Composites Part B 201 (2020) 108375

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Graphene oxide thin film structural dielectric capacitors for aviation static
electricity harvesting and storage
Kit-Ying Chan a, Duy Quang Pham b, Baris Demir c, Dan Yang a, Edwin L.H. Mayes d,
Adrian P. Mouritz e, Andrew S.M. Ang b, Bronwyn Fox f, Han Lin a, Baohua Jia a, Kin-Tak Lau a, *
a
Centre for Translational Atomaterials, Swinburne University of Technology, Hawthorn, Melbourne, VIC, 3122, Australia
b
Department of Mechanical and Production Design Engineering, Surface Engineering for Advanced Materials (SEAM), Faculty of Science, Engineering and Technology,
Swinburne University of Technology, Hawthorn, Melbourne, VIC, 3122, Australia
c
Centre for Theoretical and Computational Molecular Science, The Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane,
Queensland, 4072, Australia
d
RMIT Microscopy and Microanalysis Facility, RMIT University, Melbourne, VIC, 3001, Australia
e
School of Engineering, RMIT University, Melbourne, VIC, 3001, Australia
f
Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Melbourne, VIC, 3122, Australia

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

Keywords: In this paper, we demonstrate the feasibility of using carbon fibre reinforced polymer (CFRP) laminates for the
Polymer crosslinking dual functions on aircraft as high load-bearing structural materials as well as for the harvesting and storage of
Graphene oxide film static electricity during flight which can be used to power navigation lights and other electrical systems. CFRP
Mechanical properties
laminate was fabricated into a structural dielectric capacitor (SDC) composite by sandwiching graphene oxide
Energy harvesting and storage
Aviation applications
(GO) film between two electrically-conductive carbon fabric layers. To meet the high requirements of aviation
applications, the mechanical properties of the GO-based SDC composite were increased using a polymer cross-
linking agent in the GO film. This work opens a new concept and possibility of converting the safety threat­
ening static charges into useful electrical energy, which not only reduces the safety hazard, but also improves the
energy efficiency of aircraft without compromising the mechanical performance.

1. Introduction power electronic devices, such as monitoring sensors, on aircraft has

Carbon fibre reinforced polymer (CFRP) composites are widely used
in primary structures, including the fuselage and wings, to military,
passenger, cargo and general aviation aircraft to achieve weight saving.
The use of CFRP composites compared to traditional metallic materials
such as aluminium alloys in aircraft can improve the fuel efficiency by
up to 20% [1], as well provide other benefits including superior fatigue
strength and less corrosion. At the normal cruising altitude for com­
mercial aircraft (~11 km), the atmospheric humidity is extremely low
[2]. As such, static electricity is generated and accumulated due to
friction between the outer surface of aircraft and molecules in the at­
mosphere, as illustrated in Fig. 1(a). The accumulation of a large amount
of static electricity can adversely affect the avionics and other
electrically-powered instruments on aircraft. To tackle this issue, de­
vices are installed to eliminate the accumulation of static charge on the
surface of aircraft. Recently, the use of harvested electrostatic energy to
been proposed by using conventional capacitors [3]. Instead of using
devices to discharge static electricity, it is potentially more beneficial to
harvest the static electricity which can be stored directly in CFRP
composite structures to power electrical systems such as the navigation
lights at the wing tips. To facilitate the electrostatic charges flow in the
body of aircraft, a potential difference between two points of aircraft is
needed, as illustrated in Fig. 1(a). As the antennas have only been
implemented on one side of aircraft, the other parts of aircraft are at
relatively high potentials due to the accumulation of electrostatic
charges. As such, the negative charges will flow from a relatively high
potential to a site of lower potential causing electron flow. Therefore,
electrical energy storage can be achieved by converting the original
CFRP composite into a structural dielectric capacitor (SDC) composite.
This conversion is achieved by sandwiching an electrical insulating layer
between electrically conductive carbon woven fabrics during manufac­
ture of the CFRP laminate, as shown in Fig. 1(b) [4]. SDC composites

* Corresponding author.
E-mail address: aklau@swin.edu.au (K.-T. Lau).

https://doi.org/10.1016/j.compositesb.2020.108375
Received 13 July 2020; Received in revised form 18 August 2020; Accepted 20 August 2020
Available online 27 August 2020
1359-8368/© 2020 Elsevier Ltd. All rights reserved.
K.-Y. Chan et al.
have high mechanical properties similar to conventional CFRP laminates
with the additional functionality of storing and conducting electric
power. The use of SDC composites in aircraft structures has the potential
to improve energy efficiency without significantly altering the
manufacturing process and mechanical properties of the CFRP
composite.
A large body of research has focused on using electrically insulating
materials, including polymer films [5] and glass fibre reinforced poly­
mer (GFRP) composites [6], as the dielectric layer within carbon
fibre-based SDC composites. This research has improved the electrical
energy storage capacity and mechanical properties of SDC composites
compared to first-generation of SDCs that used different types of paper
for the dielectric layer [7]. Graphene oxide (GO) film has proven a
highly effective dielectric separator in SDC composites due to its high
mechanical and insulting properties [8–10]. The specific capacitance of
GO-based SDC composites is at least 80 times higher than SDC com­
posites containing polymer film or GFRP laminate due to the high areal
density of oxygen-functional groups (OFGs) in the GO film. The OFGs
also promote bonding interactions between the GO film and polymer
(usually epoxy) matrix phase to the carbon fibre layers of SDC com­
posites, which contributes towards the higher mechanical properties of
GO-based SDC composites compared to other types of SDC composites
[5–9]. Also, GO film can be used as an ultra-thin layer (as thin as ~5 μm)
due to the high insulation efficiency, thus adding little weight penalty
(under 2%) to the composite material.
However, a problem with GO-based SDC composites is their sus­
ceptibility to delamination cracking along the GO film, particularly
when subjected to interlaminar shear (mode II) load [8,9]. Composite
aircraft structures can be subjected to interlaminar shear loads, such as
bending of the wings under aerodynamic loading, and therefore it is
essential that GO-based SDC composites used in aircraft are resistant to
delamination cracking. Strong interlayer and intralayer interactions are
needed for the GO film to ensure effective load transfer within GO-based
SDC composites to increase the mode II delamination resistance. Several
studies have demonstrated that polymers that promote a high concen­
tration of cross-linking with OFGs, such as polyimide [11], poly­
dimethylsiloxane and poly(glycidyl methacrylate) [12] and
polyallylamine (PAA) [13], can improve the tensile properties and
toughness of GO films. In particular, Park et al. presented a simple
process to fabricate the PAA-modified GO film with a uniform dispersion
of cross-linking compounds both between the GO nanosheets within the
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Composites Part B 201 (2020) 108375
film and as well as on the outer surfaces of the film [13]. This film had
both higher bonding strength and higher tensile properties compared to
an unmodified GO film [13]. In addition, compared to other polymers (e.
g. polyimide, polydimethylsiloxane and poly(glycidyl methacrylate),
PAA is a long-chain alkyl containing a higher linear density of reactive
amine groups [14]. The high density of amine groups increases the
number of covalent bonds between PAA and GO, as well as between the
PAA and epoxy matrix phase to GO-based SDC composites. As such, the
PAA cross-linking agent not only improves the mechanical properties of
GO film but also increases the bonding strength between the film and
epoxy matrix to GO-based SDC composites. Therefore, the delamination
resistance of PAA-modified GO-based SDC composites under bending
force is expected to be improved.
In this study, we aim to improve the delamination resistance prop­
erties of GO-based SDC composites. The mechanism by which the PAA-
crosslinker increases the mechanical properties (reduced elastic
modulus, hardness and interlaminar shear strength) of GO film was
investigated. Preliminary experimental prototyping was also performed
to simulate the use of an electrostatic charge to power a lighting system
by using GO-based SDC composites, which has the potential to power
navigation lighting on aircraft with further development.
2. Results and discussion
2.1. Fabrication of crosslinked GO film and property characterization
Commercial GO solution (10 mg/ml) was chemically crosslinked
using PAA [13], as shown schematically in Fig. 2(a). Free-standing GO
films were extracted from the solution using a vacuum filtration method.
The samples with and without the use of PAA-crosslinker were termed
‘PAA/GO’ and ‘Pristine GO’, respectively. Changes to the GO due to
chemical crosslinking reactions with the PAA were systematically
characterised using various techniques. Fig. 2(b–e) presents scanning
electron microscopy (SEM) and transmission electron microscopy (TEM)
images showing the morphology of GO films. The thickness values of the
Pristine GO and PAA/GO films were ~5 μm and ~6 μm respectively,
with both films containing the same number of stacked GO sheets. This
difference in thickness is due to the intercalated PAA molecules. The
thickness of ~5 μm for GO films was chosen in this study to prevent
electrons passing between the two carbon fabric layers. From our pre­
vious studies [8–10], we found that films with thickness of ~5 μm were
Fig. 1. Illustration of application of SDC composites
to harvest and store the electrostatic energy from the
environment directly in the body of aircraft. (a)
Generation of negative charges due to friction be­
tween the external surface of aircraft and air flow and
formation of potential differences in aircraft causing
electron flow. (b) Conversion of conventional CFRP
laminate (currently deployed in airframes) into a SDC
composite with the incorporation of graphene oxide
(GO) dielectric layer (potentially applicable in future
airframes).
K.-Y. Chan et al. Composites Part B 201 (2020) 108375

Fig. 2. (a) Schematic of synthesis of PAA/GO solution. The orange box indicates the presence of PAA molecule. Note that crosslinking occurs between amine groups
of PAA and carboxylic acid groups of GO [14]. SEM cross-sectional images of (b) Pristine GO and (c) PAA/GO films. Planar TEM images of (d) Pristine GO and (e)
PAA/GO films. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

suitable as the dielectric separator (insulator) without significantly
increasing the volume and weight of the CFRP composites. Pristine GO
had typical 2D nanosheet morphology with ripples at the edge (Fig. 2
(d)) whereas the surface of PAA/GO was more wrinkled (Fig. 2(e)), and
again this difference is due to the PAA molecules which act as a spacer
between the GO sheets.
To understand the chemical bonds formed between GO and PAA,
Fourier-transform infrared (FTIR) spectroscopy was used to characterize
the Pristine GO, PAA and PAA/GO films, as shown in Fig. 3(a). From the
spectra, the OFGs of GO were identified by peaks associated with C–O
(~1050 cm− 1), C–O–C (~1220 cm− 1), C–OH (~1370 cm− 1), C– –C
(~1550 cm− 1), C– – O in carboxylic acid and carbonyl groups (~1720
cm− 1) and O–H vibration, which is a broad peak between 3000 and
3500 cm− 1 [15–19]. PAA exhibited characteristic peaks of NH2 bands at
~1590 and ~1480 cm− 1, and NH2 stretch at 3428 cm− 1. There were
additional peaks for the PAA/GO at ~1270, ~1600 and 3300–3500
cm− 1, and these correspond to C–N stretch, N–H bending and N–H
stretch, respectively [20]. Furthermore, structural changes of GO
through the chemical crosslinking were confirmed using X-ray diffrac­
tion (XRD), as shown in Fig. 3(b). Pristine GO displayed a diffraction

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K.-Y. Chan et al. Composites Part B 201 (2020) 108375

Fig. 3. (a) FTIR spectra, (b) XRD patterns and (c) XPS spectra of Pristine GO and PAA/GO. (d) C1s spectrum of Pristine GO. (e) C1s and (f) N1s spectra of PAA/GO.

peak at 2θ = 9.2◦ , which can be indexed to the (001) reflection of GO
with an interlayer spacing of 9.6 Å that was calculated using Bragg’s Law
(2d sinθ = nλ). The peak intensity was 2θ = 7.5◦ for PAA/GO, which
corresponds to the interlayer spacing of 11.8 Å. The results indicate that
the PAA molecules were successfully intercalated into GO sheets and
formed crosslinks with the OFGs in GO. X-ray photoelectron spectros­
copy (XPS) was also used to determine the chemical bonds in the GO
films, and the wide-scan spectra of Pristine GO and PAA/GO are pre­
sented in Fig. 3(c). Pristine GO exhibited two signals which are C1s and
O1s, whilst PAA/GO showed three signals corresponding to C1s, O1s
and N1s, which was due to the presence of amine groups (NH2) in PAA.
Compared to the high resolution C1s spectra of Pristine GO (Fig. 3(d)),
there was a new component for C–N bond (285.7 eV) in the spectra of
PAA/GO (Fig. 3(e)). This is further confirmed by the high resolution N1s
of PAA/GO (Fig. 3(f)) that indicates C–N and N–H bonds. This is evi­
dence of cross-linking between the OFGs in GO and the amine groups in
PAA, which is consistent with the previous study [13].
Thermogravimetric analysis (TGA) was performed to determine the
effect of PAA on the thermal stability of GO films, as shown in Fig. S1
(ESI†). Pristine GO exhibited 20% and 40% weight loss at 195 ◦ C and

Fig. 4. (a) Nanoindentation force-displacement curves of Pristine GO film and PAA/GO film. (b) Reduced elastic modulus and (c) hardness of films. (d) ILSS of SDC
composites. (e) Illustration of interlaminar shear strengthening mechanism of the composites using PAA crosslinker.

4
K.-Y. Chan et al.
445 ◦ C, respectively due to the elimination of OFGs. The 20% and 40%
weight loss of PAA/GO were 220 ◦ C and 485 ◦ C, respectively. The
temperatures for PAA/GO are higher than Pristine GO due to cross-
linking between OFGs in GO and PAA molecules, of which extra en­
ergy is needed to break down. This result also indicates the successful
intercalation of PAA molecules in GO.
2.2. Mechanical properties of GO films and GO-based SDC composites
The reduced elastic modulus and hardness of the GO films were
measured using nanoindentation. These values were calculated from the
indentation load-displacement curve using the Oliver and Pharr method
[21]. Load-displacement curves for the Pristine GO and PAA/GO using
the load control-closed loop indent at a peak load of 150 μN are shown in
Fig. 4(a). The reduced elastic modulus and hardness values determined
from at least 100 indents are presented in Fig. 4(b) and (c), respectively.
Both the reduced elastic modulus (+45.8%) and hardness (+20.5%) of
the PAA/GO film are higher than the Pristine GO. This suggests that the
OFGs in GO sheets are reactive sites to form covalent bonds with PAA
molecules, as shown in Fig. 2(a). The bonds resist both shear and
transverse movement of the GO sheets, thereby increasing the film’s
reduced elastic modulus. The significance in difference between two
groups were also tested using the Student t-test (Table S1, ESI†).
Short beam shear (SBS) tests were performed to determine the effect
of PAA-crosslinker on the interlaminar shear strength (ILSS) of the GO-
based SDC composite, as illustrated in Fig. 4(d). The ILSS of the PAA-
modified GO-based SDC composite was 26.5% higher than the Pristine
GO-based SDC composite, and this improvement is attributed to the
improved load-sharing within the GO film with the use of PAA. As shown
in Fig. 4(e), increased and stronger interlayer and intralayer interactions
occur between GO sheets due to PAA whilst the interfacial bonding
between the GO film and epoxy is retained. The high interaction pro­
moted more effective shear load transfer and sharing between GO sheets
and inside the PAA-modified composite. The formation of covalent
bonds between GO sheets increased the resistance against both shear
and transverse movement, thereby increasing the ILSS of the GO-based
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Composites Part B 201 (2020) 108375
composite. Importantly, the possibility of shear-induced cohesive
delamination in the GO film decreased from 57.2% to 14.3% with the
use of PAA-crosslinker.
2.3. Electrical properties of GO-based SDC composites
To demonstrate the feasibility of both Pristine GO and PAA/GO films
as the dielectric separator in SDC composites, electrochemical imped­
ance spectrometry (EIS) was performed to evaluate their resistivities, as
shown in Fig. S2 (ESI†). Both Pristine GO and PAA/GO films had re­
sistivity values of at least 400000 Ω m in the frequency range of
0.1–100000 Hz, thereby being insulators. In addition, the specific area
of woven carbon fabrics was measured to be ~2.9 m2/g using Bru­
nauer–Emmett–Teller (BET) theory, as shown in Fig. S3(a). The pore
volume and pore size distribution of woven carbon fabric were calcu­
lated using the Barrett, Joyner and Halenda (BJH) method from ab­
sorption and desorption isotherms, as displayed in Fig. S3(b) and (c).
The effect of PAA on the energy storage performance of the GO-based
SDC composites was investigated using cyclic voltammetry (CV) and
constant current charge and discharge (CCCD) tests. The CV curve was
measured at the voltage scan rate of 5 mV/s (within a voltage window of
±0.5 V), as presented in Fig. 5(a). Both GO-based SDC composites
exhibited a similar curve profile without redox peaks, indicating the
excellent ability of fast electrical charging and discharging. The output
current of the CV curves decreased in the presence of PAA, resulting in a
reduction in capacitance. The reduction is due to the low dielectric
constant of PAA polymer. However, the specific capacitance (~1 mF/
m2) of the PAA-modified GO-based SDC composite is higher than other
types of SDC composites containing GFRP (0.188 – 0.444 μF/m2) or
polymer films (0.206 – 2.466 μF/m2) as the dielectric separator [5–7,
22]. The higher specific capacitance of GO-based SDC composite when
compared to other SDC composites is due to the abundance of OFGs,
which are highly polarizable, in GO. As such, the GO film becomes
polarized under an externally applied electric field via the orientation of
polar molecules. The high dipole moments of OFGs induce an internal
electric field, which is in the opposite direction to the applied field, in
Fig. 5. Electrical performance of GO-based SDC
composites. (a) CV curves of GO-based SDC compos­
ites in a potential range of ±0.5 V with a scan rate of
5 mV/s (b) CCCD curves of PAA-modified GO-based
SDC composite at different applied current densities.
(c) Effect of current density on the specific capaci­
tance of PAA-modified GO-based SDC composite. (d)
Long-term stability of PAA-modified GO-based SDC
composite within a potential range of 10 V. The inset
shows the charge and discharge curves of 1st cycle
(black) and 5000th cycle (red). (For interpretation of
the references to colour in this figure legend, the
reader is referred to the Web version of this article.)
K.-Y. Chan et al.
the GO film of the SDC composite. The resultant electric field in the
composite decreases thereby causing the capacitance to increase be­
tween the carbon electrodes.
Different discharge current densities (0.05, 0.1, 0.2 and 0.5 μA/cm2)
were applied to the PAA-modified GO-based SDC composite to study its
effect on energy storage capacity, as shown in Fig. 5(b). The CCCD
curves were symmetric for all discharge current densities. These results
indicate that the ability of fast charging and discharging of the PAA-
modified GO-based SDC composite was maintained over the range of
current densities that were studied. It was found that the specific
capacitance of PAA-modified GO-based SDC composites decreased with
increasing the applied current density. This is due to the insufficient
time for molecular polarization of OFGs due to the fast charge and
discharge rate, leading to the measured reduction in charge storage
capacity.
The energy density of PAA-modified GO-based SDC composites at
different power density was calculated from the CCCD analysis, as
shown in Fig. S4a (ESI†). It should be noted that the PAA-modified GO-
based SDC composite had superior voltage range (≥10 V), as shown in
Fig. 5b, compared to supercapacitors (~3.5 V) and batteries (~1.2 V).
The voltage range was limited by the compliance voltage of the testing
system, and not by the composite itself. The GO-based SDC composites
exhibited a high working voltage, up to ~400 V [8–10] and shown in
Fig. S4b (ESI†). It is expected that the breakdown voltage will be
retained or even higher for the PAA-modified GO-based SDC composite
due to the superior dielectric breakdown strength of polymer materials.
As such, the estimated energy density and power density of
PAA-modified GO-based SDC composites are 0.21 J/cm3 and 11
kW/cm3, respectively, using the equations below [23]:
/ lamp increased at a controlled rate (Stage A→B). The rate can be varied
1
E = CV 2 Volume
2 resistor (i.e. 150 kΩ in our study) used in the electric circuit. When the
P=
ΔV 2
4 × Rs × Volume
where E is energy density (J/cm3), C is the total capacitance (F), V is the
maximum working voltage (V),Volume (cm3), P is power density (W/
R
cm3), ΔV is the potential window in CCCD curve and Rs = 2Iapplied
drop
. and produced bright and intermittent flashes, as demonstrated in our
Fig. 6. Experimental demonstration of GO-based SDC composite for lighting. (a) Electric circuit for navigation light application. (b) Voltage change across the GO-
based SDC composite obtained using multimeter (Stage A→B: capacitor charging; Stage B: Neon gas ionizes; Stage B→C: capacitor discharging). (c) Images of neon
light at different stages.
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Composites Part B 201 (2020) 108375
The excellent long-term stability of the PAA-modified GO-based SDC
composite is presented in Fig. 5(d), which retained > 97% capacitance
after 5000 cycles at the current density of 1 μA/cm2.
2.4. Preliminary experimental prototype of powering navigation lights of
aircraft using GO-based SDC composites
The specific capacitance of GO-based SDC composites is several or­
ders of magnitude lower than those of supercapacitors and batteries
[24]. However, SDC composites have a much wider voltage range and
the capacity of ultrafast charging and discharging when compared to
structural supercapacitors and batteries [4,25,26]. Therefore, SDC
composites are more suitable for applications that require high power
density with less requirements on the energy density. Together with
high mechanical properties and almost infinite cycle life, GO-based SDC
composites are excellent candidate for aviation applications that harvest
the energy during flight to power electronic devices such as navigation
lights.
To demonstrate the feasibility of using GO-based SDC composites in
aircraft, a direct current (DC) power supply and neon lamp were used to
construct a prototype for electrostatic energy harvesting from the
environment and the navigation light used in the aircraft respectively, as
shown in Fig. 6(a) and Fig. S5 (ESI†). The neon gas has an extremely high
resistance and as such the lamp does not conduct electricity unless the
neon is ionized. As depicted in Fig. 6(b), when the electrostatic energy
was continuously harvested from the environment (i.e. the DC power
supply in our experiment), the GO-based SDC composites were being
charged. The voltage across the GO-based SDC composites and neon
by changing the capacity of the SDC composites and the resistance of
voltage across the neon lamp reached ~70 V, the neon ionized with a
spark between the electrodes (Stage B). Then the SDC devices dis­
charged quickly, which caused a sudden increase to the electric current
and heated the neon gas to a plasma state, inducing conduction between
two electrodes of the neon lamp (Stage B→C). Once fully discharged
(Stage A/C), the electrostatic energy charged up the SDC devices again
experiments (Fig. 6(c) and Video 1 in ESI†).
K.-Y. Chan et al.
Supplementary video related to this article can be found at http
s://doi.org/10.1016/j.compositesb.2020.108375
3. Conclusion
This work demonstrated a high improvement in the mechanical
properties of a GO-based SDC composite using PAA-crosslinker in GO
films. A systematic characterization was performed to study the inter­
action between PAA and OFGs in GO, and thus demonstrated the suc­
cessful intercalation of PAA molecules into GO sheets. The mechanical
properties of GO films have also been investigated using nano­
indentation, and the mechanism by which the PAA-crosslinker improved
the reduced elastic modulus and hardness of GO film was discussed. The
reduced elastic modulus and hardness of PAA/GO film were 45.8% and
20.5% higher, respectively, when compared to Pristine GO. The for­
mation of covalent bonds between PAA and OFGs in GO increased the
resistance to interlaminar shear and transverse movement of GO sheets,
resulting in the higher properties of reduced elastic modulus and hard­
ness obtained by nanoindentation. The ILSS of the PAA-modified GO-
based SDC composite was 26.5% higher than the unmodified material.
The specific capacitance of the GO-based SDC composite was reduced
with the presence of PAA, although the energy storage performance was
still much higher compared to other SDC composites containing GFRP or
polymer-based dielectric films.
The first prototype of using GO-based SDC composites to harvest
static electricity generated in air and to power navigation lights and
possibly other electrical devices on aircraft has been developed. These
results have opened the new possibility in collecting and storing static
charges in the airplane body during flight. The high mechanical prop­
erties and moderate energy storage performance of GO-based SDC
composites show great potential to aviation navigation applications,
harvesting the ambient energy and thus maximizing the energy effi­
ciency of air transportation.
While the PAA-modified GO-based SDC composite shows an
improvement to reduced modulus, hardness and interlaminar shear
strength, further characterization of the mechanical properties is needed
to fully assess its suitability for aircraft structures. The in-plane me­
chanical properties (e.g. tension, compression, bending, shear), fracture
toughness, damage tolerance, environmental durability and other
properties need to be characterised to assess the composite for aero­
structures with energy harvesting and energy storage functionality. With
the application of continuous centrifugal casting technique [27],
large-scale PAA-modified GO films can be fabricated by simply modi­
fying the GO solution for the further development.
4. Experimental section
4.1. Materials
A GO solution (10 mg/ml) was produced using the modified Hum­
mer’s method (SupraG Energy Pty Ltd.). Polyallylamine (PAA, 20 wt%
aqueous suspension with Mw = 17,000) was sourced from Sigma-Aldrich
and used without further purification. Deionised (DI) water (18.2 MΩ ⋅
cm) from a Milli-Q water purification system was also used in the syn­
thesis process. T300 plain woven carbon fabric with areal weight of 196
g/m2 was supplied by Toray Industries (Japan) and the epoxy resin and
its hardener (105/206) were obtained from West System.
4.2. Synthesis and fabrication of PAA/GO films
The pristine (i.e. as supplied) GO solution was chemically modified
using PAA [13]. Briefly, the GO solution was diluted to a concentration
of 3 mg/ml using DI water, and then the diluted solution was sonicated
for 30 min to evenly disperse the GO sheets. PAA was then added to the
GO solution at the weight ratio of GO/PAA = 3.75, which resulted in the
immediate precipitation of agglomerated GO particles. The solution was
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Composites Part B 201 (2020) 108375
further diluted with DI water to 0.2 mg/ml and sonicated for 6 h to
obtain a homogeneous colloidal suspension of PAA-crosslinked GO
(PAA/GO) sheets. The filtration of both unmodified GO and
PAA-modified GO solutions was performed under vacuum using a pol­
yethersulfone (PES) membrane with a diameter of 47 mm and nominal
pore size of 0.03 μm. Prior to vacuum filtration, the solution was soni­
cated for 30 min to evenly disperse the GO sheets. The film was filtrated
and then flushed three times with DI water (3 × 10 ml) to remove excess
PAA molecules. The film was then dried at 20 ◦ C under vacuum for 24 h,
followed by further drying at 60 ◦ C for 3 h in a convection oven. The
dried film was peeled from the membrane, placed in a petri dish and
then soaked in DI water for further rinsing. The films were dried again at
60 ◦ C in a convection oven for 24 h.
4.3. Structural characterization of GO films
SEM images of the GO films were taken using a ZEISS SUPRA 40 VP
field emission scanning electron microscope (FE-SEM) operated at an
accelerating voltage of 5 kV. HR-TEM analysis was performed using a
JEOL JEM-2100F operated at 200 kV with a Gatan OneView CCD
camera. Prior to the sample preparation, the solution was dispersed in
methanol and sonicated for 30 min to ensure an even dispersion of GO
sheets. TEM specimens were prepared by dropping 10 μL of solution
onto a lacey carbon grid and then dried. FTIR spectrometry (Bruker
Hyperion 2000) was used to determine the chemical bonds in GO over
the wavelength region of 4000–500 cm− 1. XRD analysis was conducted
using a Bruker D8 Advance diffractometer to determine the interlayer
spacing of GO. The XRD pattern was acquired using a Cu Kα (λ = 0.154
nm) in the 2θ range between 5 and 55◦ at a step size of 0.05◦ . XPS was
performed to determine the chemical composition of GO. Wide-scan XPS
survey spectra and high-resolution spectra of C1s were performed to
identify the presences of elements and OFGs, respectively. The spectra
were recorded using a Thermo Scientific k-Alpha XPS instrument with a
monochromated Al Kα X-ray (1486.6 eV) source, a spot diameter of 400
μm and a pass energy of 50 eV, providing an overall resolution of 0.1 eV.
CasaXPS processing software was used to perform curve fitting and data
analysis. TGA (TGA Q500, TA Instruments) was performed to measure
the thermal stability of GO over the temperature range of 50–600 ◦ C in
N2 atmosphere at the heating rate of 10 ◦ C/min.
4.4. Mechanical characterization of GO films
Nanoindentation of the GO films was performed at ambient condi­
tion using a Hysitron TI Premier Instrument (Bruker, Eden Prairie, MN,
USA) with a Berkovich diamond indenter. The values of reduced elastic
modulus and hardness were calculated from the applied indentation
load-tip displacement response using the theory developed by Oliver
and Pharr [21]. The elastic modulus is the combined modulus of the
system and is thus termed the reduced elastic modulus. As such, the
trends in the reduced elastic modulus and the actual elastic modulus of
materials are the same [21]. To minimize the indentation size effect, the
appropriate test load for the experiment was selected to exceed the
penetration depth of ~50 nm whereby friction does not plays a signif­
icant role in the measured hardness [28]. The penetration depth should
be less than 10% of the film thickness to eliminate the effect of the
underlying substrate [21], and as such a peak load of 150 μN was used
for the GO films. Prior to nanoindentation testing, the samples were held
at 50 ◦ C to minimize the absorption of moisture that can alter the me­
chanical properties of GO films. The scanning probe microscopy (SPM)
function was employed with a constant imaging force of 2.0 μN and scan
rate of 0.5 Hz to scan the sample surface. There were at least 3 runs of
the nanoindentation on different locations across the sample, with a
total number of 100 indents performed on each run using a constant
loading rate of 700 μN/s and an indent spacing of 2 μm. The nano­
indentation measurements were conducted under a load control closed
loop with a 0.1 s hold segment to allow for thermal drift correction.
K.-Y. Chan et al.
4.5. Mechanical and electrical characterization of GO based SDC
composites
The effect of PAA-crosslinker on the ILSS of GO-based SDC com­
posites was studied using short beam shear test according to ASTM
D2344 specification. The dimension of ILSS samples was 24 mm long, 8
mm wide and 4 mm thick. The samples were loaded in three-point
bending with a support span-to-thickness ratio of 4-to-1 using MTS®
50 kN load capacity servohydraulic testing machine (Model 819, MTS
Systems Corporation). The samples were loaded at a centre-point
deflection rate of 1 mm/min until the first significant load drop
(≥30%), which was considered as failure. At least 10 ILSS samples of
each material were tested.
The electrical properties of GO-based SDC composites were deter­
mined using specimens that consisted of two CFRP plies (40 mm long ×
25 mm wide) as the conductive electrodes separated with a single layer
of GO film. The GO film used was 35 mm in diameter and had an excess
width of ≥3 mm around two sides of CFRP electrodes to prevent their
physical contact and to eliminate edge effects. Copper tape (60 mm long,
10 mm wide, 0.15 mm thick) was attached to the CFRP electrode as
current collectors. The influence of PAA-crosslinker on the electrical
energy storage capacity of GO-based SDC composites was evaluated
using cyclic voltammetry (CV) tests. The effect of current density on the
specific capacitance and long-term stability of PAA-modified GO-based
SDC composites were measured using constant current charge and
discharge (CCCD) analysis.
Author statement
Kit-Ying Chan: Conceptualization, Methodology, Formal analysis,
Data collection and analysis, Writing - original draft preparation, Visu­
alization, Duy Quang Pham: Methodology, Formal analysis, Data
collection and analysis, Writing - original draft preparation, Baris Demir:
Investigation, Writing - original draft preparation, Dan Yang: Writing -
original draft preparation, Visualization, Edwin L.H. Mayes: Data
collection and analysis, Writing - original draft preparation, Adrian P.
Mouritz: Supervision, Writing - review & editing, Andrew S.M. Ang:
Supervision, Writing - review & editing, Bronwyn Fox: Supervision,
Writing - review & editing, Han Lin: Supervision, Writing - review &
editing, Baohua Jia: Supervision, Writing - review & editing, Kin-Tak
Lau: Supervision, Writing - review & editing.
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.
Acknowledgement
This project is supported by a Swinburne University of Technology
research grant (SUPRA). The authors acknowledge the technical assis­
tance provided by the RMIT Microscopy and Microanalysis Research
Facility (RMMF), a linked lab of Microscopy Australia. K.C. acknowl­
edges the support from Faculty of Science, Engineering and Technology
HDR Publication Award. B.J. thanks the Australia Research Council
through the Discovery Project scheme (DP190103186) and the Indus­
trial Transformation Training Centres scheme (Grant No.
IC180100005).
Composites Part B 201 (2020) 108375
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compositesb.2020.108375.
References
[1] Lu B. The Boeing 787 dreamliner designing an aircraft for the future. J. Young
Investig. 2010;4026:34.
[2] Gigliotti K. Static electricity and aircraft. Wiley Encyclopedia of Composites; 2011.
p. 1–8.
[3] Xie H, Huang Z, Guo SJ, Torru E. Feasibility of an electrostatic energy harvesting
device for CFCs aircraft. Procedia Eng 2015;99:1213–22.
[4] Chan K-Y, Jia B, Lin H, Hameed N, Lee J-H, Lau K-T. A critical review on
multifunctional composites as structural capacitors for energy storage. Compos
Struct 2018;188:126–42.
[5] Carlson T, Ordéus D, Wysocki M, Asp LE. Structural capacitor materials made from
carbon fibre epoxy composites. Compos Sci Technol 2010;70(7):1135–40.
[6] O’Brien D, Baechle D, Wetzel E. Design and performance of multifunctional
structural composite capacitors. J Compos Mater 2011;45(26):2797–809.
[7] Luo X, Chung D. Carbon-fiber/polymer-matrix composites as capacitors. Compos
Sci Technol 2001;61(6):885–8.
[8] Chan K-Y, Lin H, Qiao K, Jia B, Lau K-T. Multifunctional graphene oxide paper
embodied structural dielectric capacitor based on carbon fibre reinforced
composites. Compos Sci Technol 2018;163:180–90.
[9] Chan K-Y, Yang D, Demir B, Mouritz AP, Lin H, Jia B, Lau K-T. Boosting the
electrical and mechanical properties of structural dielectric capacitor composites
via gold nanoparticle doping. Compos B Eng 2019;178:107480.
[10] Chan K-Y, Jia B, Lin H, Zhu B, Lau K-T. Design of a structural power composite
using graphene oxide as a dielectric material layer. Mater Lett 2018;216:162–5.
[11] Chen M, Yin J, Jin R, Yao L, Su B, Lei Q. Dielectric and mechanical properties and
thermal stability of polyimide–graphene oxide composite films. Thin Solid Films
2015;584:232–7.
[12] Song S, Zhai Y, Zhang Y. Bioinspired graphene oxide/polymer nanocomposite
paper with high strength, toughness, and dielectric constant. ACS Appl Mater
Interfaces 2016;8(45):31264–72.
[13] Park S, Dikin DA, Nguyen ST, Ruoff RS. Graphene oxide sheets chemically cross-
linked by polyallylamine. J Phys Chem C 2009;113(36):15801–4.
[14] Sahu M, Raichur AM. Toughening of high performance tetrafunctional epoxy with
poly (allyl amine) grafted graphene oxide. Compos B Eng 2019;168:15–24.
[15] Loryuenyong V, Totepvimarn K, Eimburanapravat P, Boonchompoo W, Buasri A.
Preparation and characterization of reduced graphene oxide sheets via water-based
exfoliation and reduction methods. Ann Mater Sci Eng 2013;2013.
[16] Thema F, Moloto M, Dikio E, Nyangiwe N, Kotsedi L, Maaza M, Khenfouch M.
Synthesis and characterization of graphene thin films by chemical reduction of
exfoliated and intercalated graphite oxide. J Chem 2012;2013.
[17] Thakur S, Karak N. Green reduction of graphene oxide by aqueous phytoextracts.
Carbon 2012;50(14):5331–9.
[18] Zhang H, Yang D, Lei C, Lin H, Jia B. Ultrahigh heating rate induced micro-
explosive production of graphene for energy storage. J Power Sources 2019;442:
227224.
[19] Wong SI, Lin H, Sunarso J, Wong BT, Jia B. Optimization of ionic-liquid based
electrolyte concentration for high-energy density graphene supercapacitors. Appl.
Mater. Today 2020;18:100522.
[20] Saini P, Singh M, Singh SP, Mahapatro AK. Spectroscopic and electronic properties
of polyallylamine functionalized graphene oxide films. Vacuum 2018;154:110–4.
[21] Pharr G, Oliver W. Measurement of thin film mechanical properties using
nanoindentation. MRS Bull 1992;17(7):28–33.
[22] Carlson T, Asp LE. Structural carbon fibre composite/PET capacitors – effects of
dielectric separator thickness. Compos B Eng 2013;49:16–21.
[23] Zhang S, Pan N. Supercapacitors performance evaluation. Adv. Energy Mater.
2015;5(6):1401401.
[24] González A, Goikolea E, Barrena JA, Mysyk R. Review on supercapacitors:
technologies and materials. Renew Sustain Energy Rev 2016;58:1189–206.
[25] Chung D. Development, design and applications of structural capacitors. Appl
Energy 2018;231:89–101.
[26] Chung DDL. A review of multifunctional polymer-matrix structural composites.
Compos B Eng 2019;160:644–60.
[27] Zhong J, Sun W, Wei Q, Qian X, Cheng H-M, Ren W. Efficient and scalable
synthesis of highly aligned and compact two-dimensional nanosheet films with
record performances. Nat Commun 2018;9(1):1–11.
[28] Li H, Ghosh A, Han Y, Bradt R. The frictional component of the indentation size
effect in low load microhardness testing. J Mater Res 1993;8(5):1028–32.