compatibility between nanofiller and
matrix. Therefore, it would be possible to add
higher amounts of nanofiller into polymer matrix,
decreasing the porosity of coating more signifi-
cantly and increasing the barrier performance of
the coating.161
4. Chemically modified carbon-based nanofillers can
alter the water contact angle on coatings and
enhance the adhesion strength of coatings to
metallic substrates. Therefore, these nanomaterials
can decrease the water sorption onto the coatings,
and also, the accessibility of water to the coating/
metal interface can be decreased.5 When the
amount of corrosive agents at coating/metal inter-
face decreases, lower corrosion products accumu-
late beneath the coating; hence, coating
delamination from substrate decreases during
immersion time and enhances the protection per-
formance of coatings.196
5. The other aspect of corrosion protection mecha-
nism is increasing the ionic resistance of polymer
coatings which can be discussed in the case of
graphene oxide and/or functionalized carbon na-
nofillers with negative charges on their surface.
The negative charges on the surface of carbon-
based nanofillers inhibit the permeation of Cl and
OH anions in the coatings. Hence, the amount of
47
J. Coat. Technol. Res., 17 (1) 19–55, 2020
Cl anions at coating–metal interface decreases.
Besides, OH anions produced in cathodic reac-
tions at coating–metal interface cannot diffuse into
the coating and the delamination of coatings can
be prevented.178
6. Besides, carbon-based nanomaterials can be di-
vided into three groups including conductive (CB,
graphene, and CNT), semiconductive (carbon
dots), and insulating (graphene oxide) nanofillers.
In the case of electrically conductive carbon-based
nanomaterials, these nanomaterials can be used in
conductive polymer coatings to improve the elec-
trical conductivity besides the barrier performance
of conductive polymer matrix. Moreover, these
conductive nanomaterials have potential applica-
tion in coatings with cathodic protection mecha-
nism such as zinc-rich epoxy coatings in order to
provide electrical contact between zinc particles
and decrease the loading of zinc particles in
coating accompanied by improving the barrier
protection against diffusion of corrosive
agents.63,64,155
Cytotoxicity of carbon nanostructures
The possibility of exposure to nanoparticles used in
coatings happens during different stages including
coating production, applying coatings on surfaces,
aging of paints (due to UV irradiation, thermal stress,
hydrolytic degradation), and removal process (by sand
blasting and drilling).227 Therefore, one important
parameter for public application of carbon-based
nanomaterials in paint and coating industry is consid-
ering the potential risks of their implementation. The
side health and environmental effects of nanomaterials
are challenging issues which should be evaluated
before their application in nanotechnology industry.228
The disposal of nanomaterials into environment (i.e.,
soil, water, and air) facilitates their entrance into
human body via inhalation and food chain and there-
fore results in side effects on human health. The
harmful effects of nanomaterials strongly depend on
physical dimension, physical state, chemical treat-
ments, and impurities.229 The interaction of carbon-
based nanomaterials with cell systems differ with each
other due to differences in morphology, synthesis
procedure, crystal structure, size, composition, chem-
ical stability, and their concentration.230,231 Herein, we
have reviewed the toxicity of carbon nanostructures.
• Fullerene: The ability of fullerene to induce toxicity
may need a light or ultraviolet source in order to
excite the surface of fullerene. Fullerene at rela-
tively high dosage (600 mg/kg for water soluble
fullerene) provides acute toxicity, and also, animal
studies showed that dermal and oral toxicity is low
even at high dosage of fullerene.232
• CNTs: Since CNTs have wide application in various
48
industries, their influence on environment and
health has drawn a great deal of attention.229
Further, the toxicity of CNT is challenging due to
structural similarities between CNT and asbes-
tos.233 In vivo studies showed that CNTs could
induce pulmonary inflammation and lung cellular
proliferation, inhibiting the growth of heart muscle
in rats. In the case of mammalian cells, well-
dispersed CNTs (i.e. functionalized CNTs with
hydrophilic groups) show lower toxicity than
agglomerated ones. However, the toxicity of well-
dispersed CNTs increases in bacterial cells.229
• Graphene: Graphene and graphene oxide na-
nosheets have great potential application in biolog-
ical and biomedical application including
antibacterial materials, drug delivery and tissue
engineering scaffolds. However, there are contra-
dictory results about toxicity and nontoxicity of
graphene.48
• Carbon dots: Fluorescent carbon dots show low
toxicity and high capacity for biological fields and
environmental engineering.234,235
There is still inadequate research on the effect of
carbon nanomaterials on environment and human
health. The results indicate that the human and
environmental health risks of organic coatings con-
taining carbon-based nanomaterials should be evalu-
ated individually.
Moreover, it should be mentioned that Smulders
et al.227 studied the inflammatory and toxic effect of
three pristine engineering nanoparticles (TiO2, Ag, and
SiO2) and three aged paints containing nanoparticles
(TiO2, Ag, and SiO2). They showed that pristine
nanoparticles have subtle inflammatory/toxic effect
on the lungs and negligible effects on the blood
parameters. However, the aged paints containing
nanoparticles did not modify neutrophils and they
mildly induced cytokine level.227 Besides, Saber
et al.236 revealed that the paint/laquer matrix is
more determinant of DNA damaging effects than the
addition of nanomaterials. Indeed, pure nanoparticles
cause greater inflammation than nanoparticles embed-
ded in paint matrix.236,237
Conclusion and outlook
It is well reported that the metal-based coatings cannot
be considered as practical choices in anticorrosion field
anymore due to their high cost and environmental
issues which necessitates the efforts to replace more
effective alternatives. Following this need, nanocom-
posite coatings have been of great interest as they
provide combined constructive characteristics of the
matrix and filler materials. In furtherance of develop-
ing novel nanocoatings possessing high performance,

polymer–nanocarbon nanocomposite coatings have
been focused and considered as the future candidate.
Therefore, organic coatings are regularly used for
metallic materials to protect them against corrosive
environments. In order to enhance the potential
application of organic coatings, nanocomposite coat-
ings seem to be an appropriate alternative choice to
replace conventional coating systems. Among different
nanomaterials, carbon nanostructures including full-
erene, carbon black, carbon nanotubes, graphene, and
graphene oxide have recently been used in coating
systems due to their unique characteristics. As studies
show, theses nanocomposite coatings provide higher
corrosion and degradation protection. Although or-
ganic coatings containing carbon black, carbon nan-
otubes, and fullerene are nowadays being used,
graphene and graphene oxide have opened a new
dimension for production of nanocomposite coatings
because of their higher barrier performance in corro-
sion protection, besides ease of dispersion in polymeric
coatings and environmentally friendly nature.
Further developments in polymer coatings contain-
ing carbon-based nanomaterials will be obtained via
improving the nanofiller dispersion in polymer matrix
via simple low-cost methods. It is evident that carbon-
based nanofillers will be used extensively in different
industries to pave the way of providing corrosion
resistance coatings with long lifetime and low cost. The
proposed nanocomposite coatings will be loaded with
significantly low amounts of carbon nanofillers, leading
to decrease in the anticorrosive pigment usage while
increase in the strength-to-weight ratio.
Acknowledgments The authors would like to thank
Iranian Elite National Foundation (Bonyad Melli
Nokhbegan) as Allameh Tabatabaei’s Award for
financial support.
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