Journal of Alloys and Compounds 691 (2017) 220e229

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Development of graphite/silicone composites for use as flexible

electrode materials
^a a, Grasielli Correa de Oliveira a,
Ana Luísa Silva a, Matheus Millen Corre
Pedro Pablo Florez-Rodriguez b, Carlos Alberto Rodrigues Costa c, Felipe Silva Semaan a,
Eduardo Ariel Ponzio a, *
a
Grupo de Eletroquímica e Eletroanalítica (G2E), Instituto de Química da Universidade Federal Fluminense, Campus Valonguinho, CEP 24020-141, Nitero i,
RJ, Brazil
b
Laborato rio de Química Supramolecular e Nanotecnologia, Instituto de Química da Universidade Federal Fluminense, Campus Valonguinho, CEP 24020-
141, Niteroi, RJ, Brazil
c
Laborato rio de Ci^
encia de Superfícies (LCS), Brazilian Nanotechnology National Laboratory (LNNano), Centro Nacional de Pesquisa em Energia e Materiais
(CNPEM), CEP 13083-970, Campinas, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Graphite/silicone composites (SGCE) in different ratios were prepared and characterized for different
Received 6 April 2016 strategies, such as thermogravimetry (TG), Raman spectroscopy, and X-ray photoelectron spectroscopy
Received in revised form (XPS). A electrochemical characterization of the different electrodes was performed by applying cyclic
10 August 2016
voltammetry; experiments covered a potential window from
0.2 to 0.8 V (vs. AgjAgCl), using as a probe
Accepted 22 August 2016
Available online 24 August 2016
a K3Fe(CN)6 5 mmol L
1 in KCl 0.5 mol L
1 solution. Voltammetric profiles for both blank and probe
solutions were suitably recorded under a 50 mV s
1 scan rate. Results from cyclic voltammetry led to
morphological and topographical assessments performed by scanning electron microscopy (SEM) and
Keywords:
Flexible electrode
atomic force microscopy (AFM), respectively. The only ratio that showed flexible and self-sustaining
Composite electrodes properties with a reversible voltammetric profile at slow scan rates (5e15 mV s
1) was SG1. The use
Graphite of the SSF/Graphite-Silicone composite electrodes for electroanalytical applications is very promising,
Silicone since these types of electrodes allow for the monitoring of electroactivity, presenting applicability even
with low graphite ratios.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction original phases [2,3]. Some particular properties make composite

Electrode composite development began with an early
description by Adams [1], in 1958, followed by more defined and
categorized studies, especially by Tallman and Petersen, who
characterized deeper aspects and gave a more concise definition of
this material. Their definition can be simplified as a mixture of at
least two phases in which at least one must present conductive
properties and the other an insulating material, generating, after
mixing and incorporating processes, a conductive material with
physical and chemical properties different to those from the
* Corresponding author. Department of Physichal-Chemical, Fluminense Federal
~o Jo~  i, RJ,
University, Morro Sa ao Batista s/n, Campus Valonguinho, 24.020-141, Nitero
Brazil.
E-mail addresses: analuisa.als89@gmail.com (A.L. Silva), eaponzio@vm.uff.br
(E.A. Ponzio).
materials an attractive choice for electroanalysis, especially those
related to applicabilities at wide pH ranges, broad potential interval
of application, low costs, easy preparation and adequate surface
renewal, among others [2e4].
Due to their widely exploited and well-established properties,
special attention has been given to the use of carbon-derived ma-
terials as conductive phases. Among the most popular examples are
vitreous carbon, boron doped diamond, graphite, graphene, ful-
lerenes and carbon nanotubes [4]. Considering the insulating
phases, focus on polymeric materials is observed, especially
regarding resins, like epoxy, polyurethane and silicone, among
others [5e9]. Amounts and ratios must be carefully studied and
defined in order to reach the best combination possible, leading to
the most suitable composition assembling the best chemical,
physical and electrical properties for certain purposes [10]. In this
context, the present study aimed to assess the use of silicone and

http://dx.doi.org/10.1016/j.jallcom.2016.08.232
0925-8388/© 2016 Elsevier B.V. All rights reserved.
 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229 221

graphite. containing 5.0 mmol L
1 of potassium ferrycianide (Mallinckrodt®,

The choice of using silicone as an insulating phase is related to Ireland) in 0.50 mol L
1 KCl (Vetec®, Brazil) were used, prepared
its numerous applications. Noteworthy among them are mold- immediately prior to use.
ability (which allows the obtainment of specific formats and
shapes), low toxicity, and insolubility in water. In addition, other 2.2. Preparation of the built-in and flexible composite electrodes
interesting characteristics, such as high chemical and physical
stability and flexibility (since it is a thermoplastic) must be taken Composite electrodes were prepared by mixing graphite (Sigma
into account. These properties have raised many new application Aldrich®, <20 mm, USA) and Multi-Use Fisher silicone (Fisher®, USA)
possibilities besides those already described in the electroanalysis in order to obtain different graphite ratios (m/m) in the composites
literature. Some of these new perspectives can be appreciated in (50%, 60%, 70% and 80%), from now on named SG1, SG2, SG3 and
the development of portable cells, flexible electrodes, and SG4. The mixtures were mechanically homogenized during 10 min,
conductive filaments, among others [11e13]. and subsequently added into the syringe body under pressure.
In 1968, Pungor and Szepesvary [14] presented their first For the built-in composite electrodes, electrical contact was
description regarding the preparation and use of silicone rubber/ established by a copper wire; in the case of flexible composite
graphite composite electrodes (SGCE). That study and other papers electrodes, the electrical contact is the composite itself, in which
by Pungor et al. [14e16] gave birth to a series of experiments using direct contact by grabbing establishes the circuit (Fig. 1).
this type of electrode in different procedures for the voltammetric
determination of various analytes in many kinds of matrices.
2.3. Characterization techniques
At this point, it becomes interesting to note that, despite the
easy manipulation and well-defined preparation and voltammetric
Thermogravimetric analyses (TGA) were carried out on a Shi-
uses of SGCE, a twenty year gap without further voltammetric
madzu TG/DTA 60 (Shimadzu®, Japan), by placing approximately
studies is observed between their description and new applications
3 mg of each sample into alumina crucibles and heating them from
raised by Ref. [17]. Such lack of studies are not necessarily due to
25  C to 1100  C (heating rate 10  C min
1) under atmospheric
lack of interest, since potentiometric applications can be found in
conditions.
the literature [18e26].
Solids were also characterized by a Raman spectroscopy alpha
Many results previously reported in the literature present the
300 system (Witec®, Germany). The experiments were performed
applicability of SGCE as sensors, such as three different studies by
at 25  C using a  100 objective lens and a Nd:YAG green laser at
Santos et al. [7,26e28], in which the proposed electrode was
532 nm, with a small entrance (726 ct) to avoid the decomposition
applied to the differential pulse voltammetric determination of
of possible organic compounds in the samples during the analyses.
rutin and propranolol in pharmaceutical formulations, and applied
XPS analyses were performed on an ESCALAB 250Xi spectrom-
in new strategies using cyclic voltammetry (CV), and square wave
eter (Thermo Fisher Scientific®, USA) using monochromatic Al Ka
voltammetry (SWV) to determine hydrochlorotiazide in commer-
X-rays with a spot size of 650 mm for survey analysis and 900 mm for
cial samples.
specific elements (C, O, Si). Surface charging of the electrically
In addition to studies focused on electrochemical and electro-
insulating materials was compensated using an integrated flood
analytical approaches, many fields of expertise can clearly take
gun with an approximate spot size of 900 mm. For better de-
advantage of the development of new flexible electrodes, from
scriptions, solids were also treated with medium level Ion Gun,
electronics, capacitors, batteries, electrochromism, smart textiles,
with an energy of 3000 V during 180 s.
soft robotics and sensors to medical diagnostic tools. Some inter-
Scanning electron microscopy (SEM) analyses were performed
esting studies can be found over the past few years, for example in
on a Zeiss DSM 940-A microscope (Zeiss®, Germany) operated at
electroencephalography (EEG) [28], soft robotics [29], smart tex-
accelerating voltage of 15 kV, at a working distance of 8 mm at
tiles [30], electroenterography (EEnG) and electrohysterography
2000  magnitude.
(EHG) [31], lithium-ion batteries [32,33], artificial muscles of
Atomic force microscopy (AFM) images were obtained on a
dieletric elastomer actuators (DEAs) [34] and health monitoring
Nanosurf FlexAFM C3000 Controller (Nanosurf®, Switzerland). Ex-
[35]. For these applications, electrodes need soft substrates to
periments were conducted using a 2.8 N/m Pt-Ir probe in inter-
support conductive phases, making the development of flexible
mitent contact (topography and phase contrast), with scans
electrodes highly promising, since they can contribute to solve the
covering an area of about 30 mm  30 mm, containing 256  256
major problems regarding rigid sensors, such as the need for the
use of substrates and the fact that they are uncomfortable, many
times causing skin irritations that usually evolve to allergies
[28,29,32,35].
This paper presents, for the first time, the development of self-
sustained flexible composite electrodes based on graphite bonded
with silicone, or, in other words, electrodes that do not need sub-
strates, as well as the characterization of the material by scanning
electron microscopy (SEM), atomic force microscopy (AFM), ther-
mogravimetry (TG), Raman spectroscopy and X-ray photoelectron
spectroscopy (XPS), in addition to cyclic voltammetry.

2. Experimental

2.1. Reagents and chemicals

All solutions were prepared by direct dissolution of suitable

reagents (of analytical grade, used as received) in Milli-Q purified
water (Millipore®, Germany). Electrochemical probe solutions Fig. 1. Electrical contact of the flexible composite electrodes.
222 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229

pixels at maximum resolution. The Gwyddion 2.40 software pack-

age was used to analyze the AFM images.
The SG1 and SG3 samples had cylindrical form of 15 mm and
4 mm (length, diameter) of total volume area of 0.58 cm3 and the
images were obtained by a mCT 510 Versa scanner (ZEISS-Xradia).
Data were acquired with the following X-ray mCT setup: a)
35 keVe50 keV of X-ray energy range; b) 50 mAe70 mA intensity
filament current of X-ray source; c) 500 to 1000 projection data per
image and d) 30 mme1000 mm of final image resolution.
A Lloyd LK-10KN universal machine was used for the determi-
nation of the mechanical properties of the composites at 8 days of
age, according to a modified version of the ASTM D039 standard
method [36]. Bending tests were performed under displacement
control at a crosshead rate of 0.5 mm/min. Three SG1 specimens
with dimensions of 15 mm and 4 mm (length, diameter) were
tested under a three-point bending.

2.4. Electrochemical apparatus

Voltammetric experiments were performed, in triplicate, using

an Ivium nStat® multi-channel potentiostat (Ivium Technologies®,
Netherlands), controlled by the IviumSoft® software (Ivium Tech-
nologies®). The electrochemical system consisted of a three-
electrode cell. An AgjAgCl electrode was used as the reference
electrode, a silver wire as the counter electrode and self-sustained
flexible silicone-graphite composite electrodes as the working
electrode. The electrochemical activation of the electrode was Fig. 2. TGA and DTA curves for doped solids (heating rate 10  C min
1 under atmo-
spheric conditions).
performed by three successive cycles, from
0.2 to 0.8 V, under a
scan rate of 100 mV s
1, with a potential step of 5 mV. An elec-
trochemical K3Fe(CN)6 probe of a known redox system was used to related to the degradation of the remaining polymer under 600  C
evaluate electroactivity, chosen due to many characteristics, such as [40e43], while for graphite a single exothermic loss above 600  C
stability of the involved Fe[(CN)6]4- and Fe[(CN)6]3- species, pre- was observed, thus facilitating the development of a quantitative
dictable behaviour, well-known diffusion coefficients and avail- study in terms of graphite concentrations. These results are dis-
ability, among others, which makes such a pair suitable and even played in Table 1.
recommended for method validation and electrode assessment Raman spectra of the different materials (pure components and
[37e39]. Graphical data presentation was plotted using the Ori- their composites) are displayed in Fig. 3. The first spectra refers to
ginPro 8.0 software. pure graphite, where three characteristic D and G bands were
observed [44,45]. For pure silicone, bands located at 486, 707, 2848,
3. Results and discussion 2912, 2792 cm
1 were present. These bands can be related to in-
teractions such as Si-O-Si stretching, Si-C symmetric stretching,
3.1. Composite characterization CH3 symmetric stretching, CH3 asymmetric stretching, and C¼C
stretching, previously described by Bae et al. [46]. In addition, a
The stability of SSF/Graphite-Silicone composite electrodes at weak photoluminescense attributed to the amorphous character of
high temperatures can be verified using thermal methods, such as the amorphous carbon species present in the sample [47] was also
thermogravimetric analysis (TGA), whether under air or inert at- noted. All SSF/Silicone-Graphite composite electrodes presented
mosphere. The results obtained for both graphite and silicone first-order characteristic D and G bands, located at 1355 and
indicated significantly different decomposition temperatures, dis- 1581 cm
1, attributed to the breathing modes of the carbon atoms
played in Fig. 2. (D) and stretching of all C-C sp2 bonds (G), as well as a second-order
Events related to pure silicone decomposition were also present G0 band observed at 2698 cm
1. The SG1 sample presented bands
in the assessed composites (SG1, SG2, SG3 and SG4), which showed related to silicon (2912 and 2792 cm
1), that showed decreased
decreased intensities according to composite proportion, as noted intensity with increases in composite graphite proportions.
when comparing SG1 and SG4. The D band in carbonaceous materials has been commonly
Three different thermal events were identified for the polymeric
matrix, also noted in their respective composites. The first char-
acteristic was related to the thermal stability of silicone; at a
temperature close to 260  C a mass loss of approximately 49% was Table 1
Weight loss analysis of silicone using TGA containing proportions different.
observed; the polymer decomposes at this temperature [40e42]. In
general, this depolymerization temperature is above 350  C, how- Sample Weight loss (%)
ever, this decrease in depolymerization temperature is due to traces 28  Ce260  C 260  Ce450  C 450  Ce700  C
of acetic acid still present in the silicone. The presence/release of
Graphite 0.23 0.41 1.44
acetic acid, thus, causes a considerable decrease in the molecular Silicone 43.59 8.99 23.14
weight of the silicone, which explains the 44% loss of the polymer SG1 19.42 8.60 10.47
in this first event. The second step decomposition, over 260  C, is SG2 10.49 4.58 3.34
related to the partial oxidation of the silicone, the formation of SiO2 SG3 7.18 2.87 1.64
SG4 4.10 2.50 2.32
and amorphous carbon, and water loss [42,43]. The third step is
 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229 223

Fig. 3. Raman spectra obtained for the assessed samples.

described as characteristic of the disorder due to different factors

[44,46]. By calculating the intensity ratios of the D and G bands,
shown in Fig. 7, it can be observed that, by decreasing graphite
concentrations, the defect density in the solid increases, which can
be associated with increased exposure of the distortion in the
graphite network produced by the presence of C-O e C¼O species,
as observed in the XPS analyses.
The XPS spectra from all samples displayed characteristic peaks
Fig. 4. C1s X-ray photoelectron spectra for samples applying etch gun.
from C, Si and O atom electrons, indicating that the preparation
method employed was efficient in obtaining contaminant-free
homogeneous solids [47]. By comparing the atomic concentra-
tions determined by applying/not-applying the etch-gun technique
on the surface of the obtained solids (displayed in Table 2), the
homogeneity of the developed materials was confirmed.
Figs. 4 and 5 show the XPS spectra for the 1s orbital carbon
electrons. When the etch-gun was not applied (Fig. 4), a charac-
teristic C-C peak located at 284.3 eV was observed for the silicone-
graphite composites, as well as a peak located at 286.2 eV. Pure
silicone presented a peak at 285.9 eV, typical of C-O species, and
peaks from carbide (Y-C) and carboxyl (C¼O) species at 283 eV and
287.9 eV, respectively. The spectra of the composite solids obtained
using the etch-gun technique (Fig. 4) showed more intense and
defined peaks associated to C-O and C¼O carbon species, located at
285.11 eV and 287.01 eV, respectively. When considering the
graphite peak at 284.34 eV, and the main silicone peak at 286.04 eV,
a displacement of þ0.3 eV for the C-C species, and of
1 eV for the
C¼O species was noted for the composite materials, associated to
an electron transfer effect from the graphite to the silicone.
XPS spectra for electrons of the 1s oxygen orbital are shown in

Table 2
XPS results of prepared solids.

Sample B.E (e.V) C1s PP At. % B.E (e.V) PP At. % B.E (e.V) PP At. %
C1s O1s O1s Si2p Si2p

Graphitea 284.3 99 1
Silicone 286.0 50 24 103.97 26
Siliconea 286.0 54 532.9/530.7 24 104.05 22
SG4 284.6 88 7 101.93 6
Fig. 5. O1s X-ray photoelectron spectra for samples without applying etch gun.
SG4a 284.6 80 532.8 11 102.37 9
SG3 284.6 82 9 101.96 9
SG3a 284.6 75 532.8 13 102.33 12
SG2a 284.6 69 532.8 16 102.31 14 Fig. 5. The spectra of the doped samples with SG4, SG3, SG2 ratios
SG1a 284.6 50 532.5/531.0 22 102.03 27 presented a peak at 532.8 eV, characteristic of silane species found
a
EG3m ¼ after applying etch-gun for 3 min. in silicone, while the doped solid with the SG1 ratio presented
224 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229

peaks at 532.6 and 530.7 eV, inherent to oxygen species found in

silicon dioxide.
Fig. 6 presents the XPS spectra for electrons of the 2p silicon
orbital. For the SG4, SG3 and SG2 composites, the spectra obtained
without applying the etch-gun technique show a doublet, typical of
silane species, located at (101.8 ± 0.1) eV, which presented slight
displacements with increasing amounts of graphite, indicating
lower electron transference from carbon to silicon. For SG1, two
doublets were observed, at 101.5 eV and 100.45 eV, typical of silane
and carbide species, respectively. For silicone, two doublets were
also observed, at 103.77 eV and 101.2 eV, typical for silicate and
silane species. Two doublets located at 102.3 eV and 100.9 eV were
observed for all composites prepared by employing the etch-gun
technique, and the same previously described peaks were noted
for silicone.

3.2. Voltammetric behavior of the built-in SGCE

Fig. 7. Cyclic voltammograms of 5.0 mmol L
1 K3[Fe(CN)6] in 0.50 mol L
1 of KCl in the
The different compositons of the SSF/Graphite-Silicone com- composites (SG1, SG2, SG3, and SG4), scan rate of 50 mV
1.
posite electrodes were evaluated by cyclic voltammetry. Fig. 7 il-
lustrates the cyclic voltammograms for each of the composites,
rates. When applying lower scan rates, the voltammetric profile
with the voltammetric scan rate systematically varying from 10 to
changed from a quasi-reversible to a reversible system.
100 mV s
1 using a 5 mmol L
1 K3Fe(CN)6 in 0.5 mol L
1 KCl so-
Although better electrochemical responses and reversibility
lution as supporting electrolyte, from
200 to 800 mV. In all cases,
behaviors were noted in ratios above those present in SG1, such
well-defined responses were observed, in which the peak current
composites are not capable of surface self-sustainment, causing
increased with increasing scan rates. However, for each composite,
graphite grains to fall when using high sweeping speeds. Even
the peak shape was sensitive to the scan rate, with sigmoidal and
though SG1, SG2 and SG3 SSF/Graphite-Silicone composite elec-
peak shaped responses being observed at slow and fast scan rates,
trodes presented the best electrochemical response, they cannot be
respectively.
used as flexible electrodes, since they break under mechanical
Previous studies on graphite-silicone [18] composites using
stress. In order to be used as flexible electrodes, the composites
cyclic voltammetry demonstrated that composites containing a 70%
should possess the ability to absorb high levels of strain without
graphite/silicon ratio presented the best electroanalytical response.
fracturing or undergoing any significant degradation in their
Herein, SG3 presented the same characteristics reported by Pungor
structure and without compromising their electronic properties
et al., [18] (reversibility behaviors). SG1 and SG2 compositions, on
[48e50]. Ratios from SG2 onwards are not flexible, as displayed in
the other hand, presented quasi-reversible behavior at high scan

Fig. 6. Si2p X-ray photoelectron spectra for samples with and without use of etch gun.
 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229
Fig. 8a, but SG1 adequately supported mechanical stress, as
observed in Fig. 8b. Thus, characterization analyses focused on the
SSF/Graphite-Silicone composite electrode.
Morphologies for pure graphite and SG1 were characterized by
SEM as shown in Figs. 9a and 10b, respectively. SEM images showed
that pure graphite grains have the appearance of flakes, with
irregular sizes ranging between 2 and 30 mm. The graphite grains
show a “film”-type covering, forming agglomerates in certain areas.
White zones are also present, displayed in Fig. 9b, due to the
presence of silicone in the composite.
Fig. 10 shows the topographic image and the AFM phase contrast
characterization image of the SG1 SSF/Graphite-Silicone composite
electrode. It was also possible to analyze how the graphite grains
were spread on the electrode surface (topography) and investigate
their viscoelastic properties (phase contrast) shown in Fig. 10a and
b, respectively.
Topography images (Fig. 10a) show undefined grain boundaries,
whereas the phase-contrast image (Fig. 10b) reveals a distinctly
different appearance, with more clear and defined details regarding
the grains and their boundaries. In addition, it qualitatively displays
the viscoelastic properties of SG1, as this composite has several
differing areas, suggesting that lighter areas are softer (silicone),
and darker areas are directly related to the graphite grains, since
they are harder than silicone. However, the lighter areas are larger
compared to the darker areas (Fig. 10b), linked to what was
observed in the SEM images for SG1, since the graphite grains can
either be fully or partially covered by silicone. Fig. 11, which was
obtained from Fig. 10b, displays a graphical representation of the
topographic profile of SG1.
X-ray Micro Computed Tomography (mCT) images were ob-
tained to demonstrate that the investigated samples are entirely
homogeneous and quite similar, indicating that the graphite is
uniformly dispersed in the silicone at all ratios. The samples were
imaged from different directions, across an angular range of at least
180 . The reconstructed total volume can be visualized in different
ways, making it possible to quantify the structure directly, without
assumptions, for example, slice by slice (also referred to as virtual
cross-sectioning), or by rendering a 3D view of individual internal
Fig. 8. SGCE being twisted (a) SG2, and (b) SG1.
225
features [51,52].
The mCT images, besides corroborating the SEM and AFM im-
ages, show an added advantage of being three-dimensional, not
limited to a surface view, but allowing for observations inside the
whole volume, and visualizations of any part of the volume, in any
direction. An example of the segmentation result is illustrated in
Fig. 12. The axial cross-section micro tomogram are displayed in
Fig. 12: SG1 is displayed in Fig. 12; SG3 is displayed in Fig. 12b, from
the image extracted from the original volume of the samples
(Fig. 12c) for SG1 and Fig. 12d for SG3.
The ability to undergo flexure is a very advantageous feature for
composite electrodes, since it will increase the range of applica-
tions of these electrodes.
Overall, no significant difference regarding the flexural modulus
of SG1 specimens was observed, indicating that the increased strain
rate does not have a deleterious effect on the energy-absorption of
the SSF/Silicone-Graphite composite electrode. Fig. 13 shows the
stress-strain curves with an average flexural modulus of 10.54 MPa
and about 33% strain, obtained through three-point bending tests
conducted with samples with total volume of 0.58 cm3, at room
temperature [48]. However, flexural modulus depends on several
factors, including sample thickness and geometry, fabrication
techniques, testing conditions such as humidity, temperature, and
strain rate, and the strain at which the modulus is measured.
3.3. Voltammetric behavior of the flexible SGCE
SG1 at high scan speeds showed a quasi-reversible behavior
(Fig. 7), so new measurements were taken at low scan rates. Fig. 14b
shows the influence of slow scan rates (5e15 mV s
1) on the
electrochemical response of the flexible electrode SG1. Foster et al.,
when analyzing a silicone-graphite composite, observed a well-
defined current plateau at a slow scan rate, of less than 5 mV
1
[53]. Herein, the defined current plateau is observed at scan rates
ranging from 1 to 50 mV s
1 as shown in Fig. 14a and, at this low
scan rate, a pseudo steady state response is achieved. A well defined
sigmoidal response was observed, with little hysteresis between
the forward and backward scans and the limiting current
226 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229

Fig. 9. SEM images of (a) pure graphite (b) SG1.

Fig. 10. (a) Topography and (b) Phase contrast images on the same region of the SG1 surface.


Fig. 11. SG1 Topographic profile: Area 30 mm  30 mm.

independent of the scan rate. This behaviour suggests a dual efect,
at first an ohmic drop, a disturbance always present in graphite/
polymer composite materials, whose magnitude depends on the
graphite content and ratio [54e58], followed by a microelectrode
array-like behavior, according to the scan rate.
By assessing data from Fig. 14 it is possible to note a relevant
capacitive behaviour on the voltammogram extremes for all scan
rates. These results are in agreement with the findings of Trijueque
et al. [55], who mentioned that, for graphite-epoxi electrodes, a
composition of 62% presents the best electroanalytical responses
based on the second threshold limits for the percolation theory.
This theory predicts the existence of unconnected particles on the
electrodic surface, that are electroactive sites isolated from each
other, forming independent microelectrodes or microarray elec-
trodes [55e59].
Fig. 14b shows that, at low scan rates (5e15 mV s
1), a steady-
state current is reached, in which each microelectrode does not
interact with each other, achieved as an integration over all mi-
croelectrodes on the electrodic surface. The insulating/conducting
composite materials can be considered a microarray. This config-
uration behaviour observed for the composites is the same
observed, for example, for Araldite-Me73.2% (m/m) graphite,
 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229
Fig. 12. Axial cross-section of SG1 (a) and of the SG3 (b) and three-dimensional images of original volume of SG1 (c) and SG3 (d) acquired by mCT.
Fig. 13. Typical three-point bending curves of specimens of SG1.
Araldite-CW2215e45.8% (m/m) graphite, and Silicone61.0% (m/m)
graphite reported by Ref. [53].
The electrochemically active areas were determined from the
slope of the RandleeSevçik plots of ip vs. v1/2 using a reversible
electrochemical probe of 5.0 mmol L
1 K3[Fe(CN)6]. The apparent
electroactive area (0.035 cm2) is significantly smaller than the
geometric area (0.096 cm2), suggesting that the SG1 composite
electrode consists of large non-conductive regions, perhaps due to
the lower graphite loading.
4. Conclusions
The present study has demonstrated that is possible produce a
self-sustained, flexible composite electrode with a 50% Graphite/
227
Fig. 14. Cyclic voltammograms of the flexible composite electrode at 5.0 mmol L
1
K3[Fe(CN)6] in 0.50 mol L
1 KCl at scans rates 5e15 mV
1.
Silicone ratio, relatively easy to prepare, low-cost and non-toxic.
The flexible SSF/Graphite-Silicone composite electrode showed a
reversible voltammetric profile only at slow scan rates
(5e15 mV s
1), resulting in a well-defined sigmoidal response with
little hysteresis between the forward and backward scan, and the
limiting current independent of the scan rate, suggesting that the
SG1 SSF/Graphite-Silicone composite electrode has a microelec-
trode array structure. Thus, from the perspective of certain appli-
cations, this flexible SSF/Graphite-Silicone composite electrode
shows significant advantages over conventional composite elec-
trodes, due to flexibility. Nevertheless, the uses of this type of
composite electrode are still undetermined, opening up a variety of
228 A.L. Silva et al. / Journal of Alloys and Compounds 691 (2017) 220e229
possible applications in several areas.
Acknowledgments
The authors are indebted to the Carlos Chagas Filho Foundation
for Research Support in the State of Rio de Janeiro (Fundaça~o Carlos
Chagas Filho de Amparo a  Pesquisa do Estado do Rio de Janeiro -
FAPERJ, E-26/102.971/2012 and E-26/111.407/2013) for the research
support, to the Surface Science Laboratory (Laborato rio de Cie
^ncia
de Superfícies e LCS), Brazilian Nanotechnology National Labora-
tory (LNNano)/National Research Center of Energy and Materials
(Centro Nacional de Pesquisa em Energia e Materiais - CNPEM) for
the use of the AFM in its open facilities, to Prof. Marcelo Camargo
Severo de Macedo (UFES) for the use of the SEM, to the State Uni-
versity of Maringa (UEM) for the use of the universal machine, to
the Laboratory for NMR and Petrophysics Applications (UFF-LAR),
for the use of the mCT, to the Reactors, Kinetics and Catalysis
research laboratory (Laboratorio de Reatores, Cine tica e Cata
lise -
RECAT) for the use of the TG and XPS, and to the Solid State
Experimental Physics research laboratory (LEFES) for the use of the
Raman spectrometer, both located at the Federal Fluminense Uni-
versity (Universidade Federal Fluminense - UFF).
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