Progress in Organic Coatings 179 (2023) 107517

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Corrosion, electrical and thermal behaviour of graphene modified polyester

powder coatings
Francesco Andreatta a, *, Alfredo Rondinella a, Matteo Zanocco a, Giovanni Capurso a,
Roberto Vendramin b, Alessandro Guarino b, Lorenzo Fedrizzi a
a
University of Udine, Polytechnic department of engineering and architecture, Via del Cotonificio 108, 33100 Udine, Italy
b
PLT GmbH, A-9065 Ebenthal in Kärnten, Miegererstrasse 40, Austria

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

Keywords: This work investigates polyester powder coatings containing graphene on aluminium alloy AA6060. The coatings
Powder coatings were developed with a multifunctional approach in order to combine efficient barrier properties and high
Polyester resin electrical and thermal conductivity. Graphene contents up to 10 wt% were introduced in the composite powder
Graphene
coatings. The barrier properties were investigated by means of electrochemical impedance spectroscopy (EIS) in
Barrier properties
0.1 M NaCl solution. This technique was also employed to obtain information about the electrical parameters of
Electrical conductivity
Thermal conductivity the coatings. Although barrier properties remain high over immersion times up to 35 days, a strong increase of
coating capacitance and a decrease of coating resistance were observed by EIS for the coatings with graphene
content above 1 wt%. Impedance data were interpreted on the base of the electrical percolation theory in order
to correlate the increase of capacitance and the decrease of the resistance to the existence of graphene-rich
agglomerates in the composites coatings. Moreover, the thermal behaviour of the composite powder coatings
was preliminarily evaluated indicating that the introduction of graphene can improve heat dissipation.

1. Introduction
Graphene and its derivatives are well-established anti-corrosion ad­
ditives for organic coatings [1–6]. This is due to the peculiar two
dimensional structure of graphene with high aspect ratio and flexibility
that enables its use as an efficient barrier for liquids and gases [7–9].
Indeed, defect-free graphene has the ability to impede diffusion of gases
and liquids through its ultrathin two dimensional structure. One of the
strategies to develop an efficient physical barrier is the preparation of a
graphene/polymer nanocomposite by physical or chemical mixing the
graphene with a polymer (matrix). Different graphene derivatives can be
employed including graphene oxide, reduced graphene oxide and
functionalized graphene oxide [1]. The graphene and its derivatives can
function as a filler in order to block diffusion of liquids and gasses trough
the polymeric matrix. This is based on the formation of a highly tortuous
path for the diffusion through the polymer nanocomposite [5,7]. The
efficiency of the barrier mainly depends on the size of the graphene
additive, its degree of dispersion and orientation in the polymeric ma­
trix. On the other hand, the marked tendency for self-agglomeration of
graphene and its derivatives is a critical factor for the formation of an
efficient barrier [10]. Indeed, this can reduce the tortuosity of the path
for diffusion of species with a negative effect on the barrier properties of
the nanocomposite [7].
The properties of graphene and its derivatives have been exploited to
improve the barrier effect of different organic coatings. Li et al. [2]
investigated the anti-corrosive behaviour of graphene oxide, reduced
graphene oxide and functionalized graphene in a waterborne poly­
urethane matrix. It was shown that 0.2 wt% of graphene oxide could be
uniformly dispersed in the polyurethane matrix strongly increasing the
barrier properties of the coatings applied on electrogalvanized steel. EIS
results reported in this work show that the impedance modulus at 0.1 Hz
remained stable at values in the order of 109 Ω cm2 after 235 h im­
mersion in 3.5 wt% NaCl solution [2]. In addition, it was shown that an
increase of the content of the graphene additive from 0.2 to 0.4 wt% led
to a further improvement of the corrosion barrier properties that was
attributed to a marked self-alignment of the additive parallel to the
substrate [11]. In the work of Li et al. [2], the barrier properties of
graphene loaded polyurethane coatings were associated to a percolation
phenomenon controlled by the aspect ratio of the graphene additive and
its dispersion in the coating. According to the percolation model, the

* Corresponding author.
E-mail address: francesco.andreatta@uniud.it (F. Andreatta).

https://doi.org/10.1016/j.porgcoat.2023.107517
Received 3 November 2022; Received in revised form 1 February 2023; Accepted 24 February 2023
Available online 6 March 2023
0300-9440/© 2023 Elsevier B.V. All rights reserved.
F. Andreatta et al.
graphene additive can form a continuous network hindering the
permeation of the electrolyte to the substrate [12]. A percolating
behaviour could be obtained with a 0.2 wt% content of the additive
since the high aspect ratio of graphene and its derivatives strongly re­
duces the percolation threshold as compared to other nanofillers like
clays or graphite platelets [2,6,12,13]. Due to tendency to agglomera­
tion of graphene and its derivatives, a percolation network is not always
formed since agglomerated graphene could result in isolated islands. In
this case, corrosion barrier properties would be mainly controlled by the
tortuous path for the electrolyte to reach the metal substrate through the
graphene islands [2]. A lot of research has been carried out in order to
improve the dispersion and compatibility of graphene and its derivatives
with waterborne epoxy coatings [1,3,14–20] and acrylic coatings
[21–24]. Teijido et al. [6] recently reviewed the state of the art and
current trends on layered inorganic-polymer coatings for corrosion
protection highlighting that most of the research has been dedicated to
study the compatibility of graphene with some of the most employed
polymeric matrixes in the coatings industry, as epoxy resins or poly­
urethanes. Loading of graphene in polyester resins found only limited
applications, mainly devoted to controlling mechanical, electrical and
thermal properties of composite materials [25–29].
Graphene and its derivatives are conductive fillers in polymer coat­
ings and composites [30–33]. The electrical conductivity of graphene is
extremely high, 6 105 S m− 1 due to the combination of high charge
carrier mobility and high charge carrier concentration [34]. The high
conductivity of graphene can induce galvanic corrosion with the
metallic substrate in corrosion protective coatings containing graphene.
As an example, Wu et al. [35] reported the formation of a galvanic
couple in defected graphene films on copper, which displayed anodic
behaviour relative to the graphene film. The risk of galvanic corrosion
issues can be mitigated by graphene functionalization, which is reported
to reduce the conductivity of graphene [1]. Nevertheless, the electrical
conductivity of graphene and its derivatives can be important for
obtaining multifunctional coatings and composite materials with
different applications including anti-static components, electromagnetic
shielding, lightning strike protection, conductive adhesives and strain
sensors [31]. The electrical conductivity of graphene loaded polymer
composites is described by the percolation theory. For a random distri­
bution of an electrically conductive filler in a polymer matrix, a con­
ducting network can be formed when the filler concentration is above
the percolation threshold. This is associated to a marked increase of
electrical conductivity. This behaviour identifies three characteristic
regimes: insulating, percolating and conductive [31]. The insulating
regime is established when there is no conductive path through the
filler, while the conductive regime is associated to the formation of a
directly connected network. The percolating regime is a quantum phe­
nomenon associated to electron tunneling trough an interface formed
between the filler and the polymeric matrix. This is well documented for
graphene and its derivatives [30,31]. The percolation properties can be
affected also by agglomeration of graphene. This leads to the phenom­
enon of selective localization, which results in conductive behaviour at
low graphene loadings [30,36]. Due to the high aspect ratio of graphene,
the percolation threshold of graphene loaded coatings is very low, in the
order of 0.5 vol% [31,37]. Percolation thresholds below 1 wt% are often
reported in literature [32].
As for electrical conductivity, the incorporation of different graphene
fillers in a polymeric matrix improves the thermal conductivity of the
composite [37,38]. Two-dimensional graphene is regarded as an ideal
thermal conductive filler due to its high specific surface area. The
thermal conductivity of graphene can be higher than 3000 W/mK at
room temperature [39]. This is higher than the conductivity of carbon
nanotubes and bulk graphite. Moreover, it is almost one order of
magnitude higher than the thermal conductivity of aluminium oxide,
aluminium nitride, boron nitride and silver nanoparticles, which are
alternative fillers employed to control thermal properties of polymer
matrix composites [39,40]. Another important aspect is that graphene
2
Progress in Organic Coatings 179 (2023) 107517
and its derivatives can induce a significant increase of thermal con­
ductivity already for volume fractions of about 2 % in a polymer matrix
[39]. The thermal properties of graphene and its derivatives are
important for applications where efficient heat removal are critical such
as thermal dissipation in electronic devices or in renewable energy
generation by photovoltaic solar cells [39]. In contrast to electrical
percolation, thermal percolation in graphene loaded polymer matrix
composites can be less pronounced because the polymeric matrix can
contribute to the thermal conductivity. Nevertheless, different works in
literature prove the existence of thermal percolation in graphene loaded
composites [40–43]. Accordingly, the thermal conductivity can be
strongly enhanced when the content of graphene reaches the percolation
threshold [40].
The literature discussed above clearly evidences that graphene
composite organic coatings can provide efficient corrosion protection.
Due to their strong potential, several commercial formulations con­
taining graphene has become available [6]. However, commercial
available paints containing graphene can provide only a limited increase
of corrosion protection (factor 2) [6]. Moreover, another critical issue is
related to the use of solvents or other environmentally dangerous sub­
stances to functionalize graphene and to control its dispersion in the
organic matrix and even during paint application. Different application
methods were employed for application of graphene loaded organic
coatings including dip coating, application by means of a bar or wire
coater, high pressure spraying, spin coating and air brushing [6]. To the
best of our knowledge, there are no applications of graphene containing
powder coatings applied by electrostatic deposition, which is considered
in this work. This application method presents several advantages
including low or no volatile organic content, high utilization rates, 100
% solid content and elimination of hazardous waste [44–46].
This work investigates polyester powder coatings containing gra­
phene deposited on AA6060. The coatings were developed with a
multifunctional approach in order to combine corrosion protection and
high electrical and thermal conductivity. In particular, efficient thermal
dissipation was the main target in the development of the multifunc­
tional composite coatings. The corrosion protection was investigated by
EIS in order to evaluate the efficiency of the barrier protection over long
immersion time (35 days). Moreover, EIS data were used to obtain in­
formation about the electrical parameters of the composite coatings. An
interpretation of impedance data is proposed based on the electrical
percolation theory in order to demonstrate that graphene-rich regions in
the composite coatings can promote percolation strongly decreasing the
electrical resistance of the coating and increasing its capacitance. The
percolating behaviour of the coating is also observed on the thermal
dissipation, which was also qualitatively evaluated in this work.
2. Materials and methods
2.1. Substrate and coating production
AA6060 was the substrate for the deposition of polyester powder
coatings loaded with graphene additive. AA6060 panels with size 10 cm
× 5 cm were ultrasonically cleaned in ethanol and rinsed in deionized
water prior to coating deposition. The polyester powder coatings were
applied by electrostatic deposition at PLT GmbH. The graphene additive
was introduced in a polyester powder by melt compounding. This led to
the production of different masters with fixed graphene/resin ratio,
which were employed for the production of all graphene loaded powder
coatings investigated in this work. In particular, three masters were
used: master 1 with 1 wt% graphene, master 2 with 7 wt% graphene and
master 3 with 10 wt% graphene. The final graphene content of the
coatings was controlled by mixing in proper ratios the master with fixed
graphene/resin ratio and virgin polyester powder. By this approach,
polyester powder coatings with the following graphene contents were
produced: 0.5, 1, 3.5 and 10.0 wt%. Polyester powder coatings without
graphene were also used in this work as a reference. Additives typically
F. Andreatta et al.
Fig. 1. Polyester powder coatings without graphene and with 0.5, 1, 3.5 and 10.0 wt% graphene (the coating thickness is also reported in the figure).
employed for the production of polyester powder coatings such as tita­
nium dioxide and barium sulphate were also included in all coating
formulations in order to evaluate the effect of the graphene additive in a
formulation similar to those commercially available. Coatings formu­
lations investigated in this work are proprietary and cannot be disclosed.
The polyester powder containing the graphene additive was applied
on the AA6060 panels using a conventional electrostatic spraying
equipment (PG 1 Powder Gunfrom Gema with 60 kV output voltage).
Successively, the coated panels underwent thermal treatment at 190 ◦ C
for 20 min in order to enable the curing of the sprayed polyester powder.
The AA6060 panels with the polyester powder coatings with and
without graphene are shown in Fig. 1. The dry coating thickness was
ranging between 85 and 100 μm for the coated panels (standard devi­
ation below 5 μm).
2.2. Characterization of the graphene-loaded master and coatings
The graphene-loaded master and the AA6060 panels coated with the
polyester powder coating containing graphene were investigated by FE-
SEM in order to evaluate the presence of the graphene additive. Sec­
ondary electron images were acquired with a JSM-7610FPlus FE-SEM
for the master and on polished sections of the graphene-loaded coatings.
In addition, Raman spectroscopy was employed to obtain further
confirmation of the presence of graphene in the master. Raman spectra
were obtained by means of a through an XploRA Plus confocal Raman
spectrometer (Horiba Jobin Yvon Srl). The sample was analysed through
a green laser (532 nm) with a power of 10 mW. The diffraction grating
had a density of 1200 lines per mm. Spectra were acquired from 500 to
3600 cm− 1, with 5 accumulations per spectrum and 60 s as the acqui­
sition time for each spectrum. The spectra were acquired on the gra­
phene additive, on the unloaded polyester powder and on two different
masters with different graphene/resin ratio (master 1 and master 2).
2.3. Characterization of the electrochemical behaviour of the coatings
The electrochemical behaviour of coated AA6060 panels was
initially investigated by electrochemical impedance spectroscopy in
order to evaluate their protective properties. Three panels for each type
of coating were investigated in this work. Impedance spectra were ac­
quired in 0.1 M NaCl solution as a function of the immersion time
employing an Autolab PGSTAT30 potentiostat. The spectra were
recorded at the open circuit potential with an applied AC amplitude of
10 mV in the frequency range from 105 Hz to 10− 2 Hz (7 points/decade).
A second set of impedance measurements was preliminarily performed
with 50 mV AC amplitude showing the same trend than those obtained
with 10 mV amplitude. In this work, only EIS data obtained with 10 mV
amplitude are presented because they were reproducible and adequate
to assess the electrical properties of the coatings. The EIS measurements
were performed with an electrochemical cell with standard three-
3
Progress in Organic Coatings 179 (2023) 107517
electrode configuration. The area of the coated sample exposed to the
electrolyte (working electrode) was 3.14 cm2. A silver/silver chloride
electrode (Ag/AgCl 3 M KCl) was employed as reference electrode. A Pt
wire was used as counter electrode.
2.4. Characterization of the electrical and thermal properties of the
coatings
In this work, impedance measurements were also employed for
evaluating the electrical properties of the polyester powder coatings
containing graphene. Electrical parameters of the coatings without
graphene and with different contents of the graphene additive were
extracted by fitting with an equivalent circuit. A single time-constant
equivalent circuit was used for fitting impedance data of the panels
with polyester powder coatings without graphene. The circuit consists of
the electrolyte resistance in series with the parallel combination of a
resistance and constant phase element (CPE) describing the electro­
chemical behaviour of the coating. The CPE was employed to take into
account that the coated panels did not display pure capacitive behav­
iour. Nevertheless, this is qualitatively treated as a capacitor in the
discussion of impedance data presented in this work. The impedance
data of the graphene loaded polyester powder coatings were fitted with
a two time-constant equivalent circuit. This approach was followed in
order to discuss impedance data considering electrical percolation,
which is a well-documented phenomenon in graphene-polymer com­
posites [30,31]. The two time-constants equivalent circuit consists of
two parallel resistance/constant phase element combinations, which are
in series with each other. The electrolyte resistance was also included in
the circuit. The first resistance/constant phase element combination
describes the behaviour of percolating regions of the coating (graphene
rich), while the second one accounts for non-percolating regions
(polyester matrix or regions with low graphene content). This approach
for fitting the behaviour of graphene loaded coatings is based on the
high tendency for agglomeration of graphene additives in organic
coatings and it is typically employed for the interpretation of electrical
conductivity measurements in graphene-polymer composites. The same
equivalent circuit was recently employed by Mollik et al. [47] to
describe the behaviour of starch/reduced graphene oxide (PS/rGO)
nanocomposites and by Li et [2] al for the interpretation of EIS data of
waterborne polyurethane coatings containing graphene. In the discus­
sion of results obtained by fitting EIS data, the constant phase element
was arbitrarily treated considering Q0 as a pure capacitance. Although
this is not correct and different equations are proposed for the conver­
sion of Q0 to an equivalent capacitance [48,49], this is not considered in
our work that aims to highlight qualitative differences between coatings
with different graphene content.
A detailed investigation of thermal conductivity of the graphene
loaded polyester coatings is beyond the scope of this work. Nevertheless,
thermal properties of the coatings were qualitatively investigated with
F. Andreatta et al.
Fig. 2. FE-SEM images of the polyester powder containing graphene (master).
an internal test developed at PLT GmbH. Two coated panels (a reference
coating without graphene and a coating containing 1 wt% graphene)
were placed in an oven at 90 ◦ C until the sample surface reached a stable
temperature, which was read with thermocouples positioned on the
coating surfaces. The temperature of the coating surface was recorded
versus time during the heating cycle and during cooling to room tem­
perature. The trend of the coating temperature during the heating and
cooling cycles provides information about the thermal behaviour of the
coated panels investigated in this work.
3. Results and discussion
3.1. Polyester powder containing graphene (master)
Fig. 2 shows representative FE-SEM images of the polyester powder
containing the graphene additive (master), which was employed for
application by electrostatic spraying on AA6060 panels after mixing
with virgin polyester powder. The particle size visible in Fig. 2A is rather
4
Progress in Organic Coatings 179 (2023) 107517
variable since rather large particles could be observed in the micro­
graph. At higher magnification (Fig. 2B), structures associated to the
typical morphology of graphene additives can be recognized: graphene
agglomerates and plate-like structures. Details of such structures are
shown in Fig. 2C and D. The layered structure of the graphene additive is
clearly visible in the agglomerate in Fig. 2C. Its size is in the order of 100
μm. Similar agglomerates are often observed in the master suggesting a
marked tendency of the graphene additive to agglomerate in the poly­
ester matrix during melt compounding. This tendency was probably
enhanced by the high graphene amounts (above the percolation
threshold) that were deliberatively added to the coatings in order to
modify their electrical and thermal properties. It is likely that a better
exfoliation of the graphene additive could limit their tendency to
aggregate during melt compounding and coating deposition. In addition
to graphene agglomerates, several regions showing plate-like structures
could be observed in the coatings (Fig. 2B). An example is given in
Fig. 2D. These regions are most likely regions of the polyester matrix
enriched with the graphene additive.
F. Andreatta et al.
Fig. 3. Raman spectra of graphene, polyester resin and two different masters
with different graphene content (master 1 with 1 wt% graphene and master 2
with 7 wt% graphene).
The presence of the graphene additive in the master was further
investigated by Raman spectroscopy. Fig. 3 shows the characteristic
Raman spectra for the graphene additive, the polyester resin and for two
different masters with different graphene/resin ratio. The spectrum of
the graphene additive displays four characteristic peaks: at 1322 cm− 1
(D band) associated to carbon atoms with sp3 hybridization or defects in
the carbon structure; at 1583 cm-1 (G band) due to carbon atoms with
sp2 hybridization; at 1615 cm-1 (D′ band) due to structural defects and
overlapping with the G band; at 2635 cm-1 (2D band) associated to the
layered structure of the graphene additive [50–52]. The spectrum of the
polyester resin exhibits two strong peaks: the band at 1630 cm− 1 that is
produced by the double carbon‑carbon bonds in the styrene and the
band at 1730 cm− 1 related to the carbonyl group. Moreover, two
superimposed peaks due to the carbon‑hydrogen bond are visible at
about 1400 cm− 1 [53]. The spectrum of master 1, employed for the
production of coatings with low graphene content (0.5 and 1 wt%),
shows a Raman spectrum very similar to that of the polyester resin. In
particular, the characteristic peaks observed for the graphene additive
are not visible in the spectrum. In contrast, the spectrum of master 2
with higher graphene/resin ratio exhibits the characteristic peaks of
graphene, while the peaks related to the polyester resin become no
longer visible. This clearly indicates that the Raman response of the
masters is determined by the graphene additive, when the graphene/
resin ratio is sufficiently high.
3.2. Cross sectional characterization of the coatings
Fig. 4 displays FE-SEM images of the cross section of AA6060 with a
polyester coating without graphene (panels A, C and E) and with a
coating containing 3.5 wt% graphene (panels B, D and F). Micrographs
at low magnification (panels A and B of Fig. 4) show that the coatings
with and without graphene are well adherent to the substrate. Pull-off
tests performed on the coated panels exhibited similar adhesion values
for all coatings (about 5 MPa) without being affected by their graphene
content. Moreover, it can be seen that the coating containing graphene is
thicker than the reference coating, in accordance with thickness values
reported in Fig. 1. At higher magnification, the polyester coating with
3.5 wt% graphene exhibits graphene-rich regions embedded in a matrix
of polyester resin (panel D of Fig. 4). The graphene-rich regions are
highlighted by dotted lines. These regions are agglomerates consisting of
plate-like exfoliated structures similar to those observed in Fig. 2 (panels
C and D). Other regions present a morphology similar to that of the
coating without graphene (panel C of Fig. 4). It is likely that these
5
Progress in Organic Coatings 179 (2023) 107517
regions correspond to the polyester resin with no or low graphene
content in the coating with 3.5 wt% graphene. Moreover, it can be seen
that both the neat polyester resin and the coating containing graphene
are characterized by the presence of particles with size in the micro­
meter range, which are associated to the additives introduced in the
coating formulation such as titanium dioxide and barium sulphate. The
micrographs in the panels E and F of Fig. 4 further highlight the different
morphology of the coating with graphene as compared to the reference
coating. The high tendency to agglomerate of graphene platelets is
confirmed also in the deposited coatings. As commented above, a better
exfoliation of the graphene additive could limit this tendency during the
production of the master and the coating deposition. The neat polyester
resin (panel E of Fig. 4) displays a rather smooth morphology with some
porosity, which should be considered typical of polyester powder coat­
ings. In contrast, panel F of Fig. 4 shows the interfacial region between a
graphene-rich region and the surrounding polyester matrix. The layered
plate-like structure of the graphene is clearly visible in this micrograph.
3.3. Electrochemical behaviour of polyester powder coatings without
graphene
The Bode and Nyquist plots of electrochemical impedance of AA6060
coated with a polyester coating without graphene in 0.1 M NaCl solution
are shown in Fig. 5A and B, respectively. The impedance modulus at low
frequency (10− 2 Hz) is 2.0 1011 Ω cm2 indicating that the polyester
coating is providing a highly efficient barrier effect (panel A of Fig. 5).
Moreover, the Bode plot shows that the impedance does not change as a
function of the immersion time (up to 840 h immersion). This means that
the barrier properties of the coating are retained for a relatively long
immersion time without any significant decrease of the barrier effect.
The Nyquist plot of the impedance clearly show that the behaviour of the
AA6060 with the polyester coating without graphene is almost purely
capacitive for all immersion times. In order to evaluate the coating
capacitance, impedance data were fitted with the equivalent circuit
shown in Fig. 5C, where Rs is the electrolyte resistance, Rc is the coating
resistance and CPEc is the constant phase element. The parameters of
CPEc are reported in Table 1. As indicated in Section 2.4, the constant
phase element was arbitrarily treated considering Q0 as a pure capaci­
tance since n values were closed to 1. Fig. 5D displays the coating
capacitance (Cc) as a function of the immersion time (up to 240 h im­
mersion).The coating capacitance is 4.6 10− 10 F cm− 2 immediately after
immersion. The capacitance increases during the first 24 h of immersion
due to water uptake of the coating and remains stable at a value of about
5.7 10− 10 F cm− 2 for longer immersion times.
3.4. Electrochemical behaviour of polyester powder coatings containing
graphene
Fig. 6 displays the Bode (panels A, C and E) and Nyquist plots (panels
B, D and F) of the impedance of AA6060 with coatings containing
different graphene content (1, 3.5 and 10 wt%). Impedance data about
the coating containing 0.5 wt% graphene are not included in the figure
because the behaviour of this sample was very similar to that observed in
Fig. 5 for the polyester coating without graphene. The coating con­
taining 1 wt% of graphene additive displays stable impedance as a
function of the immersion time (panels A and B of Fig. 6). The imped­
ance modulus at low frequency (10− 2 Hz) is 3.2 108 Ω cm2 immediately
after immersion in the testing electrolyte (panel A of Fig. 6). This is
remarkably lower than the value measured for the reference coating
without graphene (panel A of Fig. 5). Moreover, the Bode and Nyquist
plots clearly demonstrate the existence of two time constants for the
coating containing 1 wt% of graphene additive. The first time constant is
at about 102 Hz, while the second time constant is visible at the lowest
frequencies. The coating with 3.5 wt% graphene (panels C and D of
Fig. 6) displays similar behaviour to that observed for the coating with 1
wt% of graphene. The impedance of the coating is stable during the
F. Andreatta et al. Progress in Organic Coatings 179 (2023) 107517

Fig. 4. FE-SEM images of the cross section of the polyester coating without graphene (A, C and E) and of the coating containing 3.5 wt% of graphene (B, D and F).
Regions enriched of graphene are highlighted by dotted lines.

6
F. Andreatta et al. Progress in Organic Coatings 179 (2023) 107517

Fig. 5. Electrochemical impedance of the sample coated with the polyester powder coating without graphene in 0.1 M NaCl solution: Bode plot (A), Nyquist plot (B),
equivalent circuit (C) and coating capacitance vs immersion time (D).

immersion time and the impedance modulus at low frequency (10− 2 Hz)
Table 1
is 1.6 108 Ω cm2 immediately after immersion in the electrolyte. The
Parameters for CPEc in Fig. 5C.
Nyquist plot (panel D of Fig. 6) shows that the semicircle associated to
2
Immersion time / h Q0 / F cm− n the time constant at higher frequencies becomes smaller increasing the
0 4.57 10− 10
0.993 graphene content from 1 wt% to 3.5 wt%. A similar trend is observed for
10
4 5.42 10− 0.987 the coating containing 10 wt% of graphene additive. Indeed, the
10
8 5.55 10− 0.985 impedance of the coated AA6060 remains stable during the test with an
10
24 5.72 10− 0.984
48 5.70 10− 10
0.985
impedance modulus at low frequency (10− 2 Hz) of 6.4 108 Ω cm2
96 5.77 10− 10
0.983 immediately after immersion in the testing electrolyte. Moreover, the
168 5.67 10− 10
0.984 semicircle observed at higher frequencies becomes even smaller than
10
240 5.79 10− 0.982 that for the coating with 3.5 wt% graphene additive. Data in Fig. 6
10
840 5.67 10− 0.982
indicate that polyester coatings containing graphene can adequately
protect the substrate against corrosion providing a barrier effect that is
not affected by the immersion time in the testing electrolyte. All samples
investigated in this work, with and without graphene, displayed stable

7
F. Andreatta et al. Progress in Organic Coatings 179 (2023) 107517

Fig. 6. Electrochemical impedance measured in 0.1 M NaCl solution for samples coated with the polyester powder coating with 1 wt%, 3.5 wt% and 10 wt%
graphene: Bode plots (A,C and E) and Nyquist plots (B, D and F).

8
F. Andreatta et al. Progress in Organic Coatings 179 (2023) 107517

Fig. 7. Equivalent circuit employed to fit electrochemical impedance data for the samples coated with the polyester powder coating with 1 wt%, 3.5 wt% and 10 wt
% graphene (A) and schematic representation of electrically conductive paths for the coatings with graphene content above the percolation threshold (B).

barrier properties for 840 h in 0.1 M NaCl solution. No signs of corrosion
of the substrate, including possible galvanic effects related to the
introduction of graphene in the coatings were observed for the immer­
sion times considered in this work. The appearance of a second time
constant at high frequencies in the coatings with graphene content
above 1 wt% show that the electrical properties of the coatings are
modified by the addition of graphene indicating an electrical percolation
effect due to the introduction of graphene in the polyester powder
coatings.
3.5. Electrical properties of the coatings containing graphene
In order to evaluate the electrical properties of the coatings,
impedance data were fitted with an equivalent circuit to obtain resis­
tance and capacitance values for the coatings containing different
amounts of graphene. In the case of the coatings with graphene content

Fig. 8. Coating capacitance (A) and coating resistance (B) of the samples coated with the polyester powder coating without graphene and with 1 wt%, 3.5 wt% and
10 wt% graphene.

9
F. Andreatta et al. Progress in Organic Coatings 179 (2023) 107517

Table 2 composite. Since the cross sectional analysis by FE-SEM clearly shows
Parameters for the equivalent circuit in Fig. 7A for samples coated with the that the polyester powder coatings loaded with graphene consist of
polyester powder coating containing 1 wt%, 3.5 wt% and 10 wt% graphene. graphene-rich regions embedded in a polyester matrix, it was decided to
Graphene-poor regions Graphene-rich regions interpret our impedance data on the base of the electrical percolation
Graphene Immersion R1 / CPE1 R2 / CPE2
theory [30]. It is likely, that the graphene-rich regions are in contact
content time / h ohm ohm with each other due to the high amount of graphene in the coatings
cm2 cm2 investigated in our work. In particular, perhaps with the exception of the
Q01 / n1 Q02 / n2 coating with 0.5 wt% graphene, the additive contents considered in our
F F work are well above the percolation threshold that is reported to be
cm− 2 cm− 2 about 0.5 wt% [31]. Therefore, it can be expected that the network of
1 wt% 0 9.14 2.34 0.676 1.18 1.48 0.942 graphene rich-regions could provide a continuous path for electrons as
108 10− 8 108 10− 9 schematically represented in Fig. 7B.
4 1.15 3.32 0.658 1.53 1.96 0.938 Fig. 8A displays the coating capacitance obtained for polyester
109 10− 8 108 10− 9
powder coatings with and without graphene in order to assess the effect
8 9.79 3.36 0.657 1.53 2.06 0.931
108 10− 8 108 10− 9 of graphene on the electrical properties of the coatings. The coating
24 1.00 3.39 0.662 1.46 2.19 0.930 capacitance was obtained with the equivalent circuit in Fig. 5C for the
109 10− 8 108 10− 9 coating without graphene and with 0.5 wt% graphene, while they were
48 4.89 3.11 0.671 1.36 2.31 0.926 calculated with the equivalent circuit in Fig. 7A for coatings with higher
108 10− 8 108 10− 9
96 3.06 2.95 0.675 1.37 2.41 0.920
graphene content taking into account the contributions of the constant
108 10− 8 108 10− 9 phase elements CPE1 and CPE2. Table 2 displays the parameters for the
168 2.44 3.30 0.671 1.42 2.67 0.910 equivalent circuit in Fig. 7A for samples coated with the polyester
108 10− 8 108 10− 9 powder coating containing 1 wt%, 3.5 wt% and 10 wt% graphene.
240 3.43 3.46 0.665 1.57 2.59 0.914
Again, the constant phase elements were arbitrarily treated considering
108 10− 8 108 10− 9
840 2.39 3.38 0.671 1.46 2.81 0.909 Q0 as a pure capacitance (1/Cc = 1/C1 + 1/C2) since n values in Table 2
108 10− 8 108 10− 9 are close to 0.9 or higher (with the exception of the n value of CPE1 in
3.5 wt% 0 5.79 7.34 0.931 2.17 4.74 0.892 the sample with 1 wt% graphene for which there were few points at low
108 10− 8 106 10− 9 frequency for a precise fitting of the data). The capacitance Cc displays a
4 1.18 7.19 0.946 2.25 4.88 0.890
109 10− 8 106 10− 9
similar trend for all samples with an initial increase due to water uptake
8 1.54 7.08 0.950 2.30 4.98 0.888 and stationary behaviour for immersion times longer than 24 h.
109 10− 8 106 10− 9 Nevertheless, the coating capacitance is strongly affected by the gra­
24 1.18 7.41 0.947 2.22 5.27 0.887 phene content in the polyester coating. The coating without graphene
109 10− 8 106 10− 9
and that with 0.5 wt% graphene exhibit a capacitance of about 5.0
48 2.29 7.34 0.953 2.25 5.44 0.885
109 10− 8 106 10− 9 10− 10 F cm− 2 after 24 h immersion. This is about 2.0 10− 9 F cm− 2 for the
96 1.54 7.62 0.945 2.29 5.60 0.882 coating with 1 wt% graphene, 5.0 10− 9 F cm− 2 for the coating with 3.5
109 10− 8 106 10− 9 wt% graphene and 1.0 10− 8 F cm− 2 for the coating with 10 wt% gra­
168 3.21 7.48 0.950 2.28 5.64 0.882 phene. Fig. 8B displays the coating resistance measured immediately
109 10− 8 106 10− 9
240 2.68 7.70 0.944 2.34 6.02 0.877
after immersion in 0.1 M NaCl solution. The coating resistance was
109 10− 8 106 10− 9 obtained from the equivalent circuit in Fig. 5C for the coatings without
840 4.88 7.98 0.948 2.25 6.10 0.880 graphene and with 0.5 wt% graphene. In this case, a relatively high error
109 10− 8 106 10− 9 was observed for resistances calculated for these coatings due to the
10 wt% 0 4.54 2.09 0.962 4.27 1.29 0.909
highly capacitive behaviour displayed in Fig. 5. The resistance was
109 10− 8 105 10− 8
4 3.14 2.23 0.946 5.38 1.72 0.899 calculated with the equivalent circuit in Fig. 7A for coatings with 1 wt%,
109 10− 8 105 10− 8 3.5 wt% and 10 wt% graphene. In this case the coating resistance was
8 5.84 2.16 0.948 5.62 1.74 0.896 obtained considering the contribution of R1 and R2 (Rc = R1 + R2). The
109 10− 8 105 10− 8 coating resistance is strongly reduced by additions of graphene above 1
24 6.10 2.19 0.943 6.87 1.83 0.897
109 10− 8 105 10− 8
wt%, with a reduction between one or two orders of magnitude relative
48 4.34 2.27 0.948 5.74 1.85 0.896 to the coating without graphene. This trend is not affected by the high
109 10− 8 105 10− 8 error in the evaluation of the resistance of the reference coating without
96 3.30 2.16 0.942 5.99 1.75 0.897 graphene and with 0.5 wt% graphene using the equivalent circuit in
109 10− 8 105 10− 8
Fig. 5C. The increase of the coating capacitance and the decrease of the
168 3.26 2.22 0.935 6.89 1.79 0.899
109 10− 8 105 10− 8 coating resistance reflects the electrical percolating behaviour high­
240 5.59 2.27 0.948 6.89 1.95 0.894 lighted by impedance data in Fig. 6. This effect is evident already for a
109 10− 8 105 10− 8 graphene content of 1 wt%. Nevertheless, it should be considered that a
840 5.14 2.52 0.938 6.51 2.07 0.899 better exfoliation of the graphene additive during the preparation of the
109 10− 8 105 10− 8
master and coating deposition could further improve the electrical
properties of the coatings.
higher than 1 wt%, the two-time constants equivalent circuit shown in The contribution of graphene-poor and graphene-rich regions to the
Fig. 7A was employed for fitting impedance data. The circuit consists of electrical properties of the coatings can be separated according to the
two parallel resistance/constant phase element combinations (R1/CPE1 equivalent circuit in Fig. 7A (circuit parameters given in Table 2). In
and R2/CPE2), which are in series with each other and with the solution order to avoid the effect of water uptake, resistance values extracted
resistance Rs. This circuit was employed by other authors for the inter­ from impedance data are considered immediately after immersion (0 h).
pretation of electrical conductivity measurements for graphene-polymer Fig. 9 presents the resistance of graphene-poor (panel A) and graphene-
composites on the base of the theory of electrical percolation [2,47]. rich regions (panel B) for the samples coated with the polyester powder
This is based on the existence of a continuous network of graphene rich containing 1 wt%, 3.5 wt% and 10 wt% graphene. The resistance of the
regions that strongly increases the electrical conductivity of the coating without graphene and that for the coating with 0.5 wt% gra­
phene are also reported as a reference. The low-frequency parallel

10
F. Andreatta et al.
Fig. 9. Resistance of graphene-poor (A) and graphene-rich regions (B) for the samples coated with the polyester powder containing 0.5 wt%, 1 wt%, 3.5 wt% and 10
wt% graphene. The resistance of the coating without graphene is also reported in the figure.
Fig. 10. Temperature profile for a polyester powder coating with 1 wt% gra­
phene and for a coating without graphene during a heating/cooling cycle.
resistance/constant phase element combination (R1/CPE1) of the
equivalent circuit in Fig. 7 can be associated to the poor conducting
regions of the polyester matrix with no or very low graphene content. As
can be seen in Fig. 9A, the resistance Rc of graphene-poor regions in the
coating with 0.5 wt% graphene is about 3 1011 Ω cm2, which is similar to
that of the coating without graphene (about 5 1011 Ω cm2). The resis­
tance R1 remains between 5 108 and 5 109 Ω cm2 for coatings containing
1, 3.5 and 10 wt% of graphene. These high resistance values indicate
that the polyester matrix behaves as an insulator when the graphene is
not providing a continuous path to the substrate. The resistance R2 of
graphene-rich regions is shown in Fig. 9B for the coatings with different
graphene content. This resistance corresponds to the high-frequency
parallel resistance/constant phase element combination (R2/CPE2). It
can be seen that the resistance R2 strongly decreases increasing the
11
Progress in Organic Coatings 179 (2023) 107517
graphene content of the coating. The value of R1 is 1.2 108 Ω cm2 for the
coating containing 1 wt% graphene, while it is 2.2 106 Ω cm2 for 3.5 wt
% graphene content and 4.3 105 Ω cm2 for 10 wt% graphene content. In
particular, there is a reduction of resistance of about two orders of
magnitude for coatings with a high graphene content (3.5 and 10 wt%).
This reflects the contribution of the agglomerated graphene additive
that is decreasing the electrical resistance of the coating in line with the
electrical percolation theory. It is worth to note that the decrease of
electrical resistance is obtained without impairing the protective prop­
erties of the polyester composite powder coating. In fact, impedance
diagrams remain almost overlapped during the whole immersion time
up to 840 h for all graphene containing coatings. This trend is also
confirmed by data reported in Table 2.
3.6. Thermal properties of the coatings containing graphene
In order to have information about the thermal properties of the
coatings, the temperature of coated panels was measured by means of a
thermocouple positioned on the coating surface during a heating/cool­
ing cycle. Fig. 10 shows the temperature of the coated AA6060 panels for
a coating without graphene and a coating with 1 wt% graphene. During
the test, the coated panels were heated at 90 ◦ C. The panel with the
coating with graphene displays a higher temperature during the heating
cycle than the coating without graphene indicating that the addition of
graphene increases the thermal conductivity of the coating. After the
heating cycle at 90 ◦ C, the coated panels were extracted from the oven
and temperature of the coated panel was measured during air cooling at
room temperature. The temperature of the panel with the coating con­
taining graphene is lower than that of the coating without graphene
during cooling. As an example, the temperature of the coating with 1 wt
% graphene is 43.3 ◦ C after a measurement time of 6 min while it is
51.6 ◦ C for the coating without graphene. A similar, or slightly better,
behaviour was observed for samples containing higher amounts of
graphene. The trend of the temperature of the coated panels during
cooling clearly indicates that thermal dissipation is strongly promoted
by addition of graphene to the coating, which is a very important
F. Andreatta et al.
property for coatings developed in our work. A more detailed charac­
terization of the thermal behaviour of the coatings containing graphene
is the subject of a future work to further highlight the effect of graphene
additions on thermal dissipation.
4. Conclusions
This work investigated polyester powder coatings loaded with gra­
phene. Electrochemical impedance spectroscopy was employed to
evaluate corrosion protection. Moreover, this technique was used to
obtain information about the electrical parameters of the coatings with
reference to the electrical percolation theory. This was complemented
by an evaluation of the thermal dissipation of the coatings containing
graphene.
• The polyester powder coatings loaded with graphene display
graphene-rich regions embedded in a polyester matrix with lower
graphene content (graphene-poor regions). Graphene exhibits a
marked tendency to form agglomerates in the coatings.
• The powder coatings loaded with graphene (up to 10 wt%) provide
an efficient barrier against corrosion, similarly to the reference
coating without graphene. Stable impedance values were obtained
for immersion times up to 35 days in 0.1 M NaCl solution.
• The electrochemical impedance of the coatings with graphene con­
tent above 1 wt% exhibit two-time constants indicating a percolating
behaviour. This is associated to the graphene-rich regions of the
coating which provide an electrical conductive path leading to
electrical percolation for graphene contents above the percolation
threshold (above 0.5 wt%).
• Electrical percolation is also associated to thermal percolation. In
particular, addition of graphene to the coatings markedly improve
thermal dissipation.
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
The data that has been used is confidential.
Acknowledgements
This research was carried out in the framework of the Italy-Austria
Interreg project FasTher (ID ITAT1085).
References
[1] J. Mu, F. Gao, G. Cui, S. Wang, S. Tang, Z. Li, A comprehensive review of
anticorrosive graphene-composite coatings, Prog. Org. Coat. 157 (2021), 106321,
https://doi.org/10.1016/j.porgcoat.2021.106321.
[2] J. Li, J. Cui, J. Yang, Y. Li, H. Qiu, J. Yang, Reinforcement of graphene and its
derivatives on the anticorrosive properties of waterborne polyurethane coatings,
Compos. Sci. Technol. 129 (2016) 30–37, https://doi.org/10.1016/j.
compscitech.2016.04.017.
[3] R. Ding, W. Li, X. Wang, T. Gui, B. Li, P. Han, H. Tian, A. Liu, X. Wang, X. Liu, et al.,
A brief review of corrosion protective films and coatings based on graphene and
graphene oxide, J. Alloys Compd. 764 (2018) 1039–1055, https://doi.org/
10.1016/j.jallcom.2018.06.133.
[4] R. Ding, S. Chen, J. Lv, W. Zhang, X.dong Zhao, J. Liu, X. Wang, T.jiang Gui, B.
jun Li, , et al.Y.zheng Tang, Study on graphene modified organic anti-corrosion
coatings: a comprehensive review, J. Alloys Compd. 806 (2019) 611–635, https://
doi.org/10.1016/j.jallcom.2019.07.256.
[5] G. Cui, Z. Bi, R. Zhang, J. Liu, X. Yu, Z. Li, A comprehensive review on graphene-
based anti-corrosive coatings, Chem. Eng. J. 373 (2019) 104–121, https://doi.org/
10.1016/j.cej.2019.05.034.
[6] R. Teijido, L. Ruiz-Rubio, A.G. Echaide, J.L. Vilas-Vilela, S. Lanceros-Mendez,
Q. Zhang, State of the art and current trends on layered inorganic-polymer
12
Progress in Organic Coatings 179 (2023) 107517
nanocomposite coatings for anticorrosion and multi-functional applications, Prog.
Org. Coat. 163 (2022), https://doi.org/10.1016/j.porgcoat.2021.106684.
[7] B.M. Yoo, H.J. Shin, H.W. Yoon, H.B. Park, Graphene and graphene oxide and their
uses in barrier polymers, J. Appl. Polym. Sci. (2014) 131, https://doi.org/10.1002/
app.39628.
[8] Y. Su, V.G. Kravets, S.L. Wong, J. Waters, A.K. Geim, R.R. Nair, Impermeable
barrier films and protective coatings based on reduced graphene oxide, Nat.
Commun. 5 (2014) 1–5, https://doi.org/10.1038/ncomms5843.
[9] C.N.R. Rao, K. Biswas, K.S. Subrahmanyam, A. Govindaraj, Graphene, the new
nanocarbon, J. Mater. Chem. 19 (2009) 2457–2469, https://doi.org/10.1039/
b815239j.
[10] 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 (2016) 354–364, https://doi.
org/10.1016/j.surfcoat.2015.12.056.
[11] Y. Li, Z. Yang, H. Qiu, Y. Dai, Q. Zheng, J. Li, J. Yang, Self-aligned graphene as
anticorrosive barrier in waterborne polyurethane composite coatings, J. Mater.
Chem. A 2 (2014) 14139–14145, https://doi.org/10.1039/c4ta02262a.
[12] J. Li, J.K. Kim, Percolation threshold of conducting polymer composites containing
3D randomly distributed graphite nanoplatelets, Compos. Sci. Technol. 67 (2007)
2114–2120, https://doi.org/10.1016/j.compscitech.2006.11.010.
[13] C. Lu, Y.W. Mai, Influence of aspect ratio on barrier properties of polymer-clay
nanocomposites, Phys. Rev. Lett. 95 (2005) 1–4, https://doi.org/10.1103/
PhysRevLett.95.088303.
[14] Y. Tian, W. Wang, L. Zhong, X. Jiang, X. Zhang, Investigation of the anticorrosion
properties of graphene oxide-modified waterborne epoxy coatings for AA6061,
Prog. Org. Coat. 163 (2022), 106655, https://doi.org/10.1016/j.
porgcoat.2021.106655.
[15] C. Chen, S. Qiu, M. Cui, S. Qin, G. Yan, H. Zhao, L. Wang, Q. Xue, Achieving high
performance corrosion and Wear resistant epoxy coatings via incorporation of
noncovalent functionalized graphene, Carbon 114 (2017) 356–366, https://doi.
org/10.1016/j.carbon.2016.12.044. N. Y.
[16] S. Stankovich, R.D. Piner, S.B.T. Nguyen, R.S. Ruoff, Synthesis and exfoliation of
isocyanate-treated graphene oxide nanoplatelets, Carbon 44 (2006) 3342–3347,
https://doi.org/10.1016/j.carbon.2006.06.004. N. Y.
[17] S. Liu, L. Gu, H. Zhao, J. Chen, H. Yu, Corrosion resistance of graphene-reinforced
waterborne epoxy coatings, J. Mater. Sci. Technol. 32 (2016) 425–431, https://doi.
org/10.1016/j.jmst.2015.12.017.
[18] Y. He, C. Chen, G. Xiao, F. Zhong, Y. Wu, Z. He, Improved corrosion protection of
waterborne epoxy/graphene coating by combining non-covalent and covalent
bonds, React. Funct. Polym. 137 (2019) 104–115, https://doi.org/10.1016/j.
reactfunctpolym.2019.02.001.
[19] Q. Zhu, E. Li, X. Liu, W. Song, Y. Li, X. Wang, C. Liu, Epoxy coating with in-situ
synthesis of polypyrrole functionalized graphene oxide for enhanced anticorrosive
performance, Prog. Org. Coat. 140 (2020), https://doi.org/10.1016/j.
porgcoat.2019.105488.
[20] Z. Sekhavat Pour, M. Ghaemy, Polymer grafted graphene oxide: for improved
dispersion in epoxy resin and enhancement of mechanical properties of
nanocomposite, Compos. Sci. Technol. 136 (2016) 145–157, https://doi.org/
10.1016/j.compscitech.2016.10.014.
[21] K.C. Chang, W.F. Ji, C.W. Li, C.H. Chang, Y.Y. Peng, J.M. Yeh, W.R. Liu, The effect
of varying carboxylic-group content in reduced graphene oxides on the
anticorrosive properties of PMMA/reduced graphene oxide composites, Express
Polym. Lett. 8 (2014) 908–919, https://doi.org/10.3144/
expresspolymlett.2014.92.
[22] E. Aguete, B. Díaz, X.R. Nóvoa, C. Pérez, Corrosion resistance of a water-borne
resin with graphene oxide applied on galvanized steel, in: 12th Int. Work. Appl.
Electrochem. Tech. to Org. Coatings 173, 2022, p. 1, https://doi.org/10.1016/j.
porgcoat.2022.107220.
[23] M. Calovi, S. Dirè, R. Ceccato, F. Deflorian, S. Rossi, Corrosion protection
properties of functionalised graphene-acrylate coatings produced via cataphoretic
deposition, Prog. Org. Coat. 136 (2019), https://doi.org/10.1016/j.
porgcoat.2019.105261.
[24] M. Calovi, S. Rossi, F. Deflorian, S. Dirè, R. Ceccato, Graphene-based reinforcing
filler for double-layer acrylic coatings, Materials 13 (2020) 1–27, https://doi.org/
10.3390/ma13204499 (Basel).
[25] F. Serenari, M. Madinehei, N. Moghimian, D. Fabiani, E. David, Development of
reinforced polyester/graphene nanocomposite showing tailored electrical
conductivity, Polymers 12 (2020) 1–10, https://doi.org/10.3390/polym12102358
(Basel).
[26] S. Swain, Synthesis and characterization of graphene based unsaturated polyester
resin composites, Trans. Electr. Electron. Mater. 14 (2013) 53–58, https://doi.org/
10.4313/TEEM.2013.14.2.53.
[27] Z. Tang, H. Kang, Z. Shen, B. Guo, L. Zhang, D. Jia, Grafting of polyester onto
graphene for electrically and thermally conductive composites, Macromolecules 45
(2012) 3444–3451, https://doi.org/10.1021/ma300450t.
[28] M. Bastiurea, M.S. Rodeanu, D. Dima, M. Murarescu, G. Andrei, Thermal and
mechanical properties of polyester composites with graphene oxide and graphite,
Dig. J. Nanomater. Biostruct. 10 (2015) 521–533.
[29] C. Bora, P. Bharali, S. Baglari, S.K. Dolui, B.K. Konwar, Strong and conductive
reduced graphene oxide/polyester resin composite films with improved
mechanical strength, thermal stability and its antibacterial activity, Compos. Sci.
Technol. 87 (2013) 1–7, https://doi.org/10.1016/j.compscitech.2013.07.025.
[30] Y. Wang, J.W. Shan, G.J. Weng, Percolation threshold and electrical conductivity
of graphene-based nanocomposites with filler agglomeration and interfacial
tunneling, J. Appl. Phys. 118 (2015), https://doi.org/10.1063/1.4928293.
F. Andreatta et al.
[31] A.J. Marsden, D.G. Papageorgiou, C. Vallés, A. Liscio, V. Palermo, M.A. Bissett, R.
J. Young, I.A. Kinloch, Electrical percolation in graphene-polymer composites, 2D
Mater. 5 (2018), https://doi.org/10.1088/2053-1583/aac055.
[32] C. Tu, K. Nagata, S. Yan, Dependence of electrical conductivity on phase
morphology for graphene selectively located at the interface of polypropylene/
polyethylene composites, Nanomaterials 12 (2022), https://doi.org/10.3390/
nano12030509.
[33] X. Xia, J. Hao, Y. Wang, Z. Zhong, G.J. Weng, Theory of electrical conductivity and
dielectric permittivity of highly aligned graphene-based nanocomposites, J. Phys.
Condens. Matter 29 (2017), https://doi.org/10.1088/1361-648X/aa68ec.
[34] X. Du, I. Skachko, A. Barker, E.Y. Andrei, Approaching ballistic transport in
suspended graphene, Nat. Nanotechnol. 3 (2008) 491–495, https://doi.org/
10.1038/nnano.2008.199.
[35] 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 (2019)
135–144, https://doi.org/10.1016/j.jallcom.2018.10.260.
[36] H. Kim, S. Kobayashi, M.A. Abdurrahim, M.J. Zhang, A. Khusainova, M.
A. Hillmyer, A.A. Abdala, C.W. MacOsko, Graphene/polyethylene nanocomposites:
effect of polyethylene functionalization and blending methods, Polymer 52 (2011)
1837–1846, https://doi.org/10.1016/j.polymer.2011.02.017 (Guildf).
[37] B. Li, W.H. Zhong, Review on polymer/graphite nanoplatelet nanocomposites,
J. Mater. Sci. 46 (2011) 5595–5614, https://doi.org/10.1007/s10853-011-5572-y.
[38] X. Zhang, J. Zheng, Y.Q. Du, Z.W. Wang, Y.D. Wu, G. Luo, Graphene-polymer
nanocomposites for thermal conductive applications, IOP Conf. Ser.Mater. Sci. Eng.
770 (2020), https://doi.org/10.1088/1757-899X/770/1/012015.
[39] K.M.F. Shahil, A.A. Balandin, Thermal properties of graphene and multilayer
graphene: applications in thermal Interface materials, Solid State Commun. 152
(2012) 1331–1340, https://doi.org/10.1016/j.ssc.2012.04.034.
[40] L. Zhang, H. Deng, Q. Fu, Recent progress on thermal conductive and electrical
insulating polymer composites, Compos. Commun. 8 (2018) 74–82, https://doi.
org/10.1016/j.coco.2017.11.004.
[41] S. Chen, Q. Liu, L. Gorbatikh, D. Seveno, Does thermal percolation exist in
graphene-reinforced polymer composites? A molecular dynamics answer, J. Phys.
Chem. C 125 (2021) 1018–1028, https://doi.org/10.1021/acs.jpcc.0c09249.
[42] F. Kargar, Z. Barani, R. Salgado, B. Debnath, J.S. Lewis, E. Aytan, R.K. Lake, A.
A. Balandin, Thermal percolation threshold and thermal properties of composites
with high loading of graphene and boron nitride fillers, ACS Appl. Mater. Interfaces
10 (2018) 37555–37565, https://doi.org/10.1021/acsami.8b16616.
13
Progress in Organic Coatings 179 (2023) 107517
[43] M. Shtein, R. Nadiv, M. Buzaglo, K. Kahil, O. Regev, Thermally conductive
graphene-polymer composites: size, percolation, and synergy effects, Chem. Mater.
27 (2015) 2100–2106, https://doi.org/10.1021/cm504550e.
[44] S.M. Mirabedini, A. Kiamanesh, The effect of micro and nano-sized particles on
mechanical and adhesion properties of a clear polyester powder coating, Prog. Org.
Coat. 76 (2013) 1625–1632, https://doi.org/10.1016/j.porgcoat.2013.07.009.
[45] D. Czachor-Jadacka, B. Pilch-Pitera, Progress in development of UV curable
powder coatings, Prog. Org. Coat. 158 (2021), 106355, https://doi.org/10.1016/j.
porgcoat.2021.106355.
[46] N. Ayrilmis, A review on electrostatic powder coatings for the furniture industry,
Int. J. Adhes. Adhes. 113 (2022), 103062, https://doi.org/10.1016/j.
ijadhadh.2021.103062.
[47] S.I. Mollik, R.B. Alam, M.R. Islam, Significantly improved dielectric properties of
bio-compatible starch/reduced graphene oxide nanocomposites, Synth. Met. 271
(2021), 116624, https://doi.org/10.1016/j.synthmet.2020.116624.
[48] E.P.M. van Westing, G.M. Ferrari, J.H.W. de Wit, The determination of coating
performance with impedance measurements-I.Coating polymer properties, Corros.
Sci. 34 (1993) 1511–1530, https://doi.org/10.1016/0010-938X(93)90245-C.
[49] C.H. Hsu, F. Mansfeld, Concernng the conversion of the constant phase element
parameter Y0 into a capacitance, Corrosion 57 (2001) 747–748, https://doi.org/
10.5006/1.3280607.
[50] N. Diban, M. Mantecón-Oria, M.T. Berciano, A. Puente-Bedia, M.J. Rivero,
A. Urtiaga, M. Lafarga, O. Tapia, Non-homogeneous dispersion of graphene in
polyacrylonitrile substrates induces a migrastatic response and epithelial-like
differentiation in MCF7 breast cancer cells, Cancer Nanotechnol. 13 (2022) 1–29,
https://doi.org/10.1186/s12645-021-00107-6.
[51] K. Kim, K.H. Nam, J. Lee, H.J. Kim, M. Goh, B.C. Ku, N.H. You, Effect of defect-
healing in graphene nanosheets on the mechanical properties of polyimide
nanocomposites, Carbon 122 (2017) 614–621, https://doi.org/10.1016/j.
carbon.2017.06.102. N. Y.
[52] F. Jiang, W. Zhao, Y. Wu, J. Dong, K. Zhou, G. Lu, J. Pu, Anti-corrosion behaviors
of epoxy composite coatings enhanced via graphene oxide with different aspect
ratios, Prog. Org. Coat. 127 (2019) 70–79, https://doi.org/10.1016/j.
porgcoat.2018.11.008.
[53] M. Skrifvars, P. Niemelä, R. Koskinen, O. Hormi, Process cure monitoring of
unsaturated polyester resins, vinyl Ester resins, and gel coats by Raman
spectroscopy, J. Appl. Polym. Sci. 93 (2004) 1285–1292, https://doi.org/10.1002/
app.20584.