Jurnal

Chapter 13
Synthesis and Characterization of Advanced Carbon-

Based Nanowires Study of Composites Actuation
Capabilities Containing These Nanowires as Fillers
V. Salles, L. Seveyrat, T. Fiorido, L. Hu, J. Galineau,
C. Eid, B. Guiffard, A. Brioude and D. Guyomar
Additional information is available at the end of the chapter
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1. Introduction
Electromechanical properties in polymers can be employed to create a large number of sen
sors and actuators [1-2]. For example they could replace the piezoelectric materials common
ly used in Micro Electromechanical Systems (MEMS). Even if the electromechanical
coupling is relatively weak for polymers, they can generate high strains due to electrostric
tive and Maxwell effects which are a quadratic function of the applied electric field as op
posed to a linear function for piezoelectric materials. Other advantages of the polymers are
their ease of processability, flexibility and cheapness.
Actuation capabilities of polymers depend on their intrinsic electrical, dielectric and me
chanical properties. In order to optimize these properties, one way consists on the incorpo
ration of nano-objects in the polymer matrix. Due to the nanometer-scale of the fillers
dimensions, an important change of the properties can be obtained with relatively low ra
tios. In addition, the effect is more pronounced for conductive nano-objets since higher per
mittivities are expected to be obtained with a reduced amount of fillers [3]. Carbon-based
nanocomposites are good candidates for electroactive nanocomposites: some studies were
performed particularly on carbon black, carbon nanotubes, graphite or graphene fillers [4-9].
This part of the chapter is devoted to the influence of carbon-based nanowires (SiC@C,
SiC@SiO
2
, Fe
3
C@C) as fillers on polyurethanes. The microstructural, dielectric, mechanical,
electromechanical and electromagnetic properties are presented and discussed in the follow
ing sections.
2012 Salles et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
Among the available electroactive polymers, polyurethanes are of great interest for a wide
range of actuator applications due to their significant electric field-induced strains [10-11].
The total electrical field induced strain S can be expressed from electrostricition and Max
well stress [12-13].
* 2
33 electrostriction Maxwell
S S S M E = + = (1)
With M*
33
is the apparent electromechanical coefficient and E the applied electrical field.
The Mawwell stress effect comes from the interaction force between the positive and nega
tive charges present on the electrodes
'
2 0 r
Maxwell
S E
Y
e e
= - (2)
With
r
the real part of the polymer relative permittivity,
0
the vacuum permittivity, and Y
the Youngs modulus.
The electrostriction represents the coupling between the electrical polarization and mechani
cal response in the material and is related to the electrostrictive coefficient Q and the relative
permittiy
r
.
2 ' 2 2
0
( 1)
electrostriction r
S Q E e e = - (3)
It was shown in previous studies [4, 8, 14] that in such polymers as PU, the Maxwell stress
can be neglected.
Based on experimental studies [12, 14-15], the Q coefficient is found to be inversely propor
tional to the product of the Youngs Modulus and permittivity according to:
0
1
'
r
Q
Y e e
(4)
As a consequence, an empirical proportionality relationship is also obtained for the M
coefficient :
2
0
( ' 1)
'
r
r
M
Y
e e
e
-
(5)
Nanowires - Recent Advances 296
This chapter is divided into two main parts. The fabrication procedures and the characteri
zation of the as-prepared nanowires are detailed in the first part whereas the second part is
dedicated to show how these nanomaterials can act on the electromechanical properties of
EAPs when they are introduced as fillers, demonstrating their high potentiality to fabricate
innovative actuators.
2. Fabrication and characterization of carbon-based nanowires
Among the different fabrication processes able to lead to one-dimensional nanostructures,
one can distinguish two main approaches: one based on vapour deposition and one other
based on polymer pyrolysis, corresponding to two well-known methods presented in this
paper: Chemical Vapor Deposition (CVD) and electrospinning (ES) respectively. The interest
in studying such two processes lies on fabrication of nanofibers which tend to be mono-crys
talline in the first case and more polycrystalline in the second one, with nano-sized crystals.
2.1. Elaboration and characterization of silicon carbide nanowires by CVD
We report here a simple process to fabricate SiC-based nanowires coated with either silica,
SiC@SiO
2
, or carbon, SiC@C. In both cases, SiC nanocables (NC) were prepared from solid
precursors of Si and C, i.e. SiO(s) and polypropylene (PP) respectively [16]. These reactants
are much cheaper compared to high-purity gaseous reactants used in conventional CVD
syntheses. In a typical experiment, the experiments were carried out in a furnace equipped
with an alumina tube. PP was placed in an alumina boat, followed by a second alumina boat
containing an equimolar mixture of Si(s) and SiO
2
(s) or simply a SiO(s) powder, which was
partially covered by a graphite condensation plate (Figure 1). All of the experiments were
conducted under argon at a very low flow rate (10 mL.min
1
), at 1400 C during 10 h.
Figure 1. a) Experimental setup for the growth of SiC-based nanowires; b) Picture of the two alumina boats contain
ing the reagents and the graphite condensation plate [16]
Synthesis and Characterization of Advanced Carbon-Based Nanowires Study of Composites Actuation...
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At high temperature, a reaction between Si and SiO
2
involves the formation of gaseous SiO
which is able to react with carbonated species to initiate the nanowires growth. While using
a PP/SiO weight ratio of 1 (maximum), SiC@SiO
2
NCs are formed whereas a ratio of 2 leads
to the growth of SiC@C NWs (Figures 2 and 3). It is thus possible to control the silica thick
ness from 2 to 10 nm by adjusting the PP/SiO weight ratio from 1 to 0.25 for instance.
The as-obtained NWs have a diameter ranging from 20 to 40 nm. The NWs core consists of
3C-SiC, the cubic polytype of SiC, and the shell is either composed of amorphous silica (Fig
ure 2) or turbostratic carbon (Figure 3). The high-purity of such structures was confirmed by
EELS analyses and Raman investigations allowed to determine the P-type doping of the SiC-
based NWs.
Figure 2. SiC@SiO2 NCs prepared from 1 g PP and 4 g SiO(s). a) Slightly out-of-focus TEM image of the crude product,
where the amorphous silica layer can be easily distinguished from the SiC core (the corresponding well-focused image
is included as an insert); b) HRTEM image showing a 10 nm silica layer around the SiC core [16]
Figure 3. a,b) HRTEM images of a 30 nm SiC@C NC prepared by increasing the amount of PP to 8 g for every 4 g SiO(s) [16]
2.2. Elaboration and characterization of iron carbide nanowires by electrospinning
Electrospinning is a process which has been mainly studied and used during the last decade
to prepare nanowires/nanofibers. We also have noticed an increasing interest of the scientif
ic community during this period (Figure 4).
Figure 4. Histogram representing the number of scientific articles published per year during the last decade (Research
performed on 4
th
June 2012 with Web of Science, with electrospinning AND nanofiber)
A lot of effort has been focused on the electrospinning process due to its versatility, which
permits the formation of polymeric fibers as well as, after treatment, oxide and non-oxide
inorganic fibers at submicro- and nanoscales [17-18]. This process is easy to scale-up to large
amounts and has been recently employed to develop non-oxide ceramic nanowires. In this
field, the synthesis of SiC [19-20], B
4
C [21], B
4
C/SiC [22], GaN [23] and BN [24] fibers has
been reported for diameters smaller than 1m. This production technique allows to precise
ly control the chemical composition of sub-microscale and nanoscale fibers which are seri
ous candidate for applications ranging from smart textile to biomedical, including
automotive and environmental areas.
Electrospinning consists in electrostatic stretching of a molten polymer or a solution contain
ing a polymer solubilized in a solvent (the most common procedure). A high-voltage (HV) is
applied between a spinneret (needle) and a metallic target (Figure 5).
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299
Figure 5. Schema of a typical electrospinning setup
With a low and continuous flow rate of solution through the needle, the solution drops
without application of voltage but when the electric field is high enough to overcome the
surface tension, a Taylor cone is formed at the needle tip and the solution is then accelerated
toward the target in the form of a polymer jet. With stable working conditions, a continuous
filament can be produced and collected as a solid 1D-material since the main part of the sol
vent evolves during the jet acceleration, in case of wet spinning. solvent evolves during the
jet acceleration. Its final diameter, conventionally in the submicrometer scale, is about 1000
times lower than the inner spinneret diameter. Numerous parameters directly influence the
morphology of the as-spun fibers/filaments. It is possible to fabricate dense, porous, beaded,
flattened or perfectly cylindrical fibers simply by adjusting the solution properties :
surface tension,
electrical conductivity,
viscoelastcity,
polymer concentration,
solvent(s) volatility,
and/or the spinning conditions :
high-voltage,
working distance,
polymer/solution flow rate,
inner needle diameter,
type of target,
moisture degree.
In case of fabrication of inorganic fibers by electrospinning, a specific precursor is employed
[17-24]. Iron-based materials (iron oxide and iron carbide) can be fabricated from a mixture
of polyvinyl pyrrolidone (PVP), bringing the spinnability property, and iron (II) acetate
(FeAc
2
) in acetic acid and ethanol (Figure 6) [25].
Figure 6. Experimental process with the different nanostructures obtained [25]
After stirring, to obtain a homogeneous and brown colored solution, the polymer solution is
loaded into a syringe (5 mL) before being spun on a metallic target. After optimization of all
spinning parameters, homogeneous filaments characterized by a smooth surface and an
average diameter ranging from 200 to 500 nm can be obtained according to the precursor
content (i.e. FeAc
2
/PVP ratio) in the initial solution (Figure 7). An average value was calcu
lated on 100 fibers of each sample giving a linear evolution of the fiber diameter versus the
FeAc
2
/PVP ratio: 440 nm, 395 nm, 260 nm and 220 nm for ratios of 2.63, 1.75, 0.87 and 0.43
repectively. This phenomenon is mainly attributed to a decrease of solid content when the
ratio is decreased since the PVP content is the same in all the solutions (corresponding to 7
wt%). We can notice that iron acetate is stored and sampled under argon in order to prevent
it from degradation over time.
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A pyrolysis step was then carried out under argon and hydrogen (95% Ar and 5% H
2
) with a
heating rate of 3C/min and an holding time of 4h at 450C before cooling down. This ther
mal treatment allowed the organic part decomposition as well as the precursor conversion
into an inorganic material. The thermal behaviour of the filaments during the pyrolysis step
is still under investigation but we know that the last weight loss is due to PVP gaseous evo
lution up to 400-450 C. Above this temperature, there is no more weight variation of the
filaments. Temperatures above 800 C were not studied.
Figure 7. SEM images of the various PVP/FeAc
2
nanofibers with different wt ratios (FeAc2/PVP). (a) ratio = 2.63; (b)
ratio = 1.75; (c) ratio = 0.87; (d) ratio = 0.43 [25]
The weight loss occuring during treatment is logically accompanied by a shrinkage in the
macroscopic sample dimensions (already high-lighted and described in a previous work
[24]), as well as in the filament diameter (Figure 8).
Figure 8. HRTEM of Fe
3
C nanoparticles surrounded with graphitic planes. Inset: TEM images of Fe
3
C nanofibers pre
pared with FeAc
2
/PVP = 0.87 [25]
As XRD analysis was inadequate (no signal) to characterize the type of material composing
constituting the inorganic filaments, transmission electronic microscopy (TEM) was per
formed on several filaments (Figure 8). The first main information is that the filaments are
made of nanoparticles homogeneously dispersed in a matrix made of a different material.
High-resolution TEM (HR-TEM) was then used to observe that the small nanoparticles have
a spherical shape, and interplanar distances of 3.37 and 2.14 both measured on the same
nanoparticle indicating the presence of pure iron carbide, corresponding to crystalline
planes (002) and (200), repectively, of the Fe
3
C orthorhombic phase. Moreover, these cemen
tite domains are surrounded by well-known concentric graphitic planes forming a coating
layer of 2-3 nm on the particle surface. The reduction in a hydrogen atmosphere of the as-
electrospun PVP/FeAc
2
fibers is responsible for the formation of polycrystalline Fe
3
C nano
fibers embedded in carbon graphitic planes, ensuring stability and cohesion of the Fe
3
C
nanoparticles. The presence of graphiic carbon was confirmed by Raman spectroscopy with
D and G bands at 1360 and 1594 cm
-1
respectively [25].
The functionalization of organic matrices for electroactuation application has been studied
and is presented below, using either SiC-based or Fe
3
C-based nanowires as inorganic fillers.
Carbon-based fibers, SiC@C and Fe
3
C, were expected to be interesting because of their car
bon coating which should enhance the surface electrical conductivity of the fillers, thus pro
moting the charge displacement at a nano- or a submicro-scale inside the polymer matrix.
This should have a positive effect on the electrical polarization of the polymer host, directly
linked to its ability to be deformed when it is subjected to an electric field.
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3. Integration of the nanowires into polymer and study of composites
actuation capabilities
3.1. Elaboration of nanocomposites
The two polymers were polyether-based aromatic thermoplastic polyurethane (PU), pur
chased from Lubrizol Corporation: Estane 58888 NAT 0.21 (PU88) and Estane X-4977
NAT039 (PU75). They differ by the ratio of hard to soft segments. Hard segments (HS) com
prise the 4.4 methylene bis(phenyl isocyanate) (MDI) and 1,4-butanediol (BDO) and soft
segments are poly(tetramethlene oxide) (PTMO). The PU88 has a density of 1.13 g/cm
3
, a
hardness of 88 shore A and the HS content is about 46%; the PU75 has a density of 1.07 g/
cm
3
, a hardness of 75 shore A and the HS content is less, near 26% [26]. HS amount is an
important factor because the physical properties depend directly on the degree of phase sep
aration between the hard and the soft phases.
Figure 9. Elaboration of the PU88-SiC nanocomposite solution by solution casting method and spin coating [26]
PU88-SiC@C and PU88-SiC@SiO
2
nano-composite films were prepared following a solution
casting method (Figure 9). Before use, the PU granules were heated at 80C for 3 h to re
move any traces of water. They were then put in N,N-dimethylformamide (DMF, Sigma-Al
drich D158550, 99%). The solution was maintained at 80C for 2 h. The SiC nanowires were
dispersed into DMF using an ultrasonic processor (Hielsher UP400S, 400 W, 24 kHz, 7 mm
diameter sonotrode) under the following experimental conditions depending on the type of
the nanowire: 10 to 20 min duration, 80% amplitude, 80% pulse. This solution was added to
that of the polymer and the resultant mixture was heated at 80 C for 1 h under mechanical
stirring, until a homogeneous and viscous solution was obtained. This solution was de
gassed for 24 hours at room temperature before spin coating on glass plates using a Laurell
WS400 BX spin coater. This was a two steps process of 10 and 15 seconds with different rota
tional speed depending on the desired thickness: 200/300 rpm for 80 m and 500/800 rpm
for 35 m. The films were then placed in an oven at 60C for 24 hours and then removed
from the glass substrate. A second heating treatment at 125C (below the melting tempera
ture) for 3 hours was performed in order to eliminate any residual traces of solvent.
The elaboration method was improved for the PU75-Fe
3
C@C nanocomposites by using
closed recipients during the dissolution and mixing steps so that the evaporation of the
DMF solvent was avoided. In addition, the solution was applied on glass plates with an Elc
ometer 3700 doctor blade film applicator (Figure 10). This technique produced large surface
films with homogeneous thickness. The following thermal treatments were the same as de
scribed above.
Figure 10. Deposition of the PU75-Fe
3
C nanocomposite solution with Elcometer 3700 doctor blade applicator
For both methods (Figures 9 and 10), the weight fractions of fillers varied between 0 and 4 %.
It is important to note that spin coating is widely used as a shaping method for EAPs that
are introduced inside actuators devices, however, the method so-called Doctor Blade al
lows to prepare polymer or composite films with larger dimensions which is interesting for
studies necessitating numerous samples for analyses (electrostriction, mechanical test, DSC,
SEM,...), with verification of reproducible results as well.
3.2. Characterization of the nanocomposites
3.2.1. Structural characterization of the nanocomposites
Microstructural observations (Figure 11), carried out by SEM using a cryo-fracture prepara
tion, showed that the nanowires seem to be aligned preferentially in planes parallel to the
surface of the film. Whatever the shaping method used, taking into account the external
forces applied on the long chains of PU, it is assumed that there is no difference of the nano
wires organization in the polymer host. The homogeneity of this distribution was checked
over the entire width, and from the bottom to the top surface.
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Figure 11. SEM observations performed on samples PU75-Fe
3
C (2.5 wt% of Fe
3
C); Arrows indicate the presence nano
fillers with perpendicular (solid arrows) and non perpendicular (dashed arrows) orientations compared to the fracture
plane
Figure 12. DSC thermograms on heating and cooling of pure PU88, PU88-2SiC@C and PU88-2SiC@SiO
2
nanocompo
sites films
The Differential Scanning Calorimetry (DSC) technique was used to study the effect of the
nanowires on the structure of the host polymer. The thermal analysis was performed with
DSC 131 evo from Setaram, under nitrogen atmosphere. The samples (about 20 mg) were
placed in closed 100-l aluminum crucibles and cooled from ambient temperature down to
-100C, then heated to 210C and finally cooled to RT. The heating and cooling ramps were
performed at 10C.min
-1
.
The thermograms for the pure PU88, and the PU88-2SiC@C and PU88-2SiC@SiO
2
composi
tions are presented below (Figure 12).
The glass transition temperature for the soft segments (Tg), melting temperatures (T
II
and
T
III
), heat of fusion (Hm), crystallization temperature (T
c
) and heat of crystallization (Hc)
are summarized in Table 1.
Table 1. DSC results obtained for the PU88-SiC nanocomposite films
The first thermal phenomenon near -45C was related to the glass transition (Tg
SS
) of the soft
segments (SS). This value can give an estimation of the amount of hard segments (HS) dis
solved in the soft domains and as a consequence an indication of the purity of the soft phase
[27-28]. When the fraction of nanowires was increased, no significant change of Tg was ob
served. It was thus concluded that the degree of HS-SS mixing was not modified by the in
corporation of nanowires.
Some effects of relaxation of the polymer chain, a modification at the SS/HS interface or ther
mal endotherm seemed to explain the behavior of heat flow near 60C. At temperatures in
the range 150-170C, it was observed a bimodal endotherm that can be related to the micro-
mixing of non-crysytalline or semi-crystalline hard and soft phases followed by the melting
of crystalline HS [29]. Another interpretation of the bimodal peak could be the melting of
crystalline hard segments: the two peaks represent the two characteristic lengths of HS [27].
In both cases, the increase of the samples crystallinity would be accompanied by an increase
of these temperatures and/or an increase of the total enthalpy of the 2 phenomena.
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With the incorporation of SiC@C nanowires, the endothermal peaks remained unmodified,
temperature and corresponding enthalpy did not change. With SiC@SiO
2
, one can observe
only a slight decrease of the temperature of the first endotherm related to the micromixing
of hard and soft phases.
During the cooling experiments, a more important influence of the nanowires on the crystal
lization behavior was observed. When the amount of nanowires was increased, the crystalli
zation temperature was raised but without a significant change in enthalpy. The nanowires
seemed to act as nucleating agents improving the crystallization. There is a more important
effect on the crystallization of the polyurethane with the incorporation of SiC@C compared
to SiC@SiO
2
(Figure 12).
The same study has been performed on nanocomposite films based on PU75 and Fe
3
C@C
nanowires and the values of Tg and melting temperatures and heat of fusion are summar
ized in Table 2. The PU75 is less rigid than the PU88, as indicated by the value of the glass
transition temperature which is 25C under the PU88 one. With the incorporation of
Fe
3
C@C, there is no modification of the thermal properties during heating and cooling, and
so no morphological change of the PU75 polymer host.
Tg (C) T
II
(C) T
III
(C) Hm (J/g)
Pure PU75 -68.6 153 174 2.3
PU75-2.5Fe
3
C@C -69.0 152 175 3.0
PU75-5Fe
3
C@C -71.7 152 174 2.4
Table 2. DSC results obtained for the PU75-Fe
3
C@C nanocomposite films
It can be concluded from these DSC results that, whatever the PU, no major microstructural
modification of the matrix was observed with the incorporation of nanowires.
3.2.2. Dielectric properties of the nanocomposites
Prior to the electrical measurements, the samples were coated with 20 nm thick gold by
sputtering. The relative permittivity , the dielectric loss factor tan and the real part of the
electrical conductivity were obtained with a Solartron 1255 impedance / gain-phase ana
lyzer and a 1296 dielectric interface. The voltage was set at 1 V
RMS
and a frequency range was
performed in the range 0.1-10
5
Hz.
Figure 13 presents the electrical conductivity versus frequency of some PU88/SiC nanowires
composites. In all samples, two frequency regions can be observed: one for which the con
ductivity was almost constant (low frequencies < 10Hz) and which is attributed to charge
displacements and another one (high frequencies > 10Hz) where the conductivity increased
with the frequency and corresponds to the dielectric losses [30].
Compared to the SiC@SiO
2
, the SiC@C nanowires lead to a slightly more important increase
of the polyurethane conductivity. This is in goog agreement with the conductive carbon lay
er which covers the SiC wires, instead of the SiO
2
one.
Figure 13. The electrical conductivity versus frequency for pure PU and PU88-2SiC composites
The frequency/conductivity curves show that even if the conductivity is slightly enhanced
with the incorporation of nanowires, the percolation threshold is not reached even with
higher concentrations of SiC (3% tested) or SiO
2
(4% tested). This threshold could be estimat
ed as the content located between that for which the conductivity still depended on the fre
quency and that for which it became completely independent of the frequency.
Figure 14 exhibits the permittivity versus frequency of some PU88/SiC nanowires composites
Figure 14. The relative permittivity versus frequency for pure PU and PU88-2SiC composites.
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309
Whatever the sample, the permittivity increases as the frequency is lowered, which is in
good agreement with Maxwell Wagner mechanism [31]. The composites present an higher
permittivity than the pure polyurethane one: for example, at 0.1 Hz, it increases from 9 for
pure PU to 12 for PU88-2SiC@SiO
2
and to 18 for PU88-2SiC@C.
The effect is more pronounced for the SiC@C compared to SiC@SiO
2
certainly because the
first type of filler has a conductive carbon layer on the surface instead of the insulating SiO
2
layer.
For the PU75-Fe
3
C system, the same dielectric characterization was made (Figure 15).

Figure 15. The conductivity (a) and relative permittivity (b) versus frequency for composites with varying SiC contents
(a) PU88-SiC@C and (b) PU88-SiC@SiO
2
The conductivity curves for the PU75 system shows like for the PU88 two regions depend
ing on the value of the frequency. Whatever the frequency, the conductivity is not really
modified with or without Fe
3
C.
Compared to the SiC@C filler, the Fe
3
C@C has a very slight influence on the permittivity of
the samples at low frequency. But at a frequency near 1 kHz, the gain was of the same order
of magnitude for the two fillers i.e. 1.35 fold.
3.2.3. Mechanical properties of the nanocomposites
The mechanical behaviour of the composite films was evaluated on 25 x 10 mm
2
samples, us
ing a house made tensile test (Figure 16). On one end, the sample was clamped onto a New
port platin and the other end onto a force sensor. The stage was moved using a function
generator at a frequency of 50 Hz and the dynamic force was acquired on an oscilloscope.
Measurements were performed over a deformation range from 0 to 100%. The Youngs modu
lus was determined at the beginning of the curve strain / stress for elongations less than 4%.
Figure 17 exhibits the evolution of the Youngs modulus of the nanocomposites films as a
function of the content of nanowires.
Figure 16. Experimental set-up for measuring the mechanical properties of the nanocomposite films
Figure 17. The Youngs modulus versus the content of nanowires for PU88-Si@C and PU75-Fe
3
C@C
For the two polyurethane systems, it is observed an expected little increase of the Youngs
modulus with the incorporation of nanowires. For the same content of nanowires, for exam
ple 2.5%, there is a 1.3 gain factor for PU88-SiC@C and 1.2 gain factor for PU75-Fe
3
C@C.
3.2.4. Electromechanical capabilities
a. Electric field-induced thickness strain measured by a double-beam interferometer at
low frequency (0.1Hz).
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The electric field-induced thickness strain S was measured with a double-beam laser inter
ferometer (Agilent 10889B), with a precision in the order of 10 nm. The film samples of 25
mm diameter were placed on a horizontal stainless steel disc (20 mm in diameter), and a sec
ond brass disc placed on the upper side of the film allowing the application of a bipolar elec
tric field at 0.1 Hz. The voltage was supplied by a function generator (Agilent 33250A)
amplified 1000-fold through a high-voltage lock-in amplifier (Trek 10/10B). A guard ring
was added to the sample surface and grounded so as to eliminate any surface leakage cur
rents. Figure 18 gives photographs of the experimental set-up for strain measurements.

High voltage wire
Oscilloscope
Function generator
Voltage amplifier
Current amplifier
Laser interferometer
Disc shaped polymer
Ground wire
Brass disc
Electrode
suprieur
e
Mirror
Laser
HT
sample
Figure 18. Experimental set-up for strain measurements with laser interferometer at 0.1 Hz.
Figure 19-a) presents the thickness strain amplitude S
3
(S
3
is negative since the film is com
pressed) versus the electric field amplitude of pure and filled with 0.5% SiC@C PU88 films
of different thicknesses.
All studied films exhibited the same type of strain variations (except the 20 m thick nano
composite because electric breakdown occurred above 18V/m): a first region where the
strain increases regularly with the electric field amplitude indeed and a second region at
higher fields where an asymptotic value is reached. This is the result of the hyperelastic be
haviour of such PU materials.
The deformation depends on the thickness of the film: lower electric fields were required to
obtain a given strain level before saturation as the films thickness increased. The 20m-
thick nanocomposite film presented the maximal thickness strain of about 18% at 18 V/m.
At moderate electric values, the greatest effect was observed for the 100 m-thick PU-SiC@C
film since the strain was equal to 10% at a field as low as 6 V/m.
Figure 19. Evolution of the strain amplitude versus the electric field amplitude for various thicknesses of pure PU88
and PU88-0.5SiC@C films at 0.1 Hz. (b) The evolution of the strain amplitude versus the thickness of pure PU88 and
PU88-0.5SiC@C films at E= 6.5 V/m [11]
As the relative permittivity was found to be higher in the SiC@C composites, the results
showed an increase of the interfacial polarization induced by a pronounced space charges
effect. Space charges accumulate in PU and more effectively in PU-SiC@C composites and it
was still evidenced by the large dependence of the strain on the film thickness, particularly
for low and medium electric field values (E < 10 V/m). These charges are generally elec
trons injected in the bulk from the electrodes and/or impurities (ions) in the sample which
are trapped to the different structural interfaces of the material. The consequence of the
presence of space charges is the appearance of high electric field local densities, located at
the various trapping sites (defects, interfaces), thus yielding a non-uniform field distribution
in the film thickness and consequently a high deformation [32].
However, the film must be thick enough to present such a strain improvement by space
charges effect, as it is shown in Figure 19-b which gives the evolution of strain at 6.5 V/m
electric field versus thickness. If the film was too thin, the strain was not increased because
the interfaces that were able to trap the space charges started to overlap and as a conse
quence charge homogenization occured [14, 33]. When the film thickness increased, the
strain also increased, with a more pronounced effect for the nanocomposite. It should be
emphasized that the polyurethane exhibited a considerable ability to collect space charges
certainly due to the two-phase structure composed of hard and soft segments inducing
many interfaces. The presence of space charges were experimentally evidenced by studying
the steady-state current electric field characteristic of the films [11].
http://dx.doi.org/10.5772/54384
313
DSC measurements presented in previous section were performed in order to determine
whether the SiC@C nanowires themselves or polymer chains/nanowires interfaces behaved
as additionnal space charge traps and/or if they increased the level of phase mixing between
soft and hard segments and consequently the structural interface density. The DSC results
show that there is no modification of the phase mixing so it can be concluded that space
charge effects in the composites were not enhanced by an increase of the structural interface
density, but rather by the SiC@C nanowires themselves, acting as charge traps.
Another study was performed with SiC@SiO
2
nanowires as fillers with the laser interferome
ter method at low frequency [34]. The electric field induced thickness strain response has
been investigated for the polystyrene-grafted silica coating of SiC NWs
(PU88-2SiC@SiO
2
@PS) nanocomposites and compared to the pure polyurethane film and the
PU88-2SiC@SiO
2
nanocomposite without polystyrene grafting.
Polyurethane polymer filling with both types of nanowires leads to a higher electromechani
cal response than for the pure PU88 film. At a moderate electric field of 10 V/m,
2SiC@SiO
2
@PS loading increased the strain level of pure PU88 by a factor of 2.2. The im
provement came partially from polystyrene grafting since the PU-2SiC@SiO
2
films showed
only a 1.7 times increase. It was shown in the article that since a higher strain was observed
for the PU88-2SiC@SiO
2
@PS films, the polystyrene chains grafting seemed to act as a dis
persing agent, thus yielding a homogeneous distribution of NWs in the composite.
b. Deflection strain under electric field of a diaphragm type dielectric actuator working at
high frequency (near 1kHz).
Another way to investigate the electromechanical properties of polymer films is to measure
the expension in the 31 direction (which is directly proportional to the 33 contraction). It was
chosen to investigate it using a diaphragm, which is also a good candidates for integration
of these polymer films into Microsystems [35].
The diaphragm device (Figure 20) comprised a sample holder and the electroded sample.
Figure 20. Diaphragm device used for the measurement of the deflection strain under electrical field at high frequen
cy [35]
The sample holder was fabricated in thick PMMA sheets. Two diameter holes of 5.5 mm and
20 mm were drilled into the two parts of the device. The 5.5 mm hole constituted the dia
phragm. Gold electrode was sputtered onto each part for electrical connections. Samples of
25 mm in diameter were electroded using gold sputtering as shown in the figure 19 and
then aligned with the 5.5 mm hole and the electrode on the rear part of sample holder. The
sample adhered onto the sample holder by electrostatic forces.
The polymer film was excited in a pseudo piezoelectric mode by applying a DC electrical
field in addition to the AC excitation. The sinusoidal voltage was applied using a function
generator (Agilent 33200A) and amplified by the Trek Model 10/10 high voltage power am
plifier The DC component induces a constant polarization of the membrane, and thus, a pie
zoelectric behavior. In this study, all data were recorded in pseudo-piezoelectric mode and
at the first resonant frequency. In addition, the DC bias voltage was chosen equal to the AC
voltage magnitude. The membrane deformation was recorded using a Polytech OFV-5000
vibrometer equiped with a OFV-505 sensor head. The reflectivity of the gold electrode was
used to monitor the deflection. The deflection strain is defined as S
d
=S/d where d is the de
flection and h the sample thickness. The deflection is caused by the compressive strain un
dergone by the film rigidily clamped at the edge.
The deflection strain magnitude for PU75 loaded with 0, 2.5 and 5wt% of Fe
3
C@C has been
studied as a function of the square applied electrical field magnitude [36]. The results are
presented in figure 21.
Figure 21. The deflection strain versus the square applied electrical field for PU75-Fe
3
C@C nanocomposites films
At low and medium electric fields (E < 10 V/m), the deflection strain increased quasi-line
arly with E
2
, thus confirming the electrostrictive nature of the electromechanical response.
For higher electric field, a saturation effect corresponding to an asymptotic constant value of
strain was observed and can be attributed to the saturation of the electrical polarization [37].
The deflection is increased by 2 to 7 fold from pure PU75 to 2.5% load PU depending on the
electrical field magnitude, and is higher than that measured on the same PU filled with car
bon black [35]. A considerable deflection strain of more than 130 % was found for the
PU75-2.5Fe
3
C@C nanocomposite for a 18 V/m electrical field.
http://dx.doi.org/10.5772/54384
315
With higher amount of Fe
3
C nanowires, the deflection decreases. This decrease could be re
lated to an agglomeration of the nanowires. Some complementary structural charateriza
tions are under progress by SEM and Focused Ion Beam in order to fully understand this
behavior. Even if the global permittivity and dielectric loss do not increase dramatically, it is
possible that some agglomerates appear locally inside the film and contribute to decrease
the interfacial polarization and consequently the density of trapped charges. This effect
yields a decrease in the deflection strain amplitude.
By using the same method, measurements have been performed on different PU88-SiC@C
nanocomposites. Figure 22 exhibits the strain deflection versus the square of the electric
field. Even if the polyurethane host is not the same for the study, it is possible to compare
the influence of the two types of nanowires, ie SiC@C and Fe
3
C@C, on the actuation per
formances.
Figure 22. The deflection strain versus the square applied electrical field for PU88-SiC@C nanocomposites films
The electric field induced a deflection of PU88 films which was lower than that of the PU75
films; it is in agreement with a similar value of the relative permittivity in both cases and a
lower value of Youngs modulus of the PU75 films. Indeed the strain depends directly on
the ratio of permittivity over Youngs modulus as shown in the equation (5).
At high electrical fields, the PU88-3SiC@C shows a 25% deflection strain which is 6 times
higher than for pure PU88. The gain in actuation is similar to that measured on
PU75-2.5Fe3C@C. This is consistent with results presented in previous section: dielectric
studies for both nanocomposites have shown an increase of the relative permittivity near 1
kHz with a gain of 1.35. Moreover, the mechanical reinforcement was also comparable for
the 2 types of composite films.
4. Conclusions
Two different methods of synthesis were investigated and exploited to develop new carbon-
based nanowires, SiC@SiO
2
, SiC@C and Fe
3
C, used as fillers in PU matrices to improve the
deflection capabilities of these electroactive polymers.
Polyurethane composites filled with low amounts of SiC@C and Fe
3
C@C nanowires (0 5 wt
%) were prepared by two solvent methods and yielded to very large surface films in the
range of 30-80 m in thickness. It can be noted that the deposit way was different for the
two systems: spin coating for PU88-SiC@C films and doctor blade application for PU75-
Fe
3
C@C, both methods being used for preparation of actuators made of polymers.
The dielectric properties were studied at different frequencies and showed an increasing of
the relative permittivity of the composites with the amount of nanowires. Permittivity and
conductivity results showed also that the percolation threshold was not reached whatever
the studied system. The mechanical properties were performed by using a simple tensile test
and it was shown that the increase in the Youngs modulus induced by the nanowires was
only moderate.
Based on DSC analysis, only a very slight modification of the polyurethane host was detect
ed with the incorporation of the nanowires and no difference in the degree of hard seg
ments/soft segments mixing was found.
The actuation capabilities were studied by measuring the strain under an applied electric
field with two methods.
The first method consisted in the measure of the electric field-induced thickness strain S
with a double-beam laser interferometer at low frequency (0.1 Hz). At a moderate electrical
field (6V/m), it was found a 3 fold increase of the electrostriction coefficient for only
0.5%wt of SiC@C into PU88 polymer. The polyurethane is a good candidate for electrome
chanical applications, it has a good ability to collect space charges due to its special structure
consisting of a mixing of hard and soft segments. It was shown that the nanowires acted as
charge traps and then enhanced the electrical field induced deformation.
The second method is to measure the deflection strain of a diaphragm type dielectric actua
tor working at high frequency (near 1kHz). The deflection strain was considerably enhanced
with the incorporation of either Fe
3
C@C and SiC@C nanowires into polyurethane films
whatever the type of the polyurethane host. The maximum deflection strains measured at
high electrical fields (18 V/m) reached 130 % for the PU75-Fe3C@C nanocomposites and
25% for the PU88-3SiC@C. These values are considerable and at least 6 times higher than
those obtained with corresponding pure polymer films.
Due to their evident large actuation capabilities, these new nanocomposites based on poly
urethane and carbon-based nanowires are very promising materials for micro electrome
chanical systems.
Acknowledgments
Authors thank the Institut Carnot for its financial support and Veronique Perrin from LGEF
(EA682 INSA Lyon) for mechanical tests and thickness strain measurements with laser inter
ferometer. The authors also acknowledge the CT (Centre Technologique des Microstruc
tures) of the Universit Lyon 1 for access to the SEM.
http://dx.doi.org/10.5772/54384
317
Author details
V. Salles
1
, L. Seveyrat
2*
, T. Fiorido
1
, L. Hu
1
, J. Galineau
2
, C. Eid
1
, B. Guiffard
2
,
A. Brioude
1
and D. Guyomar
2
*Address all correspondence to: [email protected]
1 Laboratoire des Multimatriaux et Interfaces, UMR 5615 CNRS, Universit Lyon1, Univer
sit de Lyon, Bat. Berthollet, France
2 Laboratoire de Gnie Electrique et Ferrolectricit, LGEF INSA Lyon, France
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