Surface & Coatings Technology 385 (2020) 125418

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Surface & Coatings Technology

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

Cobalt/graphene electrodeposits: Characteristics, tribological behavior, and T

corrosion properties
⁎
Amirhosein Toosinezhad, Mohammad Alinezhadfar, Soheil Mahdavi
Research Center for Advanced Materials, Faculty of Materials Engineering, Sahand University of Technology, Tabriz 5331817634, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: Cobalt/graphene composite coatings were electrodeposited from the baths containing 0.1–0.5 g/L graphene
Co/graphene particles. The effect of graphene particles on structure, morphology, hardness, tribological behavior, and cor-
Electrodeposition rosion of the coatings was studied. The results revealed that the pyramidal morphology of the pure Co film
Composite became smaller at low graphene concentrations, and changed to needle-shaped at the high concentrations. The
Tribology
presence of graphene in the composite films resulted in the reduction of the cobalt crystallite size and thereby
Corrosion
increased the hardness of the coatings. The hardness of Co/0.2 g/L graphene composite coating was 530 Hv that
was about 1.6 times higher than the pure Co film. The composite coatings also had better tribological behavior
than the steel substrate and the Co film. The lowest volume loss achieved in a composite coating deposited from
a bath with 0.2 g/L graphene particles. The most corrosion resistance samples were those electrodeposited from
baths with 0.2–0.4 g/L graphene particles. The corrosion current density of these samples in 3.5 wt% NaCl
solution was < 1 μA/cm2.

1. Introduction
Cobalt is a hard metal with suitable electrical and magnetic prop-
erties, which is used in the rechargeable batteries, or as catalysts in the
petroleum and chemical industries, along with the corrosion and wear-
resistant products [1–4]. In the last three decades, 70% of the cobalt-
containing products in the world have been used as the coating [4].
Electrodeposition is one of the economical and straightforward ways to
deposit these coatings. The mechanical properties and corrosion beha-
vior of the obtained electrodeposits can be improved by the in-
corporation of the hard particles [5–9]. Arai et al. [10] studied the
tribological properties of Co and Co/MWCNT coatings. Examination of
the wear path of the samples showed that in the composite samples, due
to the reduced contact area of the alumina pin with the coating surface,
the path width was narrow, and the surface scratches were dis-
continuous. The MWCNT walls acted as a lubricant at the start of the
test and reduced the coefficient of friction and weight loss of the
composite specimens. Liu et al. [11] added the graphene oxide nano-
particles to the cobalt coatings and investigated their wear and corro-
sion behavior. The addition of these nanoparticles to the coatings cre-
ated a lubricating property, which reduced the coefficient of friction.
The presence of graphene oxide nanoparticles also resulted in grain
refinement and increased hardness, thereby the wear resistance of the
coatings was improved comparing with the cobalt films. The corrosion
behavior of these coatings also enhanced due to the presence of gra-
phene oxide, which was embedded in the crevices, gaps, and micro-
holes of the films and prevented the corrosive medium from penetrating
the coating.
In spite of research works on different cobalt-based composite films,
the lack of studies on Co/graphene electrodeposits is pronounced.
Graphene is one of the carbon allotropes, which is considered to be one
of the best options for enhancing the properties of the coatings.
Excellent mechanical properties, high wear and corrosion resistance, as
well as its use as a solid-lubricant, are some of the desirable features of
graphene [12,13]. The findings show that the incorporation of gra-
phene particles reduces the coefficient of friction and enhances corro-
sion resistance [14–16].
In this study, the electrodeposition technique with the direct current
was used to attain Co/graphene composite coatings using different
percentages of graphene particles. The purpose of this study was to
investigate the morphology, structure, and tribological behavior of the
coatings. Considering the importance of corrosion in different industrial
applications, the corrosion resistance of the coatings was examined and
compared with the corrosion behavior of the pure cobalt and the St37
substrate.

⁎
Corresponding author.
E-mail address: mahdavi@sut.ac.ir (S. Mahdavi).

https://doi.org/10.1016/j.surfcoat.2020.125418
Received 4 December 2019; Received in revised form 14 January 2020; Accepted 25 January 2020
Available online 27 January 2020
0257-8972/ © 2020 Elsevier B.V. All rights reserved.
A. Toosinezhad, et al. Surface & Coatings Technology 385 (2020) 125418

Table 1 Table 2
Bath composition and electrodeposition operating conditions. The wear tests conditions.
CoSO4.7H2O 200 g/L Sliding speed 0.1 m/s, 137 rpm
Na2SO4 100 g/L
H3BO3 50 g/L Load 5N
SDS 0.1 g/L Sliding distances 300 m
Graphene particles 0.1, 0.2, 0.3, 0.4 and 0.5 g/L Testing temperature Room temperature
pH 3 ± 0.1
Current density 83 mA/dm2
Stirring speed 180 rpm around 64 HRC were chosen as the counter-body. Before and after the
Temperature 45 °C
Electrodeposition time 30 min
tests, the samples were ultrasonically washed with acetone for 1 min.
After drying with hot compressed air, they were weighed by using a
Sartorius CPA224S analytical balance with the resolution of 0.1 mg.
2. Material and methods The coefficient of friction (COF) was also measured during the tests.
The operating parameters are listed in Table 2.
2.1. Preparation of the substrate
2.5. Corrosion tests
Samples of St37 steel plates with dimensions of 30 × 30 × 2 mm3
were selected as the cathode. To prepare the surface of the samples, The corrosion experiments were performed in a three-electrode cell,
abrasion with emery papers was performed from 80 to 1200 grit. Then, where a platinum plate (1 cm2), an Ag/AgCl (3 M KCl) electrode, and
the substrates were ultrasonically cleaned in an acetone bath for 5 min. the specimens (with a bare area of 1 cm2) were the counter, reference,
Later, they were degreased in a 20% NaOH solution at 75 °C for 15 min, and working electrodes, respectively. All the tests were performed in
followed by deionized water cleaning. Finally, the surface activation 3.5 wt% NaCl solution at the ambient temperature through an elec-
was carried out in an 18% HCl solution for 45 s. trochemical workstation (WonATech Zive SP2). Before the electro-
chemical experiments, the specimens were placed in the solution for
2.2. Bath composition and deposition conditions 20 min. The electrochemical impedance spectroscopy (EIS) tests were
conducted at the open circuit potential with the amplitude fluctuation
The bath composition and the deposition conditions are shown in of 10 mV, and in the frequency range of 100 kHz to 10 mHz. The po-
Table 1. Analytical grade chemical components were provided and tentiodynamic polarization tests were done in the range of −250 to
utilized to prepare the deposition electrolytes. The pH was adjusted by 500 mV relative to the open circuit potential with a scanning rate of
adding 1 M sulfuric acid or 1 M sodium hydroxide. For developing the 1 mV/s.
composite coatings, different concentrations of the graphene particles
(Sigma-Aldrich with CAS number of 7782-42-5) were added to the
baths as follows: Initially, a given content of these particles was mixed 3. Results and discussion
in a solution of distilled water and 0.1 g/L SDS. The suspension was
stirred at 250 rpm for 90 min, and then it was placed in an ultrasonic 3.1. Structure of the coatings
bath at room temperature for 15 min. The stirring and ultrasonic
treatment were repeated three times before adding the suspension to XRD pattern of the graphene particles in Fig. 1 shows a (002) sharp
the main bath. peak at 2θ = 26.83° corresponding to a d-spacing of 0.334 nm, which is
close to the graphite d-spacing. Reflection of this sharp peak indicates a
crystalline structure for graphene particles and also confirms that the
2.3. Characterization
graphene particles are not in the oxidative state. This was also corro-
borated by Gutić et al. [18], who investigated the XRD patterns of
The morphology and cross-sectional area of the electrodeposited
graphene particles. The observed peak at 55.6° in the XRD pattern is
coatings were inspected by the scanning electron microscopes (Cam
assigned to the graphite (004) plane, confirming that some of the gra-
Scan MN2340 and TESCAN Mira 3 FE-SEM). The structure of the
phite layers are not entirely separated [19].
coatings was examined using X-ray diffraction (XRD) technique. A
Fig. 2 shows the XRD patterns of pure Co and Co/graphene coatings.
Bruker D8 Advance diffractometer with Cu Kα (λ = 1.542 Å) and step
The hexagonal close-packed (hcp) structure of Co does not change with
size of 0.02° was used for this purpose. The Scherrer equation was used
the incorporation of graphene particles, and all the coatings have hcp
for calculating the crystallite size of the electrodeposits. Moreover, the
structure. However, the peak indicating (100) crystallographic plane is
relative texture coefficient (RTC) values were calculated by using Eq.
only present in the patterns of the composite films depositing from
(1) [8,17].
I(hkl) /I0 (hkl)
RTChkl = × 100 (%)
∑ I(hkl) /I0 (hkl) (1)

where I(hkl) and I0(hkl)

are the (hkl) peaks intensities related to the XRD
patterns of the coatings and the standard diffraction pattern of the
cobalt powder (96–151-2502), respectively.

2.4. Microhardness and wear tests

The microhardness tests were performed by using a Vickers micro-

hardness testing machine (MDPEL-M400GL) under the load of 100 g for
20 s. The average amount of at least five measurements on all over the
coatings was reported as the final hardness value.
The wear tests were conducted using a pin-on-disc tribometer. The
AISI52100 steel pins with a diameter of 5 mm and microhardness of Fig. 1. XRD pattern of purchased graphene particles.

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A. Toosinezhad, et al. Surface & Coatings Technology 385 (2020) 125418

Fig. 2. XRD patterns of pure cobalt and cobalt-graphene composite coatings.

Fig. 3. Cathodic polarization curves for cobalt electrodeposition bath with/
Table 3 without the addition of graphene particles.
Calculated RTC and crystallite size based on XRD patterns.
Sample RTC(110) RTC(100) Crystallite size (nm)

Co 100 0 30
Co/0.1 g/L G 100 0 26
Co/0.2 g/L G 100 0 17
Co/0.3 g/L G 96 4 21
Co/0.4 g/L G 91 9 23
Co/0.5 g/L G 73 27 23

baths with > 0.3 g/L graphene particles. For further investigations, the
RTC(hkl) values and the average crystallite size of the coatings are
presented in Table 3. Adding the graphene particles to the bath up to
0.2 g/L does not affect the RTC of the coatings. When the graphene
concentration exceeds 0.3 g/L, the RTC(100) increases, indicating a
variation of crystallographic orientation. The change of RTC values can
be due to the formation of the new nucleation sites by the incorporation
of graphene particles and deposition of metal on the surface of them
[16].
The crystallite size is affected by the co-deposition of graphene
particles (Table 3). The effect of low concentration (0.1 g/L) of these
particles on crystallite size is negligible. The smallest crystallite size of
about 17 nm is obtained by raising the graphene concentration to 0.2 g/
L. These particles act as a barrier against the excessive growth of cobalt
crystallites and reduce the final crystallite size. Moreover, the adsorp-
tion of graphene sheets on the cathode surface provides the new nu-
cleation sites. The nucleation in new locations also results in grain re-
finement [11,20].
As graphene is a conductive material [21], its co-deposition may
increase the active surface area, where the reduction reactions have
occurred. In this case, two factors should be considered. First, the
growth of the surface area at which both the metal ion and hydrogen
reduction reactions arise. Second, decrement of the applied over-
potential or the real current density (as the applied current density was
constant), as shown in Fig. 3. It seems that the effect of the first factor in
raising the released hydrogen is more pronounced than the influence of
the second one in reducing the hydrogen reduction rate. At high con-
centrations of graphene in the bath, the increment of hydrogen reduc-
tion enhances the pH near the cathode surface, as well as the prob-
ability of formation of the hydroxide compounds [17,22,23]. The
creation of hydroxide compounds can be another reason for RTC
changes with the co-deposition of graphene (Table 3). However, de-
crement of the overpotential decreases the nucleation rate of metal. It
increases the crystallite size [24,25], as can be observed in Table 3 for
high concentrations of the graphene in the bath.
Fig. 4. SEM image from the surface of pure cobalt coating.
3.2. Surface morphology
The morphology of the Co film is shown in Fig. 4. The surface is
relatively uniform, containing pyramidal grains. This morphology may
be due to the preferential growth of the coating in the [110] direction
(Fig. 2 and Table 3). Other researchers also report similar results under
the same deposition conditions [11,26]. It should be noted that the
average thickness of the coatings was about 50 μm.
SEM micrographs from the surface of the composite coatings de-
posited from the baths containing 0.1–0.3 g/L graphene are exhibited in
Fig. 5a-c. The morphology of pure cobalt does not change with the co-
deposition of particles, which is consistent with the XRD results.
However, the surface protrusions become smaller, and the graphene
particles can be observed on the surface of the composite films. The
high carbon percentage in the EDS analysis result also confirms the
presence of graphene particles on the surface (Fig. 5d). The inset image
in Fig. 5b shows that the graphene particles have relatively large di-
mensions and a low transparency level. The higher the number of layers
of graphene, the thicker the sheets become, and their transparency level
gets lower [21].
The suitable distribution of the graphene particles within the com-
posite coatings is evident in the cross-sectional image in Fig. 6. The
relatively large dimensions of the graphene particles with a length of
several micrometers are also observable in this micrograph. However,
the particles are thin and composed of the nano-sheets, as it is clear in

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A. Toosinezhad, et al.
Fig. 5. (a–c) SEM images from surface of the Co/graphene composite coatings electrodeposited from the baths with (a) 0.1, (b) 0.2, and (c) 0.3 g/L graphene
particles. (d) EDS analysis from the specified region in (b).
the inset image in Fig. 6b. The thickness of each sheet in a graphene
particle is approximately 10 nm.
As shown in Fig. 7, the morphology of the coatings significantly
changes at high concentrations of graphene in the bath. Graphene is
readily adsorbed on the cathode surface due to its high surface ad-
sorption property and forms the new nucleation sites through the sur-
face activation [27]. Therefore, a new peak defining the (100) cobalt
plane is appeared in the XRD patterns (Fig. 2), and the morphology is
changed. The pyramidal grained have almost been removed from the
surface in the presence of 0.4 g/L graphene particles in the bath
(Fig. 7a). The negligible formation of needles can also be observed on
the surface of this coating. Increment of the graphene concentration of
the bath to 0.5 g/L completely changes the surface morphology to the
needle-shaped (Fig. 7b).
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Surface & Coatings Technology 385 (2020) 125418
3.3. Microhardness and wear behavior
The microhardness of the coatings and the substrate is represented
in Table 4. The coatings have higher hardness than the substrate. The
hardness of pure Co is about 83% higher than the steel substrate. The
composite coatings exhibit even higher hardness compared with the
pure Co film. However, after an ascending trend of the hardness at first
(up to 0.2 g/L), the hardness starts to decrease as the concentration of
graphene particles increases to 0.5 g/L. The highest hardness obtained
in the coating deposited from a bath containing 0.2 g/L graphene
particles. The hardness of this sample is about 1.6 times higher than
that of the pure Co coating.
Distribution of graphene particles in the cobalt matrix reduces the
movement of dislocations, which results in the prevention of plastic
A. Toosinezhad, et al. Surface & Coatings Technology 385 (2020) 125418

Table 4
The average coefficient of friction, volume loss, and microhardness of the
coatings.
Sample COF Volume loss (mm3) Microhardness (Hv)

St37 0.87 0.28 180 ± 5

Co 0.8 0.11 330 ± 5
Co/0.1 g/L G 0.57 0.04 495 ± 5
Co/0.2 g/L G 0.6 0.02 530 ± 5
Co/0.3 g/L G 0.65 0.05 430 ± 5
Co/0.4 g/L G 0.72 0.07 410 ± 5
Co/0.5 g/L G 0.7 0.08 385 ± 5

affecting the coefficient of friction is the real contact area. As the

Fig. 6. SEM micrograph from a cross-section of Co/graphene composite coating
electrodeposited from a bath with 0.2 g/L graphene.
flow and enhanced microhardness [28]. The small crystallite size of the
composite coatings (Table 3) can be another reason for their high mi-
crohardness. However, the inhomogeneous distribution and agglom-
eration of graphene platelets at high concentrations of graphene in the
bath (> 0.2 g/L) decrease the hardness of the coatings.
The volume loss and the average coefficient of friction values are
also reported in Table 4. The volume loss values are following with the
measured hardness. Generally, the coatings display better wear re-
sistance compared to the substrate. The composite coating deposited
from a bath containing 0.2 g/L graphene has the lowest volume loss
among the other samples. The volume loss of this film is 5.5 times
smaller than the pure Co electrodeposit. Based on Archard's theory, the
volume loss is inversely proportional to the hardness [29]. As the
hardness decreases with raising the graphene concentration of the bath
to > 0.2 g/L, the volume loss of the resultant coatings increases. The
morphological variations from pyramidal to needle-shaped can be an-
other reason for the observed volume loss results [30].
The coefficient of friction of the pure cobalt coating is lower than
that of the substrate. Likewise, composite coatings exhibit less coeffi-
cient of friction values than the pure Co, which is in accordance with
the results of microhardness and volume loss. One of the factors
contact area of the pin with the sample surface rises, the friction
coefficient increases as well. Due to the lower hardness of the steel
substrate and the cobalt coating compared to the composite specimens,
the contact area in these specimens is higher, and the coefficient of
friction is higher too [31]. Moreover, the graphene particles may act as
a solid lubricant and reduce the coefficient of friction [12]. Among the
composite specimens, the samples obtained from the baths with low
concentrations of graphene (0.1–0.3 g/L) have a lower friction coeffi-
cient, due to their higher hardness, pyramidal morphology, and pre-
sumably better distribution of the graphene particles.
SEM images in Fig. 8 illustrate the worn surface of the steel sub-
strate. The grooves along the wear path confirming the abrasive wear
mechanism in this specimen. The deformed areas can also be detected
on the worn surface (as indicated by circles in this figure), which are a
result of the plastic deformation of the detached wear debris by the
steel pin. These areas are darker than the other places on the worn
surface in the backscattered electron micrograph (Fig. 8b), indicating
the partial oxidation of the detached debris due to the increment of the
temperature during the sliding.
The SEM images from the worn surfaces of the pure cobalt and also
composite coatings are exhibited in Fig. 9. Comparing this figure with
Fig. 8, the coatings have a narrower wear path than the substrate, and
the wear grooves have been almost disappeared, confirming better wear
behavior of the electrodeposits than the substrate. However, by ex-
amining through higher magnification (the inset image in Fig. 9a), it is
observed that the shallow grooves were still present on the worn sur-
face, which is an indication of the mild abrasion as the dominant wear
mechanism.
The wear path width decreases with the incorporation of graphene
particles within the Co matrix. There are two reasons for such an im-
provement in the tribological behavior of the composite coatings. First,
graphene reduces the load intensity through its network structure and
fabrication of a protective tribological layer [32]. Second, as mentioned

Fig. 7. SEM image of the composite coatings obtained from the baths containing (a) 0.4, and (b) 0.5 g/L graphene.

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A. Toosinezhad, et al. Surface & Coatings Technology 385 (2020) 125418

Fig. 8. (a) Secondary and (b) backscattered SEM images from the wear path of the steel substrate.

earlier, as hardness gets higher, the volume loss of the composite
coatings decreases, which results in a reduced depth of grooves (the
inset image in Fig. 9c) and narrower wear path. However, at high
concentrations of graphene (Fig. 9e and f), the width of the wear path is
increased again. This increment is because of the inappropriate dis-
tribution and agglomeration of graphene sheets in the matrix, which
reduces the mechanical properties of the composite coatings. Mechan-
ical properties have a key role on the tribological behavior of the
samples. Hence, the higher percentages of graphene reduce the me-
chanical properties and, consequently, tribological behavior of the
coatings [33].
3.4. Corrosion
The polarization diagrams of cobalt and cobalt/graphene coatings
with different amounts of graphene particles, as well as the steel sub-
strate, are presented in Fig. 10. Also, the numerical information cor-
responding to these curves reported in Table 5. All of the coatings have
a more noble corrosion potential and a significantly lower corrosion
current density than the substrate, which indicates an improved cor-
rosion resistance.
All the coated samples exhibit almost identical corrosion potentials.
However, the corrosion current densities of the composite coatings are
smaller than the cobalt film. The corrosion current densities of the
coatings deposited from baths with 0.2–0.4 g/L graphene particles are
approximately 8 times lower than that of the pure Co deposit. The

Fig. 9. SEM images form the wear path of (a) Pure Co, (b) Co/0.1 g/L G, (c) Co/0.2 g/L G, (d) Co/0.3 g/L G, (e) Co/0.4 g/L G, (f) Co/0.5 g/L G coatings.

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A. Toosinezhad, et al. Surface & Coatings Technology 385 (2020) 125418

Fig. 10. The polarization curves of the cobalt and cobalt graphene composite coatings.

Table 5 plots (Fig. 11), plus the existence of one slope in Bode diagrams
The calculated electrochemical parameters of different samples. (Fig. 12a) and one peak in Bode-phase curves (Fig. 12b) confirm there is
Sample Ecorr icorr βa βc only one time constant in the equivalent electrical circuit [34,35]. A
(V vs Ag/AgCl) (μA cm−2) (mV decade−1) (mV decade−1) similar equivalent circuit has been proposed by other authors [11]. In
the equivalent circuit, Rs, Rp, and CPE are the solution resistance, po-
St37 −505 21.0 100 293 larization resistance, and a constant phase element, respectively. The
Co −408 7.0 182 245
Co-0.1 g/L G −398 2.5 158 221
CPE is used instead of a pure capacitor for more precise fitting [34,36].
Co-0.2 g/L G −391 0.8 136 202 The impedance of CPE is defined as:
Co-0.3 g/L G −400 0.9 106 219
1
Co-0.4 g/L G −394 0.8 191 239 ZCPE =
Co-0.5 g/L G −402 1.3 140 256 (jω) nY0 (4)

where in this equation, ω is the angular frequency, Y0 is the general

graphene nano-sheets, incorporated into the cobalt coating, create the
corrosion-resistant layers throughout the deposited film and block the
penetration of corrosive ions into the coating. These particles also de-
crease the metallic area in contact with the corrosive solution.
However, the morphological changes and agglomeration of the gra-
phene nano-sheets may increase the porosity of the coatings and cause
an increase in the corrosion current density at the high concentrations
of the particles in the bath [15].
The Nyquist and Bode plots are shown in Figs. 11 and 12, respec-
tively. The electrical circuit inserted in Fig. 11 was employed to fit the
resulted curves. The existence of one capacitive loop in the Nyquist
admittance function, and n is an empirical exponent of the CPE which
0 ≤ n ≤ 1 (n = απ/2, α is the phase angle constant). If n = 1, the
interface has pure capacitive behavior, and if n = 0, the interface be-
haves as a pure resistance. In general, the magnitude of α illuminates
the Nyquist plot depression, surface roughness, and deviation from pure
capacitor [34,35,37,38]. Using the mentioned parameters, the calcu-
lation of double-layer capacitance is resulted by the presented equation
[39,40]:
C = Y10− α × R (1 − α)/α
p (5)
The calculated equivalent electrical circuit components are listed in

Fig. 11. The Nyquist plots of the samples and the used electrical equivalent circuit to fit the experimental data.

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A. Toosinezhad, et al. Surface & Coatings Technology 385 (2020) 125418

Fig. 12. (a) Bode, and (b) Bode-phase plots of different samples.

Table 6 from a bath with 0.1 g/L graphene particles. However, the other
Calculated values for the proposed components in the equivalent circuit. composite coatings have smaller capacitance than the pure cobalt. The
Sample RS (Ω RP (Ω cm2) Y0 (μΩ−1 sn α C (μF cm−2) capacitance of the composite coatings slightly increases with raising the
cm2) cm−2) graphene concentration to > 0.2 g/L. The observed trend is a result of
two competing factors. First, the morphological changes (refinement of
St37 9.4 733 619.9 0.77 272.9
the cobalt pyramidal morphology at low graphene concentrations, and
Co 10.5 4675 69.5 0.82 24.8
Co-0.1 g/L G 21.4 13,835 55.6 0.68 39.4
variation of morphology to needle-shaped at high concentrations), that
Co-0.2 g/L G 18.1 34,971 9.6 0.75 2.9 increases the active surface area. Second, co-deposition of graphene
Co-0.3 g/L G 19.1 28,533 10.8 0.80 3.5 nano-sheets and their presence on the surface, which reduces the active
Co-0.4 g/L G 16.8 31,010 11.5 0.77 3.9 area.
Co-0.5 g/L G 20.6 19,986 15.0 0.82 5.0

Table 6. The composite coatings, electrodeposited from baths with
0.2–0.4 g/L graphene particles, have the highest Rp between the sam-
ples. The resistance of these coatings is considerably higher than the
St37 and the pure Co film. These results are consistent with the po-
larization outcomes. It can be concluded that adding the proper
amounts of the graphene nano-sheets to the electrodeposition bath
improves the corrosion resistance of the coatings. This improvement
can be due to the closure of pores, which prohibits the entry of the
corrosive ions (such as Cl−) [11,15].
By comparing the double layer capacitance values, it can be con-
cluded that the corrosion reactions have occurred on a large portion of
the substrate when it is compared to the coatings. The pure Co film had
lower capacitance in comparison with the composite coating obtained
4. Conclusions
The results of this study can be summarized as follows:
1) The incorporation of graphene particles did not alter the hexagonal
close-packed (hcp) structure of cobalt coatings. However, the cobalt
crystallographic plane of (100) appeared in the XRD patterns by
adding over 0.3 g/L graphene particles.
2) By adding graphene particles, the coarse pyramidal morphology of
the pure cobalt coating became finer and eventually changed to the
needle-shaped.
3) The microhardness of optimum composite coating (Co/0.2 g/L
graphene) was 1.6 and 2.9 times higher than the pure Co coating
and the steel substrate, respectively.
4) The composite coating deposited from a bath with 0.2 g/L graphene

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A. Toosinezhad, et al.
exhibited the lowest volume loss (about 14 and 5.5 times less than
the St37 and pure Co coating, respectively) between the specimens.
The abrasion was the primary wear mechanism in all the samples.
5) The composite films electrodeposited from the baths with 0.2–0.4 g/
L graphene particles had the highest corrosion resistance with a
corrosion current density of below 1 μA/cm2.
CRediT authorship contribution statement
Amirhosein Toosinezhad: Methodology, Investigation,
Visualization, Writing - original draft. Mohammad Alinezhadfar:
Formal analysis, Writing - review & editing. Soheil Mahdavi:
Conceptualization, Methodology, Resources, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
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