Materials Chemistry and Physics 303 (2023) 127731

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Materials Chemistry and Physics

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

Development of graphene incorporated acrylic-epoxy composite hybrid

anti-corrosion coatings for corrosion protection
Sachin Sharma Ashok Kumar a, I.A. Wonnie Ma a, K. Ramesh a, b, *, S. Ramesh a, b
a
Centre for Ionics Universiti Malaya, Department of Physics, Faculty of Science, Universiti Malaya, Kuala Lumpur, 50603, Malaysia
b
Department of Physics/Saveetha School of Engineering, Saveetha University(SIMATS), Chennai, India

H I G H L I G H T S

• Acrylic-epoxy/graphene based composite coatings for mild steel substrate.

• Graphene nanofiller enhances the protective performance of the organic coatings.
• Electrochemical impedance spectroscopy investigates corrosion protection properties.
• FTIR verifies the chemical structures of the composite coatings.

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

Keywords: Corrosion-induced damages have resulted in malfunctions as well as failures in metallic structures and led to
Graphene economical loss. In addition, the wonder material, graphene, is widely applied in the corrosion protection
Corrosion protection coatings due to its excellent chemical stability, superior mechanical properties, and high corrosion resistance.
Nanocomposite coatings
Herein, the remarkable features of graphene-based nanofillers to improve the barrier performance of the acrylic-
Epoxy
epoxy based polymer coatings are demonstrated. In different weight percentages, graphene nanoflakes were
Electrochemical impedance spectroscopy (EIS)
added to the blended polymer coatings and the hybrid coatings were characterized using Fourier-transform
infrared spectroscopy (FTIR), Contact angle (CA), Field emission scanning electron microscopy (FESEM) and
Electrochemical impedance spectroscopy (EIS) to investigate the chemical structure, surface roughness, surface
morphology and coating dispersibility and corrosion protection properties, respectively. All the coatings were
prepared using solution intercalation technique (sonication process) to overcome the nanoparticle agglomera­
tion. Furthermore, the obtained results suggested that incorporation of 1 wt% graphene remarkable improved the
protective properties of the polymer coatings due to the excellent dispersion and even distribution of the gra­
phene nanoparticles. Moreover, an increment of the CA was displayed with a decreasing trend in the water
absorption rate particularly for 0.5–3 wt% loading rates of graphene nanoparticles within the polymeric matrix.
At higher graphene concentrations, the large agglomeration led in the overall reduction of the corrosion resis­
tance. However, at different immersion time, the FESEM micrographs revealed that a strong anticorrosion barrier
was provided by the graphene nanofillers over a period of 90 days of immersion. Overall, due to the fascinating
properties of graphene, the inclusion of graphene-based nanofillers in the polymer matrix enhanced the barrier
and protective properties of the coatings.

1. Introduction reported to be at approximately USD $2.5 trillion [3]. In addition, pit

Corrosion is often referred to as the degradation of a material upon
its interaction with the surrounding environment [1,2]. Globally, the
industrial challenges associated with corrosion has resulted an immense
impact on the world economy, whereby the annual global losses were
formation, intergranular corrosion, uniform corrosion, galvanic, crevice
formation, stress, erosion-corrosion, and leaching corrosion respectively
are some forms of the corrosion [4,5]. For instance, many industrial
practices namely oil well acidizing, acid cleaning, acid pickling etc. have
led in the direct contact of the metal surface with the concentrated acids,

* Corresponding author. Centre for Ionics Universiti Malaya, Department of Physics, Faculty of Science, Universiti Malaya, Kuala Lumpur, 50603, Malaysia.
E-mail address: rameshkasi@um.edu.my (K. Ramesh).

https://doi.org/10.1016/j.matchemphys.2023.127731
Received 13 November 2022; Received in revised form 27 March 2023; Accepted 5 April 2023
Available online 7 April 2023
0254-0584/© 2023 Elsevier B.V. All rights reserved.
S.S. Ashok Kumar et al.
thus, resulting the metals and alloys to experience severe corrosion
[6–9]. Generally, metallic materials have been utilized in various in­
dustrial applications namely water treatment plants, heat exchangers,
boilers, cooling systems, etc. and in the presence of saline media con­
taining chloride ions, this has further resulted in an aggressive attack on
the metallic structures [10–13]. Hence, considerable efforts have been
devoted to develop new corrosion prevention strategies to increase the
lifespan of the material and to delay the rate of degradation [14,15]. For
instance, the anti-corrosion coatings and corrosion inhibitors were re­
ported to be the most popular approaches among the different meth­
odologies used for corrosion protection. In other words, numerous
polymers, inorganic/organic compounds and nanomaterials have been
employed as promising candidates to produce effective and efficient
coatings and as corrosion inhibitors [4,5,16].
In the academic and industrial world, graphene has been considered
as a wonder material due to possessing a specific combination of phys­
icochemical properties. In general, graphene is composed of sp2 -hy­
bridized carbon atoms that are hexagonally arranged in two-
dimensional (2D) structure [17–19]. Furthermore, its excellent proper­
ties namely thermal conductivity, electrical conductivity, chemical and
thermal stability, high mechanical resistance, and impermeable nature
makes graphene a perfect candidate as a barrier material for
anti-corrosive coatings application [20–25]. With all of these mentioned
above, with high technological impact, this fascinating material has
been widely utilized in industrial fields such as aerospace, electronics,
bioengineering sectors etc. In addition, one of the most successful ap­
plications of graphene was reported to be the reinforcement of com­
posite coatings, regardless of ceramic, metallic or polymer matrix
[26–30]. For instance, the inclusion of graphene to resins have signifi­
cantly enhanced the electrical and mechanical attributes of the poly­
meric matrices, thus, resulting in the generation of multifunctional
coatings [31,32]. Moreover, it has been previously reported that gra­
phene has remarkably protected the substrate on which it was being
deposited. Also, as a reinforcing filler, graphene has enabled the reali­
zation of flame-retardant barriers, anti-fouling coatings and wear
resistant layers respectively [33–35]. Interestingly, when graphene was
added to a polymeric matrix, it was revealed that the corrosion resis­
tance performance of the composite coating was significantly enhanced
[36–39]. Here, a tortuous path for the absorption of aggressive species
was provided by the graphene due to the combination of high aspect
ratio and very low permeability to small molecules [40,41]. Addition­
ally, the barrier effect exerted by the graphene nanoparticles resulted in
the improvement of the corrosion protection of the metal substrates due
to be evenly distributed in the polymer matrix, hence, further preventing
the phenomena of agglomeration which could possibly harm the per­
formance of the composite coating [42]. However, there are limitations
with regards to graphene as a filler distribution in the resin, whereby the
presence of the strong Van der Waals forces within the graphene caused
it to agglomerate [43,44]. In addition, the microscopic phase separation
attributed by the uneven dispersion of the inorganic particles within the
polymer matrix was considered as a crucial issue. On an important note,
despite particles being dispersed well within the polymer matrix along
with the blending steps, the agglomeration could occur during the cure
time. Importantly, with the addition of higher percentage of nano­
particles, the viscosity of the coating was observed to increase, thus,
resulting in a difficulty with coating applications [45].
In this study, the effects of graphene nanofillers inclusion into the
polymer coatings was investigated to evaluate the corrosion protection
performance on mild steel substrate. Furthermore, using a fixed weight
ratio of 90:10 (acrylic: epoxy), the polymer coatings were mixed along
with the addition of 1 wt% of polydimethylsiloxane (PDMS). Here, as a
modifier, the PDMS was added into all samples to develop acrylic-epoxy-
PDMS polymeric coating systems with graphene nanofillers to enhance
their surface wettability. The electrochemical impedance spectroscopy
(EIS) and Fourier transform infrared spectroscopy (FTIR) were
employed to evaluate performance of the corrosion protection and
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Materials Chemistry and Physics 303 (2023) 127731
barrier properties as well as to determine the functional groups of all the
developed coating systems respectively. Moreover, the contact angle
(CA) and the water absorption (Φ) rates of the developed coatings were
evaluated and the field emission scanning electron microscopy (FESEM)
was utilized to investigate of the dispersibility of the nanoparticles and
the presence of the corrosion products on the coatings at different im­
mersion periods.
2. Experimental methods and procedures
2.1. Materials
All the chemicals obtained from the suppliers were used without any
purification. Epoxy resin (EPIKOTE 828) with an equivalent weight of
184–190 g/eq and viscosity of approximately 12,000–14, 000 at 25 ◦ C
and the low viscosity cycloaliphatic amine (EPI-KURE 3388) as curing
agent (amine value as KOH 260–285 mg/g) were both purchased from
Asachem, Selangor, Malaysia. Acrylic polyol resin, (A) (Product Name
Desmophen A 870 BA) with a viscosity of 3500 ± 700 mPA.s at 23 ◦ C
and a density of 1.09 g/mL at 20 ◦ C was obtained from Synthese,
Malaysia and aliphatic poly-isocyanate resin, designated as NCO (curing
agent), with a viscosity of 250 ± 75 mPA.s at 23 ◦ C and a density of 1.07
g/ cm3 at 20 ◦ C was purchased from Bayer Material Science, Germany.
Hydroxyl-terminated PDMS (HT-PDMS) with a viscosity of 750 cSt and a
density of 0.97 g/mL at 25 ◦ C was purchased from Sigma-Aldrich,
Malaysia. Isophorone diamine (IPDA) was utilized as a cross-linker for
the combined mixtures of acrylic and epoxy resins and PDMS resins. The
hydrophobic graphene nanoplatelets in powder form (PCode: 806668-
25G) composed of carbon (>95 wt %) and oxygen (<2 wt %) and
bulk density of 0.04 g/mL was purchased Sigma-Aldrich, Malaysia. For
all the samples, without any modification, both the host binder and
curing agent were incorporated in the way it was collected.
2.2. Preparation of the graphene-based coatings
Firstly, using a weight ratio of 90:10 (acrylic: epoxy), 9 g of acrylic
resin and 1g of epoxy resin were taken in a beaker after measuring using
a weighing scale. This binder resin composition has been successfully
proven as the best performing combination. Subsequently, 0.5 wt % of
graphene content was then added into the beaker containing the mixed
resins. The experiment was then repeated with the same steps but with
different graphene content (1, 2, 3, 5, and 7 wt %) into the mixed resin
respectively. The mixture in the beaker was then stirred constantly for
15 min at room temperature, between 300 rpm and 400 rpm. A magnetic
stir bar was used to ensure the homogenous blending of mixture. All
apparatus used were initially cleaned with distilled water. The mixture
was then sonicated for an additional 15 min followed by the addition of
IPDA. For instance, the IPDA was calculated based on the amount of
epoxy used (10g of epoxy: 1g of IPDA), therefore, in this approach, 0.1 g
of IPDA was incorporated. The mixture was then further sonicated for 2
min followed by the addition of 1 wt % of PDMS (0.1 g). The mixture was
then stirred again for another 15 min between 300 rpm and 400 rpm at
room temperature. The stoichiometric amount of NCO resin curing
agent was calculated based on, NCO = 2.47∗0.0295
0.196 * amount of acrylic
resin (g), were then added into the mixture. In other words, 3.35 g of the
NCO was incorporated followed by manual stirring of the mixture for
approximately 3 min using a clean glass rod. Finally, using a brush
coating approach, the blended coatings were coated on the front and
back sides of the cold-rolled mild steel substrates, having dimensions of
0.5 mm × 73 mm × 65 mm (thickness × width × length). Before the EIS
tests were performed, the steel panels that were sandblasted according
to the ASTM D609 standard to achieve Sa 2 1/2 surface profile and
cleaned with acetone. Subsequently, at room temperature, the panels
were left to dry for five days. Once the coatings have fully cured and
dried, the thickness at various locations per coated panel were measured
S.S. Ashok Kumar et al. Materials Chemistry and Physics 303 (2023) 127731

using an Elcometer 456 thickness gauge. Furthermore, tabulated in water absorption (Φ) was calculated based on the reported approach
Table 1 are the compositions of all the prepared coating samples along [46]. For instance, it was reported that the coating capacitance and the
with their corresponding designation and the average thickness of dry Φ of the nanocomposite coatings can be calculated by the following
coating film after being applied on the substrate surface. Depicted in formulas [46]:
Fig. 1 are the coated microscope slides (glass) substrates for each cor­
1
responding sample respectively. C= eq. (1)
|Z|0.01 Hz
3. Characterization ( )
log CCot
Φ= eq. (2)
3.1. EIS log ԑH2 O

The corrosion protection performance of the fabricated nano­ Where:

composite coatings was determined by the EIS. Here, a classical three- Φ Is the volume fraction of the absorbed water.
electrode cell with 3.5 wt% NaCl solution was used to conduct these Ct is the coating capacitance at time t
investigations for the entire immersion time of 90 days. Furthermore, Co is the coating capacitance at time t = 0
the electrochemical cell was developed by vertically placing a 2.0 cm ԑH2 O is the dielectric constant of water at 25 ◦ C = ~78.3
inner diameter of polyvinyl chloride (PVC) tube to the coated substrate
surface. Here, the PVC tube was glued appropriately to avoid leaking of 4. Results and discussion
the solution. On the other hand, the uncoated part of the metal substrate
was selected as the working electrode and a platinum electrode and the 4.1. EIS measurement
saturated calomel electrode (SCE) were selected as the counter electrode
and the reference electrode respectively. Gamry PC14G300 potentiostat In order to investigate the influence of graphene nanoparticles on the
(Warminster, PA, USA) with a frequency of 100 kHz to 10 mHz and an anticorrosion performance of the nanocomposite coatings, the EIS tests
amplitude of sinusoidal voltage at 10 mV was used to perform the test. were carried out after the coated substrates were exposed to 3.5 wt%
NaCl solution. Furthermore, this measurement was employed to observe
3.2. FTIR the influence of PDMS in enhancing the electrochemical attribute of the
graphene-based polymer coatings against corrosion. After different im­
The FTIR was conducted to perform the qualitative analysis and to mersion periods, the impedance plots were fitted using two models of
trace the cross-linking process. The ATR-Nicolet iS10 Spectrometer was equivalent circuits as depicted in Fig. 2.
utilized to record the FTIR spectra in the transmittance mode. In addi­ In addition, at 1st day, 60th day and 90th day, the obtained results
tion, an A32-scan data accumulation in the wavenumber of 4000 to 400 were graphically expressed using Bode plots as shown in Figs. 3–5
cm− 1 at a resolution of 4.0 cm− 1 was used to obtain the spectrums. respectively. In this analysis, Model A consisted of solution resistance
(Rs ), coating resistance (Rc ), constant phase element of the coating
3.3. FESEM capacitance (CPEc ), constant phase element of double layer capacitance
(CPEdl ) and the charge transfer resistance (Rct ) respectively. On the other
Purchased from Eindhoven, Netherlands, the FESEM (Quanta FEG hand, Model B which is an extended equivalent circuit of Model A,
450, EDX-OXFORD) equipment was employed to examine the surface consisted of the diffusion resistance (Rdiff ) and the constant phase
morphology and the dispersion state of the graphene nanoparticles element of diffusion capacitance (CPEdiff ) respectively.
within the polymer matrix (free films). Moreover, at different immersion From Fig. 3a, the Bode plot revealed that all the hybrid coating
times, the FESEM micrographs were obtained to examine the coating systems demonstrated high impedance modulus values (|Z|0.01 Hz ) after 1
morphology and to identify the possible formation of corrosion products day of immersion, ranging between 108 to 1010 Ω cm2 . For instance, the
within the polymeric matrix. Before the surface morphology was |Z|0.01 Hz for 0.5, 1, 2, 3 and 5% G were in the range of between 109 to
examined, all the free film samples were coated with platinum by using 1010 Ω, whereas, 7% G had a |Z|0.01 Hz of 108 Ω cm2 respectively. Among
platinum sputter coater (Bio-Rad, Watford, England) to minimize the all the hybrid coating systems, it was observed that the 1% G exhibited
charging effects. the highest |Z|0.01 Hz , approximately 1010 Ω cm2 , whereby the Bode and
Nyquist plot exhibited a straight line with a gradient of − 1 and with one
3.4. Contact angle (CA) and water absorption measurements capacitive loop respectively (Fig. 3c). Furthermore, Holyoake et al. re­
ported that the measured |Z|0.01 Hz can be used as the key for coating
An optical contact angle (OCA) 15 EC apparatus was utilized to
screening [46]. For instance, |Z|0.01 Hz of 104 Ω cm2 demonstrated poor
investigate the surface wettability of the fabricated coating systems. In
corrosion protection, however, as the |Z|0.01 Hz increases from 106 Ω cm2
addition, water droplets, with a volume equal to 5 μL distilled water
were dispensed on the surface of the specimens. On an average of three to 108 Ω cm2 , the protection begins and the barrier properties against
measurements taken on different points on the surface, the CA was corrosion enhances and finally when the |Z|0.01 Hz equals or exceed 1010
evaluated accordingly for each coating system. On the other hand, the Ω cm2 , this indicates that the coating has exhibited excellent corrosion
protection performance respectively [46]. Additionally, from Fig. 3b,
Table 1
the phase angle for 1%, 2%, 3% and 5% G respectively was observed to
Compositions of all the prepared coating samples along with their corresponding be close to 80◦ at high frequency. However, compared to 1% G, the
designation. increase in the phase angle in the lowest frequency range (10− 2 to 100
Hz) was observed for 0.5% G and 7% G, thus, indicating that these
Sample Acrylic Epoxy Graphene Dry coating film
Code resin (g) resin (g) nanoparticles (g) thickness, μm (Avg.) coatings had poor barrier protection ability which resulted the electro­
lyte to penetrate the substrate at the early stage of immersion. This could
0.5% G 9 1 0.05 123
1% G 9 1 0.1 131 be due to the poor dispersion of graphene content within the polymer
2% G 9 1 0.2 176 matrix. However, among these stated coating systems, it was clearly
3% G 9 1 0.3 278 indicated that the 1% G coating system blended well and inhibited the
5% G 9 1 0.5 380 corrosion reaction to initiate and at the same time exhibiting the highest
7% G 9 1 0.7 477
|Z|0.01 Hz in the Bode plot. On the other hand, after 24 h of immersion in

3
S.S. Ashok Kumar et al. Materials Chemistry and Physics 303 (2023) 127731

Fig. 1. The images of the coated microscope slides (glass) substrates for each corresponding sample (0.5%–7% G) respectively.

Fig. 2. Schematic diagram illustrates the models used to fit the impedance plots.

3.5 wt% NaCl, a slightly lower |Z|0.01 Hz in the range of 109 Ω cm2 and
108 Ω cm2 was exhibited by 0.5%, 2%, 3% and 5% G and 7% G
respectively.
From Fig. 3 (c-e), the Nyquist plot exhibited a semi-circle particularly
for 0.5% G coating sample, thus, revealing that the electrolyte had
started to penetrate into the polymer coating, hence, initiating the
corrosion reaction. This could be due to the lack of graphene content
within the polymer matrix to completely cover the entire surface of the
metal substrate. In addition, one capacitive loop was exhibited by 1%,
2%, 3%, 5% and 7% G coating system. Here, it was clearly revealed that
the incorporation of higher loading rates of graphene had resulted in the
enhancement of the anticorrosion performance of the coatings as only a
slight bend was observed at the lower frequency region in the Bode plots
and one semi-circle in the Nyquist plots. Alternatively, OCP, which is
another form of electrochemical method was conducted to evaluate the
corrosion performance of organic coatings. Fig. 3f illustrates the OCP for
all the coatings after 24 h of immersion. Some researchers utilized OCP
measurements data to confirm their results obtained by EIS [47]. For

4
S.S. Ashok Kumar et al.
Fig. 3. The representations of (a) Bode plots, (b) Phase angle plots, (c–e) Nyquist plots and (f) OCP for all the graphene composite coating samples modified with
PDMS after 1 day of immersion.
instance, Gowri et al. reported that the obtained maximum corrosion
resistant specimen exhibited a rise in potential to a more positive value
and the remaining samples exhibited constant potential or became more
negative [48]. In this investigation, similar trends were reported
whereby it was observed that 0.5%, 1%, 3% and 5% G having higher
|Z|0.01 Hz exhibited a more positive OCP, whereas, 2% G and 7% G
exhibited a lower positive OCP approaching toward zero. From all the
above findings, it was proven that the 1% G exhibited the best results
compared to other samples after 24 h of immersion.
In addition, even after 60 days of immersion, as illustrated in Fig. 4a,
the |Z|0.01 Hz for 1% G was observed to be maintained as high as 1010 Ω.
cm2 . Furthermore, the remaining coating systems (0.5%, 2%, 3%, 5%
and 7% G) also did not show any significant change in the Bode plot,
where the |Z|0.01 Hz were approximately maintained in the same range as
the 1st day, as illustrated in Fig. 3a. Here, all the coatings were intact,
and no delamination had occurred. Among all the coating systems, the
1% G exhibited the best corrosion performance, since the Bode plot at
the lower frequency region had no slight bending. As illustrated in
Fig. 4b, at high frequency, the phase angle of 1% G exhibited a value of
90◦ , whereas 3% G and 5% G exhibited a phase angle of close to 80◦ . The
remaining coating systems exhibited a lower phase angle value ranging
between 30◦ to 70◦ , whereby the 0.5% G revealed the lowest phase angle
value at the high frequency region. From these findings, the 1% G
5
Materials Chemistry and Physics 303 (2023) 127731
coating system exhibited the best phase angle mainly due to the ability
to completely fill the coating porosity by dispersing uniformly with the
polymer matrix, hence, resulting to a more compact and effective
coating. On an important note, from Figs. 3a & 4a respectively, the 0.5G
coating system exhibited a slightly different trend in the Bode plot at
higher frequency range compared to the rest of the coating systems.
Similarly, as mentioned above, from Figs. 3b–5b respectively, it was
clearly observed that the 0.5G exhibited the lowest phase angle value at
high frequency. To support this phenomenon, it was reported that the
variation of phase angles may reflect the coating performances [49]. For
instance, at high frequency range, the appeared time constant can be due
to the coating/solution interface, whereas at low frequency range, it
corresponded to a corrosion process that occurred at the metal/coating
interface. This clearly indicated that despite the 0.5G coating system
exhibited high |Z|0.01 Hz values at low frequency range in the Bode plot,
the corrosion had been initiated whereby the corrosive ions have started
to penetrate through the coating interface. Furthermore, in the up­
coming section, the Bode plot trend exhibited by the 0.5G coating sys­
tem are in complete agreement with the results exhibited in Figs. 6a–8a,
where the resistive region was observed to be dominant over the
capacitive region. Therefore, along with the aforementioned description
above, these results indicated the loading rate of 0.5 wt% graphene
nanoparticles were insufficient to completely cover the surface of the
S.S. Ashok Kumar et al.
Fig. 4. The representations of (a) Bode plots, (b) Phase angle plots, (c–e) Nyquist plots and (f) OCP for all the graphene composite coating samples modified with
PDMS after 60 days of immersion.
metal substrate, thus, revealing that the corrosion phenomenon cannot
be prevented over the immersion time in 3.5 wt% NaCl, as confirmed by
the Bode and phase angle plots.
Fig. 4 (c-e) illustrated the Nyquist plots for all the coatings. Here, the
1% G exhibited one capacitive loop and showing the character of one
time constant, thus, revealing it to be the best coating system among
remaining coating samples. These findings revealed the importance of
adding graphene nanoparticles to modify the network structure of the
polymer matrix where the incorporated nano reinforcing agents
contributed in reorganizing the polymeric matrix by the physical in­
teractions due to the presence of the strong Van der Waals which assisted
to close up the pores in the matrix, thus, forcing the penetrated elec­
trolyte to travel a longer distance to reach the metal substrate and lead
to the initiation of the corrosion reaction [50]. In short, no changes were
demonstrated by 1% G over the immersion time period up to 60 days,
and this further implied that the incorporation of 1% G nanoparticles
was sufficient to disperse evenly and uniformly with the polymeric
matrix, thus, resulting in the enhancement of the overall corrosion
performance, and the results here was strongly proved with all previ­
ously reported results [50]. Lastly, Fig. 4f illustrated the OCPs for all the
coating upon 60 days of exposure. It was observed that 1%, 2%, 3% and
5% G exhibited the more positive OCP values, whereas, 0.5% G and 7%
6
Materials Chemistry and Physics 303 (2023) 127731
G exhibited negative values. Overall, the 1% G exhibited the highest
OCP value, indicating that this coating system provided the best corro­
sion barrier performance.
After 90 days of immersion, it was observed that 1% G coating sys­
tem still maintained the highest |Z|0.01 Hz of 1010 Ω cm2 at low-frequency
range compared to the other coating systems (Fig. 5a). Here, it was
concluded that the most pronounced effect of graphene nanoparticles
was revealed when 1 wt% was added into the polymeric matrix. Also, as
mentioned previously, the uniform dispersion of the nanoparticles in the
matrix resulted in the reduction of porosity and zigzagging the diffusion
pathway. On the other hand, the |Z|0.01 Hz for 0.5%, 2%, and 3% were
still observed to be maintained at 109 Ω .cm2 and finally, the |Z|0.01 Hz for
5% G and 7% had no significant changes, maintaining at 108 Ω. cm2 and
107 Ω .cm2 respectively (Fig. 5a). On an important note, it was clearly
observed that any further increase in the weight percentage of graphene
does not significantly improve the corrosion performance. In fact, from
all of the above findings, as mentioned above, an increase in the weight
percentage of graphene beyond 5%–6% might deteriorate the properties
of the coatings [51]. With regards to this statement, up to the 90th day,
the |Z|0.01 Hz were seen to be lowest specifically for the 7% G coating
system, hence, such weight percentage of graphene could possibly result
in the formation of large clusters, whereby the contact among the
S.S. Ashok Kumar et al. Materials Chemistry and Physics 303 (2023) 127731

Fig. 5. The representations of (a) Bode plots, (b) Phase angle plots, (c–e) Nyquist plots and (f) OCP for all the graphene composite coating samples modified with
PDMS after 90 days of immersion.

7
S.S. Ashok Kumar et al.
Fig. 6. Bode plots with f b determination for all the coating systems, 0.5%, 1%, 2%, 3%, 5% and 7% G (in the sequence of a-f) after 24 h of immersion.
graphene nanoparticles and the polymeric matrix could be altered, thus,
resulting their interaction to be narrowed and causing issues associated
with the interfacial adhesion. Moreover, from Table 1, the thickness
variation of each of the coating sample was illustrated. In fact, this
thickness variation of the coating samples contributed to the effect in
EIS, and this phenomenon is also directly related to the composition and
the inclusion of different loading rates of graphene nanoparticles within
the polymeric matrix. As described above, the increment in the loading
rates of graphene nanoparticles resulted the coating thickness to in­
crease, thus resulting in the changes of the EIS results which were mainly
due to the agglomeration and connectivity of the graphene nano­
particles which directly connects the substrate to the electrolytes. In
short, large agglomeration was observed by the 7% G coating system
which resulted in the overall reduction of the corrosion resistance per­
formance [52].
In addition, as illustrated in Fig. 5b, at high frequency, the phase
angle of 1% G % 3% G exhibited a value of 90◦ , whereas 2% G and 5% G
exhibited a phase angle close to 80◦ . The 0.5% G and 7% G exhibited a
lower phase angle value ranging between 40◦ to 75◦ , where the 0.5% G
8
Materials Chemistry and Physics 303 (2023) 127731
revealed the lowest phase angle value at the high frequency region.
From here, it was concluded that the 1% G coating system exhibited the
best phase angle. Furthermore, the observation deduced from the
Nyquist plots, illustrated in Fig. 5 (c-f), showed that after 90 days of
immersion, the 1% G exhibited one capacitive loop and showing the
character of one time constant, thus, revealing it to be the best coating
system among remaining coating samples. On an important note, the
remaining coating systems did not show a two semi-circle trend in both
the Bode and Nyquist plots, thus, confirming that these samples having
the lowest (0.5% G) and highest (7% G) concentration of graphene
nanoparticles still provided a high performance in resistance to corro­
sion. However, the lowest performance of corrosion resistance was
exhibited by 7% G, thus, this coating was unable to provide an effective
barrier against corrosion for a longer-term due to graphene agglomer­
ation [52]. To support this findings, Chang and Liu et al. reported the
impacts of the dispersion of graphene on the coating performance,
whereby, it was observed that the dramatic material degradation
occurred when a higher content of graphene was added (>0.5 wt%) due
to the agglomeration of the nanoparticles [20–22,37,53,54]. However,
S.S. Ashok Kumar et al. Materials Chemistry and Physics 303 (2023) 127731

Fig. 7. Bode plots with f b determination for all the coating systems, 0.5%, 1%, 2%, 3%, 5% and 7% G (in the sequence of a-f) after 60 days of immersion.

Yu et al. revealed that a good barrier performance against corrosion was
still provided when higher content of graphene was utilized [55]. Last
but not the least, the OCPs for all the coatings after 90 days of immersion
were illustrated in Fig. 5g. Here, it was observed that 1%, 2%, 3% and
5% G exhibited the more positive OCP values, whereas, 0.5% G and 7%
G exhibited a border line positive (0 mV) and − 0.1 mV respectively.
Finally, Table 2 illustrates all the recorded |Z|0.01 Hz values for all the
graphene-based coating systems from 1st up to 90th day of immersion,
which were in complete agreement with the explanations provided
above.

9
S.S. Ashok Kumar et al.
Fig. 8. Bode plots with f b determination for all the coating systems, 0.5%, 1%, 2%, 3%, 5% and 7% G (in the sequence of a-f) after 90 days of immersion.
4.2. Breakpoint frequency (f b )
As mentioned previously, as the electrolyte penetrates and reaches
the substrate surface, the corrosion process is initiated as the electrolyte
will have the tendency to settle in the microporous at the coating-
substrate interface. Therefore, the performance at these specific re­
gions/points are considered as a resistive behaviour. Hence, with the
10
Materials Chemistry and Physics 303 (2023) 127731
assistance of the f b values, the areas under the Bode plot can be inves­
tigated and interpreted. For instance, the values of the f b is determined
via the measurement of the Bode phase angle as a function of exposure
time at which the phase angle falls to − 45◦ . In addition, this analysis is
essential to obtain a better understanding on the phenomena of corro­
sion processes that occurs at the coating-substrate interface and its im­
plications for the loss of adhesion and film delamination that result in
S.S. Ashok Kumar et al.
Table 2
The recorded |Z|0.01 Hz values for all the graphene-based coating systems
throughout the immersion time.
Coating system |Z|0.01 Hz values (Ω. cm2 )
1st Day 60th Day 90th Day
0.5%G 3.64 x 10 9
2.89 x 10 9
2.27 x 109
1%G 8.92 x 109 1.55 x 1010 1.75 x 1010
2%G 1.93 x 109 5.26 x 109 6.91 x 109
3%G 2.99 x 109 2.40 x 109 2.77 x 109
5%G 1.26 x 109 6.17 x 108 7.16 x 108
7%G 4.04 x 108 6.55 x 107 5.89 x 107
the degradation of corrosion protection performance. Furthermore,
Fig. 6 (a–f), Fig. 7 (a-f) and Fig. 8 (a-f) respectively illustrates the Bode
plot with f b determination for all the coating systems, 0.5%, 1%, 2%,
3%, 5% and 7% G (in the sequence of a-f) after 1, 60 and 90 days of
immersion. Moreover, separated by the f b borderline, it can be observed
that two characteristics regions have appeared at low-to-high frequency
of the impedance spectra, consisting of capacitive (green) and resistive
(red) regions respectively [56]. Additionally, the damage of the coating
and its lost intact with the metal substrate can be indicated if the area
under the Bode plot is a domain by only resistive region. Firstly, the
0.5% G f b results will be discussed from the first up to the 90th day
followed by the remaining coating systems. From Fig. 6a, it was
observed that both resistive and capacitive areas under the Bode plot
were present after the immersion period of 24 h. However, as the im­
mersion time elapsed and as illustrated in Figs. 7a–8a, the majority area
under the Bode plot was observed to be dominated by the resistive re­
gion, thus, further revealing the poor corrosion protection performance
of the 0.5% G coating system. Secondly, after 24 h, the increase in the
size of capacitive region over the resistive region for the 1% G was also
observed, as depicted in Fig. 6b. Here, a lower f b value was recorded,
whereby smaller resistive regions at the lower frequency range and large
capacitive regions were observed. Interestingly, Figs. 7b and 8b further
revealed that only the capacitive region was present, indicating that the
incorporation of 1% G into the matrix remarkably improved the barrier
properties of the coating. Next, in Fig. 6c, the 2% G showed that the
capacitive region was more dominant compared to the resistive region
after 1 day of immersion. Moreover, after 60 days of immersion, Fig. 7c
illustrated the opposite trend whereby higher f b values and the size of
resistive region significantly increased compared to the capacitive re­
gion. However, after 90 days of immersion, only capacitive region was
observed, as illustrated in Fig. 8c. Furthermore, no significant changes
were observed from 1st up to 90th day of immersion time for the 3% G.
As illustrated in Figs. 6d and 8d, the results were consistent whereby the
size of the capacitive region was relatively larger than the resistive re­
gion. Similarly, for 5% and 7% G respectively, Fig. 6 (e-f) illustrated a
complete capacitive region after 24 h of immersion time. On the other
hand, after 60 and 90 days, the area under the Bode plot exhibited both
resistive and capacitive regions, whereby the size of the capacitive re­
gion was significantly larger, as shown in Fig. 7(e and f) and 8 (e-f). At
this point of time, no further enhancement was observed by increasing
the weight percentage of graphene nanoparticles into the polymer ma­
trix due to tendency of the graphene nanoparticles to agglomerate and
forming large clusters. In addition, as reported in previous research
works, the damage index (DI) method was also employed to understand
the corrosion resistance for the coatings and to quantify the coating
degradation over a wide frequency range, which also exhibited similar
graphs related to the f b values [38,57,58]. For instance, according to the
DI theory, the maintained − 1 slope of the impedance curve implied that
the coating behaved as an intact protective layer, whereby only the
capacitive region had appeared in the plot. On the other hand, the
decrease in the slope of the impedance curve specifically at low fre­
quency zones implied that the degradation of the coating layer has been
initiated, hence, resulting the impedance plot to consist both resistive
11
Materials Chemistry and Physics 303 (2023) 127731
and capacitive region respectively. In other words, a higher DI value
indicated a lesser coating degradation, whereby the plot consisting only
capacitive region or 100% DI value indicated that the coating film
behaved as an intact layer to protect the substrate. Interestingly, the
concept described by the DI method was in complete agreement with all
the illustrated f b graphs. In conclusion, due to the non-significant
changes in the f b values up to throughout the immersion time, the 1%
G coating system exhibited the optimum results compared to the other
coating systems, whereby the coating layer had a remarkable stability to
successfully prevent the penetration of the corrosive agents. These
findings along with the described EIS results above were in agreement
with the previously reported literatures whereby the |Z|0.01 Hz exceeding
107 Ω. cm2 were considered as good corrosion protection coatings [59,
60].
4.3. FTIR
As depicted in Fig. 9, the FTIR spectrometer was utilized to investi­
gate and identify the appearance of the main functional groups in all the
graphene-based binder coatings from 4000 to 400 cm− 1 . Moreover, from
the previous results discussed, the FTIR analysis was conducted for all
coating samples except for 5% and 7% G. The presence of the shifts in
the peak of the functional groups revealed that the cross-linking had
occurred between the resins. In previous studies, it was reported that the
presence of the epoxy ring was indicated at an absorption peak of 915
cm− 1 [61,62]. However, for all samples, the absorption peak was at
approximately 900 cm− 1 corresponded to the C–C band. The NCO was
used as a hardener for all the hybrid coating systems. Previously, the
identical peak for NCO group in the FTIR spectra was reported to be at a
peak of 2280 cm− 1 [63,64]. For instance, NH bond will be formed when
the hardener cures the binder systems. As a result, NCO band should not
appear but NH vibration should be observed in the FTIR spectra. In this
FTIR spectra, no NCO bands were present in the peak range for all the
hybrid coating samples. Furthermore, a new peak appeared at approx­
imately 1517 cm− 1 , which indicated the formation of NH- bond. This
peak was expected to appear due to the crosslinking between the resins
and the curing agent. In addition, Song et al. reported that the graphene
sheet C–– C skeleton vibration corresponded to a peak at 1631 cm− 1 [65].
However, in this FTIR spectra, an obvious peak was observed at
approximately 1680 cm− 1 for all the hybrid coating systems. Further­
more, the broad intense peaks at 3432 cm− 1 and 1163 cm− 1 respectively
corresponded to the stretched vibrations of OH and CO functional
groups at the edges of the graphene [66]. Here, since it is a source of
hydrogen bonds, it can be concluded that the presence of OH functional
group is significantly important in the adhesion and crosslinking process
[63,67]. The symmetric and antisymmetric stretching vibrations of CH2
groups that were observed in the graphene corresponded to the vibra­
tion peaks at approximately 2923 cm− 1 and 2853 cm− 1 respectively. To
support these findings, Spitalsky and Dong et al. reported similar results
in relation to the graphene peaks [68–70]. More importantly, in the FTIR
spectra, the main graphene peaks were observed to be visible without
any shifts. Hence, the confirmation of graphene structure was validated
by the FTIR analysis and formation of crosslinking network among the
components of the coatings.
4.4. FESEM morphology
The FESEM was employed to closely examine the surface
morphology of the graphene-based polymer nanocomposite coating
systems, as shown in Fig. 10 (a-f). Moreover, the distribution of the
particle, surface failure and the nature of the surface can be deduced
from the obtained FESEM representations. In addition, due its large
surface area along with other fascinating properties, it was observed that
the graphene-based polymer coatings possessed much richer interfaces,
hence, resulting more conductive networks to be formed [14].
S.S. Ashok Kumar et al.
Fig. 9. The FTIR spectra of the graphene-based hybrid coatings (0.5%–3% G).
Furthermore, the coating surface wettability which is generally known
to be affected by the surface roughness and microstructure can be
investigated by the obtained surface morphology micrographs. Inter­
estingly, a heterogenous morphology with the increase in the surface
roughness was clearly observed in the micrographs. For instance, the
surface roughness had increased particularly when the loading rates of
graphene nanoparticles increased from 0.5 to 1 wt%. In other words, the
existence of the inter-crosslinking structure of the PDMS with
graphene-based coatings was revealed. Additionally, Yang and Wang
et al. reported that the high surface irregularity was resulted due to the
high tendency of graphene nanoparticles to aggregate in polymeric
matrices [43,44]. Moreover, Liu et al. demonstrated that coatings with
good physical barrier properties have excellent protective properties
and the dispersion state of fillers in composite coatings was significant
on the physical barrier properties of the coatings [71]. Furthermore, the
loading rates of 0.5, 1 and 2 wt% of graphene nanoparticles into the
polymer matrix were observed to dispersed uniformly and no obvious
agglomeration of graphene was found, as illustrated in Fig. 10 (a-c). On
the other hand, the presence of some small holes was observed when 3
wt% of graphene nanoparticles were employed into the polymeric ma­
trix, as illustrated in Fig. 10d. Here, it was indicated that a slight
agglomeration has resulted as a result of incorporating higher content of
graphene nanoparticles. Previously, it was reported that the emergence
of some individual graphene flakes from the surface of the layer can be
clearly observed, hence confirming that the graphene agglomeration
represented an essential source of defects in the coating, whereby this
drawback cannot be avoided specifically when higher content of gra­
phene (e.g., 5 wt% and 7 wt%) as nanofillers were incorporated into the
polymer matrix, as illustrated in Fig. 10 (e-f) [23]. In overall, the 1% G
coating system revealed the best surface morphology in terms of being
evenly dispersed, no cracks or holes, no obvious agglomeration, thus,
confirming the good adhesion properties of the coating.
4.5. CA and water absorption (Φ) of graphene-based coatings
By using the EIS methods, the water absorption or water perme­
ability can be measured which is based on the determination of changes
of the coating capacitance [46]. Also, in the previous years, Ramesh and
12
Materials Chemistry and Physics 303 (2023) 127731
Rau et al. have utilized the capacitance measurements to determine the
water absorption in organic coatings [60,63]. From the results depicted
in Table 2, the coating capacitance and the Φ can be evaluated using
equations (1) and (2) as described in section 3.4. Hence, Table 3 illus­
trates the calculated Φ values for all the coating systems. By referring to
Tables 2 and 3, it can be clearly observed that there is a close correlation
between the |Z|0.01 Hz and the Φ values, thus indicating, that a decrease
in the |Z|0.01 Hz was attributed to the Φ of the coatings. Moreover, the
data obtained further confirmed that the all the coating systems
exhibited small porosity and possessed good barrier properties.
The primary cause of the coating failure is generally due to the water
transportation through the organic coatings. In general, the Φ of the
coatings is divided into two stages [72]. Firstly, the pores and interstitial
sites in the coating are rapidly filled up with water and secondly, the Φ
smoothly reached to a stable saturation level respectively [72]. From
Table 3, it can be observed that the 7G coating system demonstrated the
highest Φ value throughout the immersion time. It is also noteworthy to
mention the reason of higher Φ for 7G, which their graphene contents
are also adequate for isolating water is the presence of more coating
porosity which were attributed to the graphene agglomeration, as
revealed in the FESEM micrographs (section 4.4). Moreover, over the
90th day of immersion, the Φ rates exhibited an upward trend, thus,
indicating that the absorption and saturation of water in the coating was
higher. On the other hand, Table 4 illustrated the CA values for all the
coating samples containing different content of graphene nanoparticles
(0.5–7 wt%). Interestingly, the Φ results were in complete agreement
with CA values. For instance, the Φ rate of the 7G coating system was
observed to exhibited the highest value, while exhibiting the lowest CA
of approximately 81◦ . Hence, these results further indicated that the
formation of film defects had occurred due to the agglomeration of
graphene nanoparticles at the highest loading rate. On the other hand,
for the coating systems containing lower loading rates of graphene
nanoparticles, in this case, 0.5G-3G, it was observed that the Φ exhibited
much lower rates throughout the immersion period [72]. For instance,
the 0.5G, 1 G and 3G respectively exhibited the lowest Φ rates as
compared to 7G coating system. In other words, this decreasing trend
indicated that inclusion of lower loading rates of graphene nanoparticles
(<5 wt%) resulted in excellent barrier properties [72]. Similarly, the
S.S. Ashok Kumar et al. Materials Chemistry and Physics 303 (2023) 127731

Fig. 10. FESEM micrographs of the fracture surface of (a) 0.5% G, (b) 1% G, (c) 2% G, (d) 3% G, (e) 5% G and (f) 7% G based hybrid polymer coating systems.

Table 3 Table 4
The recorded Φ values for all the graphene-based coating systems throughout CA measurements (degrees) for all the graphene-based coating
the immersion time. systems with the incorporation of PDMS.
Coating system Water Absorption (Φ) Coating System ~ CA measurements (◦ )

Immersion time (Days) 0.5G 90

1G 100
60 90
2G 95
0.5G 0.053 0.11 3G 92
1G 0.13 0.16 5G 86
2G 0.23 0.29 7G 83
3G 0.05 0.02
5G 0.16 0.13
7G 0.42 0.44 systems exhibited high |Z|0.01 Hz values. However, the capacitance was
found to be lower particularly for 0.5-3G coating systems which is
comforting the barrier performance of the coatings. As mentioned pre­
results exhibited here were in complete agreement with Table 4,
viously, the highly dispersed graphene nanoparticles within the poly­
whereby the decrease in the Φ rate resulted in a much higher CA value.
meric matrix could provide a torturous path to prevent oxygen, water
For instance, the 0.5G-3G coating systems that exhibited low Φ rates had
and electrolyte to penetrate through the coating [73]. In overall, the
demonstrated higher CA values exceedingly above 90◦ . Among all the
previously discussed EIS results along with Tables 2–4 results clearly
coating systems, the highest CA of approximately 100◦ and the lower Φ
indicated that the coating system containing lower graphene content
rate was exhibited by the 1G coating system. Furthermore, when the Φ
had a better barrier property against corrosion, thus these results were in
increase, the dielectric constant of water increases, thus, leading to a
agreement with the previous research conducted on graphene-based
higher capacitance. From Table 2, it was revealed that all coating

13
S.S. Ashok Kumar et al.
nanocomposite coatings [72,74].
4.6. FESEM morphology at different immersion time
In this approach, after 30 h and 300 h of immersing the coating
samples in 3.5 wt% NaCl solution respectively, the FESEM micrographs
of the graphene-based coating systems were captured to microscopically
investigate their corrosion morphology and the possible formation of
corrosion products within the coatings, as illustrated in Figs. 11 and 12
(a-f) respectively. Firstly, the corrosion morphology after 30 h of im­
mersion will be discussed. The presence of graphene was observed for all
the coating samples with apparently different levels of thickness, as can
be seen from Fig. 11 (a-f). Furthermore, without having strong adhesion
to the metal substrates, it was extensively reported in the previous years
that multilayer graphene coatings can effectively function as inert
Fig. 11. FESEM micrographs illustrates the corrosion morphology of (a) 0.5% G, (b) 1% G, (c) 2% G, (d) 3% G, (e) 5% G and (f) 7% G based polymer nanocomposite
coating systems after 30 h of immersion in 3.5 wt% NaCl solution.
14
Materials Chemistry and Physics 303 (2023) 127731
protective layers, thus preventing diffusion of aqueous solutions [75].
Moreover, with the increment of the loading rates (0.5–7 wt%) of gra­
phene nanoparticles, the presence of folds, wrinkles and edges in the
graphene layers was observed and these findings were in complete
agreement with the previously reported results [75,76]. Last but not the
least, it is also noteworthy to point out that the loading rates of up to 3
wt% of graphene particles exhibited a homogenous and smooth surface,
while at higher loading rates of graphene particles (>5 wt%), the
agglomeration of graphene has started to take place. However, no for­
mation of corrosion products was observed in all the coated samples and
the results exhibited here were in agreement with the results obtained
from the EIS analysis, whereby the |Z|0.01 Hz were all well above 108 Ω
cm2 after 24 h of immersion. In other words, the obtained micrographs
indicated that the graphene coatings acted as a barrier to the underlying
metal surface, thus, decreasing the substrate dissolution in 3.5 wt% NaCl
S.S. Ashok Kumar et al. Materials Chemistry and Physics 303 (2023) 127731

Fig. 12. FESEM micrographs illustrates the corrosion morphology of (a) 0.5% G, (b) 1% G, (c) 2% G, (d) 3% G, (e) 5% G and (f) 7% G based polymer nanocomposite
coating systems after 300 h of immersion in 3.5 wt% NaCl solution. The red dashed arrows indicate the corrosion products (white spots). (For interpretation of the
references to colour in this figure legend, the reader is referred to the Web version of this article.)

solution. Hence, all the above findings confirms that due to its chemical
inertness, impermeability and along with other fascinating properties,
the inclusion of graphene into the polymer coatings substantially results
in high protection of metal surface in corrosive environment containing
chloride ions even over a long exposure time [75].
On the other hand, after 300 h of immersion, the coated samples
exhibited some interesting trends, as illustrated in Fig. 12 (a-f). First and
for most, it is essential to understand that different corrosion degree of
graphene-based coatings coated on metal substrate with a diverse layer
of graphene indicated that there were obvious differences in the diffu­
sion speed of corrosive medium permeated into the graphene coatings.
As illustrated in Fig. 12a, it was observed that the corrosion products
(white spots) had started to form on the surface of the coated sample
(0.5G). Here, it is important to note that despite the corrosion process
had been initiated, however, the presence of the smallest content of
graphene nanoparticles had the ability prevent and prolong the chloride
ions from reaching the substrate. These findings were in complete
agreement with the described EIS results, whereby the exhibited
|Z|0.01 Hz were above 109 Ω cm2 throughout the immersion time. In
addition, as depicted in Fig. 12 (b-d), it was also noteworthy to mention
that there were only a few corrosion products observed on the coated
surface. As expected, the morphology of these coatings was observed to
be smoother and more encouraging since the graphene nanoparticles
filled the pores and sealed the cracks [77]. This clearly indicated that it
was difficult for the corrosive medium to permeate and penetrate
through the coating interface. In other words, as the inclusion of loading
rates of graphene nanoparticles increased up to 3 wt%, it can be
concluded that the lateral diffusion of the corrosive medium was found

15
S.S. Ashok Kumar et al.
to be insurmountable when compared to the 0.5G coating system.
Moreover, the FESEM micrographs revealed the presence of graphene
distributed homogenously on the coated surface, thus, preventing
corrosion. Hence, these findings were again in completed agreement
with the EIS results. However, at much higher loading rates of graphene
nanoparticles (5 and 7 wt%), it was clearly observed that the corrosion
degree was accelerated by high diffusion pathways for corrosive me­
dium, as illustrated in Fig. 12 (e-f). Also, slight corrosion pits and
globular corrosion products were observed on the surface of the coated
samples, whereby the corrosion on the substrate had started to decrease
the binding force between the graphene nanoparticles and the substrate.
As mentioned previously, this was due to the agglomeration and defects
that had occurred when incorporating higher graphene content within
the polymer matrix. All the above findings were in complete agreement
with the previous works related to graphene coatings [78]. Despite such
observations, all the coating systems still demonstrated high |Z|0.01 Hz
even after 300 h of immersion, thus revealing that the nano-interlocking
interface feature associated with the graphene layers endowed them to
exhibit superior anti-corrosive performance.
5. Conclusion
In different weight percentages, the graphene nanoparticles were
added to the acrylic-epoxy polymer coatings along with employment of
PDMS via the intercalation technique. All the coating systems were
evaluated for their potentials as high-performance coatings. The coating
systems were prepared by incorporating 0.5, 1, 2, 3, 5 and 7 wt% of
graphene nanoparticles into the polymer coatings. The EIS and FTIR
appropriately quantified the overall protection performance of the
fabricated hybrid coatings. The FTIR analysis proved that a proper
crosslinked structure of the graphene-based polymer coatings was ach­
ieved. Furthermore, the EIS data of the coating systems revealed that the
hybrid nanocomposite with 1% G offered effective barrier properties for
corrosion mitigation in both short and long-term performances. Despite
having high |Z|0.01 Hz throughout the immersion time, however, with the
increase in the wt.% of graphene nanoparticles, for instance, 3%, 5% and
7% G, some levels of reduction in the corrosion resistance was observed
due to the agglomeration. The detailed data of the f b determination of all
the coating systems were demonstrated, whereby the 1% G exhibited the
most consistent and best result, exhibiting a full capacitive region with
reducing f b values over a period of 90 days. In addition, by incorporating
higher nanofiller loadings into the polymeric matrices, the coating
surface hydrophobicity was observed to decrease due to the aggregation
of the nanofiller. For instance, at loading rates above 3 w.t% graphene
nanoparticles, the CA of the coating surface was observed to decrease,
thus, losing its hydrophobic nature. Moreover, the 1% G coating sample
had the most pronounced effect compared to other coating samples,
whereby it exhibited the highest hydrophobicity with a CA of 100◦ .
Hence, there was clear evidence that the low surface energy of PDMS
resin resulted in the alteration of the wettability of the nanocomposite
coatings towards a more hydrophobic behaviour. With regards to the CA
values, a higher CA resulted in a lower Φ rate, whereby this reduction
indicated that inclusion of lower loading rates of graphene nanoparticles
(<5 wt%) resulted in excellent barrier properties. Additionally, the
FESEM micrographs proved that the sonication process was effective to
develop a good level of nanoparticle dispersion in the polymeric matrix.
However, the amount of nanoparticles in the unit area was observed to
increase with the increment of the loading ratios of the graphene
nanoparticles. Therefore, relatively larger agglomerated nanoparticles
were generated. The most pronounced dispersion state within the hybrid
polymeric matrix was exhibited by the 1% G coating system. Last but not
the least, at different immersion time, the morphology of the coatings
was closely observed to identify the possible formation of corrosion
products within the coatings. The FESEM micrographs compared and
indicated the formation of corrosion products in all the coating systems
after 30 h and 300 h of immersion Overall, a detailed overview of the
16
Materials Chemistry and Physics 303 (2023) 127731
corrosion performance of graphene-based polymeric coating has been
provided in this research, whereby the reinforcement of the graphene
nanofillers within the polymeric matrix displayed promising results in
terms of enhancing the barrier properties and corrosion protection
ability of the coating film, hence, offering the potential for widespread
real-world applications, particularly where corrosion issue is concerned.
CRediT authorship contribution statement
Sachin Sharma Ashok Kumar: He has carried out the experiment,
collected & analysed data, written the manuscript. I.A. Wonnie Ma:
contributed in writing this manuscript and editing. K. Ramesh:
responsible for designing the project, Funding acquisition, He has
checked and revised the manuscript. S. Ramesh: the supervisor of the
student, has monitored the project and revised the manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper
Data availability
Data will be made available on request.
Acknowledgements
We want to thank the Ministry of Higher Education for the Funda­
mental Research Grant Scheme (FRGS/1/2022/STG05/UM/02/15)
awarded to Ramesh Kasi. The authors are extremely thankful to Uni­
versiti Malaya for providing necessary laboratory facilities for this
research and for providing the research facilities and SATU Joint grant
ST031-2021.
References
[1] R.W. Revie, Uhlig’s Corrosion Handbook, vol. 51, John Wiley & Sons, 2011.
[2] M.A. Quraishi, D.S. Chauhan, V.S. Saji, Heterocyclic Organic Corrosion Inhibitors:
Principles and Applications, Elsevier, 2020.
[3] D.S. Chauhan, M. Quraishi, K. Ansari, T.A. Saleh, Graphene and graphene oxide as
new class of materials for corrosion control and protection: present status and
future scenario, Prog. Org. Coating 147 (2020), 105741.
[4] V.S. Sastri, Corrosion Inhibitors: Principles and Applications, vol. 1, Wiley, New
York, 1998.
[5] V.S. Sastri, Green Corrosion Inhibitors: Theory and Practice, John Wiley & Sons,
2012.
[6] A. Cizek, Corrosion inhibitors used in acidizing, Mater. PerformanceUnited States
33 (1) (1994).
[7] W. Frenier, F. Growcock, V. Lopp, Mechanisms of corrosion inhibitors used in
acidizing wells, SPE Prod. Eng. 3 (1988) 584–590, 04.
[8] G. Schmitt, Application of inhibitors for acid media: report prepared for the
European federation of corrosion working party on inhibitors, Br. Corrosion J. 19
(4) (1984) 165–176.
[9] M. Finšgar, J. Jackson, Application of corrosion inhibitors for steels in acidic media
for the oil and gas industry: a review, Corrosion Sci. 86 (2014) 17–41.
[10] M. Finšgar, I. Milošev, Inhibition of copper corrosion by 1, 2, 3-benzotriazole: a
review, Corrosion Sci. 52 (9) (2010) 2737–2749.
[11] A. Kokalj, N. Kovačević, S. Peljhan, M. Finšgar, A. Lesar, I. Milošev, Triazole,
benzotriazole, and naphthotriazole as copper corrosion inhibitors: I. Molecular
electronic and adsorption properties, ChemPhysChem 12 (18) (2011) 3547–3555.
[12] A. Kokalj, S. Peljhan, M. Finsgar, I. Milosev, What determines the inhibition
effectiveness of ATA, BTAH, and BTAOH corrosion inhibitors on copper? J. Am.
Chem. Soc. 132 (46) (2010) 16657–16668.
[13] K. Xhanari, M. Finšgar, Organic corrosion inhibitors for aluminum and its alloys in
chloride and alkaline solutions: a review, Arab. J. Chem. 12 (8) (2019) 4646–4663.
[14] S.S.A. Kumar, S. Bashir, K. Ramesh, S. Ramesh, New perspectives on Graphene/
Graphene oxide based polymer nanocomposites for corrosion applications: the
relevance of the Graphene/Polymer barrier coatings, Prog. Org. Coating 154
(2021), 106215.
[15] S.S.A. Kumar, S. Bashir, K. Ramesh, S. Ramesh, A comprehensive review: super
hydrophobic graphene nanocomposite coatings for underwater and wet
applications to enhance corrosion resistance, FlatChem 31 (2022), 100326.
[16] P.A. Sørensen, S. Kiil, K. Dam-Johansen, C.E. Weinell, Anticorrosive coatings: a
review, J. Coating Technol. Res. 6 (2009) 135–176.
S.S. Ashok Kumar et al.
[17] S.S.A. Kumar, S. Bashir, K. Ramesh, S. Ramesh, Why is graphene an extraordinary
material? A review based on a decade of research, Front. Mater. Sci. 16 (2) (2022),
220603.
[18] S.S.A. Sharma, S. Bashir, R. Kasi, R.T. Subramaniam, The Significance of Graphene
Based Composite Hydrogels as Smart Materials: A Review on the Fabrication,
Properties, and its Applications, FlatChem, 2022, 100352.
[19] A.K. Geim, K.S. Novoselov, The rise of graphene, in: Nanoscience and Technology,
Co-Published with Macmillan Publishers Ltd, UK, 2009, pp. 11–19, https://doi.
org/10.1142/9789814287005_0002.
[20] A. Wirth-Lima, M. Silva, A. Sombra, Comparisons of electrical and optical
properties between graphene and silicene—a review, Chin. Phys. B 27 (2) (2018),
023201.
[21] P. Bøggild, et al., Mapping the electrical properties of large-area graphene, 2D
Mater. 4 (4) (2017), 042003.
[22] Y.-J. Kim, Y. Kim, K. Novoselov, B.H. Hong, Engineering electrical properties of
graphene: chemical approaches, 2D Mater. 2 (4) (2015), 042001.
[23] M. Calovi, S. Rossi, F. Deflorian, S. Dirè, R. Ceccato, Graphene-based reinforcing
filler for double-layer acrylic coatings, Materials 13 (20) (2020) 4499.
[24] R. Ding, et al., A brief review of corrosion protective films and coatings based on
graphene and graphene oxide, J. Alloys Compd. 764 (2018) 1039–1055.
[25] M. Wang, et al., Graphene-armored aluminum foil with enhanced anticorrosion
performance as current collectors for lithium-ion battery, Adv. Mater. 29 (47)
(2017), 1703882.
[26] D. Cai, K. Yusoh, M. Song, The mechanical properties and morphology of a graphite
oxide nanoplatelet/polyurethane composite, Nanotechnology 20 (8) (2009),
085712.
[27] S. Ansari, E.P. Giannelis, Functionalized graphene sheet—poly (vinylidene
fluoride) conductive nanocomposites, J. Polym. Sci., Part B: Polym. Phys. 47 (9)
(2009) 888–897.
[28] F. Chen, J. Ying, Y. Wang, S. Du, Z. Liu, Q. Huang, Effects of graphene content on
the microstructure and properties of copper matrix composites, Carbon 96 (2016)
836–842.
[29] O. Tapasztó, et al., High orientation degree of graphene nanoplatelets in silicon
nitride composites prepared by spark plasma sintering, Ceram. Int. 42 (1) (2016)
1002–1006.
[30] S.S. Ashok Kumar, S. Bashir, K. Ramesh, S. Ramesh, A review on graphene and its
derivatives as the forerunner of the two-dimensional material family for the future,
J. Mater. Sci. 57 (26) (2022) 12236–12278.
[31] D.G. Papageorgiou, I.A. Kinloch, R.J. Young, Mechanical properties of graphene
and graphene-based nanocomposites, Prog. Mater. Sci. 90 (2017) 75–127.
[32] R. Atif, I. Shyha, F. Inam, Mechanical, thermal, and electrical properties of
graphene-epoxy nanocomposites—a review, Polymers 8 (8) (2016) 281.
[33] B. Yu, X. Wang, W. Xing, H. Yang, L. Song, Y. Hu, UV-curable functionalized
graphene oxide/polyurethane acrylate nanocomposite coatings with enhanced
thermal stability and mechanical properties, Ind. Eng. Chem. Res. 51 (45) (2012)
14629–14636.
[34] D. Zhuo, et al., Flame retardancy effects of graphene nanoplatelet/carbon
nanotube hybrid membranes on carbon fiber reinforced epoxy composites,
J. Nanomater. 2013 (2013), 83–83.
[35] R.J. Young, I.A. Kinloch, L. Gong, K.S. Novoselov, The mechanics of graphene
nanocomposites: a review, Compos. Sci. Technol. 72 (12) (2012) 1459–1476.
[36] B. Ramezanzadeh, E. Ghasemi, M. Mahdavian, E. Changizi, M.M. Moghadam,
Covalently-grafted graphene oxide nanosheets to improve barrier and corrosion
protection properties of polyurethane coatings, Carbon 93 (2015) 555–573.
[37] K.-C. Chang, et al., Room-temperature cured hydrophobic epoxy/graphene
composites as corrosion inhibitor for cold-rolled steel, Carbon 66 (2014) 144–153.
[38] B. Ramezanzadeh, S. Niroumandrad, A. Ahmadi, M. Mahdavian, M.M. Moghadam,
Enhancement of barrier and corrosion protection performance of an epoxy coating
through wet transfer of amino functionalized graphene oxide, Corrosion Sci. 103
(2016) 283–304.
[39] N.H. Othman, M.C. Ismail, M. Mustapha, N. Sallih, K.E. Kee, R.A. Jaal, Graphene-
based polymer nanocomposites as barrier coatings for corrosion protection, Prog.
Org. Coating 135 (2019) 82–99.
[40] S.C. Ray, Application and uses of graphene oxide and reduced graphene oxide,
Appl. Graphene Graphene-Oxide Based Nanomater 6 (8) (2015) 39–55.
[41] H.-D. Huang, P.-G. Ren, J. Chen, W.-Q. Zhang, X. Ji, Z.-M. Li, High barrier
graphene oxide nanosheet/poly(vinyl alcohol) nanocomposite films, J. Membr. Sci.
409 (410) (Aug. 2012) 156–163, https://doi.org/10.1016/j.memsci.2012.03.051.
[42] M. Calovi, S. Rossi, F. Deflorian, S. Dirè, R. Ceccato, Effect of functionalized
graphene oxide concentration on the corrosion resistance properties provided by
cataphoretic acrylic coatings, Mater. Chem. Phys. 239 (Jan. 2020) 121984, https://
doi.org/10.1016/j.matchemphys.2019.121984.
[43] S.-Y. Yang, et al., Synergetic effects of graphene platelets and carbon nanotubes on
the mechanical and thermal properties of epoxy composites, Carbon 49 (3) (Mar.
2011) 793–803, https://doi.org/10.1016/j.carbon.2010.10.014.
[44] X. Wang, W. Xing, P. Zhang, L. Song, H. Yang, Y. Hu, Covalent functionalization of
graphene with organosilane and its use as a reinforcement in epoxy composites,
Compos. Sci. Technol. 72 (6) (Mar. 2012) 737–743, https://doi.org/10.1016/j.
compscitech.2012.01.027.
[45] E. Amerio, P. Fabbri, G. Malucelli, M. Messori, M. Sangermano, R. Taurino, Scratch
resistance of nano-silica reinforced acrylic coatings, Prog. Org. Coating 62 (2) (Apr.
2008) 129–133, https://doi.org/10.1016/j.porgcoat.2007.10.003.
[46] K. Holyoake, J. Yuan, Electrochemical impedance spectroscopy measurements of
barrier coatings, Corros. Prev (2000) 2001, 2000.
[47] M. Mahdavian Ahadi, O.C.P. Measurement, A method to determine CPVC, Sci. Iran.
14 (4) (2007).
17
Materials Chemistry and Physics 303 (2023) 127731
[48] S. Gowri, K. Balakrishnan, The effect of the PVC/CPVC ratio on the corrosion
resistance properties of organic coatings, Prog. Org. Coating 23 (4) (May 1994)
363–377, https://doi.org/10.1016/0033-0655(94)87005-5.
[49] T. Monetta, A. Acquesta, F. Bellucci, Graphene/epoxy coating as multifunctional
material for aircraft structures, Aerospace 2 (3) (Jun. 2015) 423–434, https://doi.
org/10.3390/aerospace2030423.
[50] T. Monetta, A. Acquesta, A. Carangelo, F. Bellucci, The effect of graphene on the
protective properties of water-based epoxy coatings on Al2024-T3, Int. J. Corros.
2017 (2017) 1–9, https://doi.org/10.1155/2017/1541267.
[51] N. Nuraje, S.I. Khan, H. Misak, R. Asmatulu, The addition of graphene to polymer
coatings for improved weathering, ISRN Polym. Sci. 2013 (Nov. 2013) 1–8,
https://doi.org/10.1155/2013/514617.
[52] X. Wang, X. Qi, Z. Lin, D. Battocchi, Graphene reinforced composites as protective
coatings for oil and gas pipelines, Nanomaterials 8 (12) (Dec. 2018) 1005, https://
doi.org/10.3390/nano8121005.
[53] S. Liu, L. Gu, H. Zhao, J. Chen, H. Yu, Corrosion resistance of graphene-reinforced
waterborne epoxy coatings, J. Mater. Sci. Technol. 32 (5) (May 2016) 425–431,
https://doi.org/10.1016/j.jmst.2015.12.017.
[54] D. Liu, W. Zhao, S. Liu, Q. Cen, Q. Xue, Comparative tribological and corrosion
resistance properties of epoxy composite coatings reinforced with functionalized
fullerene C60 and graphene, Surf. Coat. Technol. 286 (Jan. 2016) 354–364,
https://doi.org/10.1016/j.surfcoat.2015.12.056.
[55] Y.-H. Yu, Y.-Y. Lin, C.-H. Lin, C.-C. Chan, Y.-C. Huang, High-performance
polystyrene/graphene-based nanocomposites with excellent anti-corrosion
properties, Polym. Chem. 5 (2) (2014) 535–550, https://doi.org/10.1039/
C3PY00825H.
[56] A.A. Javidparvar, R. Naderi, B. Ramezanzadeh, Epoxy-polyamide nanocomposite
coating with graphene oxide as cerium nanocontainer generating effective dual
active/barrier corrosion protection, Compos. B Eng. 172 (Sep. 2019) 363–375,
https://doi.org/10.1016/j.compositesb.2019.05.055.
[57] X. Wang, M. Pearson, H. Pan, M. Li, Z. Zhang, Z. Lin, Nano-modified functional
composite coatings for metallic structures: Part I-Electrochemical and barrier
behavior, Surf. Coat. Technol. 401 (Nov. 2020) 126286, https://doi.org/10.1016/
j.surfcoat.2020.126286.
[58] Sh Ammar, et al., Studies on SiO2-hybrid polymeric nanocomposite coatings with
superior corrosion protection and hydrophobicity, Surf. Coat. Technol. 324 (Sep.
2017) 536–545, https://doi.org/10.1016/j.surfcoat.2017.06.014.
[59] S.R. Rao, Development of an Anti Corrosion Coating Using Organic Resins Hybrid
System/Ramis Rao Subramanian, 2016.
[60] S.R. Rau, B. Vengadaesvaran, K. Ramesh, A.K. Arof, Studies on the adhesion and
corrosion performance of an acrylic-epoxy hybrid coating, J. Adhes. 88 (4–6) (Apr.
2012) 282–293, https://doi.org/10.1080/00218464.2012.659646.
[61] Sh Ammar, K. Ramesh, B. Vengadaesvaran, S. Ramesh, A.K. Arof, Amelioration of
anticorrosion and hydrophobic properties of epoxy/PDMS composite coatings
containing nano ZnO particles, Prog. Org. Coating 92 (Mar. 2016) 54–65, https://
doi.org/10.1016/j.porgcoat.2015.12.007.
[62] P. Bednarczyk, I. Irska, K. Gziut, P. Ossowicz-Rupniewska, Synthesis of epoxy
methacrylate resin and coatings preparation by cationic and radical
photocrosslinking, Molecules 26 (24) (Dec. 2021) 7663, https://doi.org/10.3390/
molecules26247663.
[63] K. Ramesh, N. Nor, S. Ramesh, B. Vengadaesvaran, A. Arof, Studies on
electrochemical properties and FTIR analysis of epoxy polyester hybrid coating
system, Int. J. Electrochem. Sci. 8 (2013) 8422–8432.
[64] A. Castela, A. Simoes, M. Ferreira, EIS evaluation of attached and free polymer
films, Prog. Org. Coating 38 (1) (2000) 1–7.
[65] C. Song, D. Wu, F. Zhang, P. Liu, Q. Lu, X. Feng, Gemini surfactant assisted
synthesis of two-dimensional metal nanoparticles/graphene composites, Chem.
Commun. 48 (15) (2012) 2119, https://doi.org/10.1039/c2cc16890a.
[66] J. Wang, J. Liu, Y. Cai, F. Cheng, Z. Niu, J. Chen, Super P carbon modified lithium
anode for high-performance Li− O 2 batteries, Chemelectrochem 5 (13) (Jul. 2018)
1702–1707, https://doi.org/10.1002/celc.201800289.
[67] G. Li, X. Wang, A. Li, W. Wang, L. Zheng, Fabrication and adhesive properties of
thin organosilane films coated on low carbon steel substrates, Surf. Coat. Technol.
201 (24) (Oct. 2007) 9571–9578, https://doi.org/10.1016/j.surfcoat.2007.04.032.
[68] F. Yue, L. Shuai, Editorial: advances in the structural elucidation and utilization of
lignins, Front. Energy Res. 9 (Jul. 2021) 724825, https://doi.org/10.3389/
fenrg.2021.724825.
[69] H. Dong, M. Li, Y. Jin, Y. Wu, C. Huang, J. Yang, Preparation of graphene-like
porous carbons with enhanced thermal conductivities from lignin nano-particles by
combining hydrothermal carbonization and pyrolysis, Front. Energy Res. 8 (Sep.
2020) 148, https://doi.org/10.3389/fenrg.2020.00148.
[70] Z. Spitalsky, M. Danko, J. Mosnacek, Preparation of functionalized graphene
sheets, Curr. Org. Chem. 15 (8) (Apr. 2011) 1133–1150, https://doi.org/10.2174/
138527211795202988.
[71] S. Liu, et al., Degradation of organic pollutants by a Co3O4-graphite composite
electrode in an electro-Fenton-like system, Chin. Sci. Bull. 58 (19) (Jul. 2013)
2340–2346, https://doi.org/10.1007/s11434-013-5784-4.
[72] C. Chen, et al., Achieving high performance corrosion and wear resistant epoxy
coatings via incorporation of noncovalent functionalized graphene, Carbon 114
(Apr. 2017) 356–366, https://doi.org/10.1016/j.carbon.2016.12.044.
[73] Y. Cui, S.I. Kundalwal, S. Kumar, Gas barrier performance of graphene/polymer
nanocomposites, Carbon 98 (Mar. 2016) 313–333, https://doi.org/10.1016/j.
carbon.2015.11.018.
[74] H. Wang, et al., Polyisocyanate bridged environmental graphene/epoxy
nanocomposite coatings with excellent anticorrosion performance, Prog. Org.
S.S. Ashok Kumar et al.
Coating 153 (Apr. 2021) 106167, https://doi.org/10.1016/j.
porgcoat.2021.106167.
[75] F.Z. Bouanis, P. Moutoussammy, I. Florea, N. Dominique, T. Chaussadent,
D. Pribat, Graphene nanoplatelets coating for corrosion protection of aluminum
substrates, CORROSION 75 (7) (Jul. 2019) 799–808, https://doi.org/10.5006/
2960.
[76] X. Li, et al., Large-area synthesis of high-quality and uniform graphene films on
copper foils, Science 324 (5932) (2009) 1312–1314, Jun, https://doi.org/
10.1126/science.1171245.
18
Materials Chemistry and Physics 303 (2023) 127731
[77] A. Fattah-alhosseini, M. Molaei, M. Nouri, K. Babaei, Review of the role of
graphene and its derivatives in enhancing the performance of plasma electrolytic
oxidation coatings on titanium and its alloys, Appl. Surf. Sci. Adv. 6 (Dec. 2021)
100140, https://doi.org/10.1016/j.apsadv.2021.100140.
[78] Y. Wu, X. Zhu, W. Zhao, Y. Wang, C. Wang, Q. Xue, Corrosion mechanism of
graphene coating with different defect levels, J. Alloys Compd. 777 (Mar. 2019)
135–144, https://doi.org/10.1016/j.jallcom.2018.10.260.