Frequency selective microwave absorption induced by controlled orientation of

graphene-like nanoplatelets in thin polymer films

Henok Mebratie Mesfin, A. C. Baudouin, Sophie Hermans, Arnaud Delcorte, Isabelle Huynen, and Christian
Bailly
Citation: Applied Physics Letters 105, 103105 (2014); doi: 10.1063/1.4895674
View online: http://dx.doi.org/10.1063/1.4895674
View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/105/10?ver=pdfcov
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APPLIED PHYSICS LETTERS 105, 103105 (2014)

Frequency selective microwave absorption induced by controlled orientation

of graphene-like nanoplatelets in thin polymer films
Henok Mebratie Mesfin,1 A. C. Baudouin,1,a) Sophie Hermans,2 Arnaud Delcorte,1
Isabelle Huynen,3 and Christian Bailly1,b)

1
Institute of Condensed Matter and Nanosciences (IMCN), Division of Bio and Soft Matter (BSMA),
Croix du Sud 1, Universit
e catholique de Louvain, B-1348 Louvain-la-Neuve, Belgium
2
Institute of Condensed Matter and Nanosciences (IMCN), Division of Molecules, Solids and Reactivity
(MOST), Place Louis Pasteur 1, Universit
e catholique de Louvain, B-1348 Louvain-la-Neuve, Belgium
3
Institute of Information and Communication Technologies, Electronics and Applied Mathematics (ICTEAM),
Place du Levant 3, Universit
e catholique de Louvain, B-1348 Louvain-la-Neuve, Belgium

(Received 12 August 2014; accepted 30 August 2014; published online 10 September 2014)
Highly ordered polycarbonate films containing parallel graphite nanoplatelets have been produced
by squeezing the corresponding random nanocomposites in the melt. Orientation of the conductive
fillers is observed in the plane of the film, i.e., perpendicular to the squeezing direction. It only
appears above a critical concentration of 15 wt. % and results from a confinement effect. Oriented
samples show a resonance-like sharp increase of the conductivity at a given frequency in the
microwave region, with the possibility to control the value of this frequency and the resulting
absorption by changing the nanoplatelets concentration. Above this frequency, the oriented polymer nanocomposites show a high level of electromagnetic absorption, which opens the possibility
to tailor materials with effective electromagnetic interference shielding by absorption in selected
frequency ranges. The in-plane stacking of conductive nanoplatelets separated by insulating polymer induces their strong capacitive coupling to the signal propagating in the plane of the polymer
film. As a result, the equivalent circuit of this propagation becomes a resonant system composed
C 2014
of capacitors, inductors, and resistors, which agrees well with the experimental results. V
AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4895674]

Wireless microwave electronic devices are nowadays

ubiquitous and exacerbate the pervasive issue of electromagnetic interference (EMI).1,2 As classical EMI shielding by
reflection becomes problematic for compact electronic systems (crosstalk issues), the alternative of shielding by
absorption is receiving renewed attention.3 Polymer composites containing conductive (nano) fillers such as graphite,1
carbon nanotubes,4 and graphene5 have shown to be effective for EMI shielding but they still so far mostly function by
reflection. The thermal shock method described by Chung6
and Furdin7 to expand graphite into graphite nanoplatelets
(GNPs) offers interesting and underexploited opportunities
for EMI shielding8 as the nanoplatelets can be oriented in
nanocomposites to tailor properties, as shown already for
mechanical or optical characteristics.9,10 Indeed, oriented
nanoplatelets in a polymer matrix offer the possibility of
resonant-like behavior at microwave frequencies and the
resulting very high absorption.
This letter reports the microwave electromagnetic properties of highly loaded polymer nanocomposites containing
oriented graphite nanoplatelets. First, a very simple method
is used to achieve orientation. Next, morphological and electromagnetic characterizations are discussed and the link
between the two in terms of resonant behavior and resulting
cut-off frequency of the propagation is clearly established,
with the help of a simple equivalent circuit.

Samples of MakrolonTM polycarbonate (OD2015 from

Bayer) were melt-mixed for 10 min with graphene-like
expanded graphite nanoplatelets (TIMREX, BNB 90 from
TIMCAL11) at 250  C, concentrations ranging from 1 to
25 wt. %, using a co-rotating twin screw extruder DSM
micro 15. To achieve orientation, the extrudates were further
hot-pressed for 3 min in a mold with a thickness of 400 lm.
The resulting samples were flexible opaque dark films.
Morphological characterization was conducted with the
help of a JEOL JSM-7600F scanning electron microscope
(SEM) at an accelerating voltage of 30 kV. Electromagnetic
measurements were performed with the microstrip method
by taping a copper strip as line and an Aluminum film as
ground on the nanocomposite films12 (Figure 1). In this configuration, the microwave signal is propagating in the plane
of the film used as substrate, along the direction of the microstrip line. An Agilent PNA-X 67 GHz vector network

a)

FIG. 1. Microstrip line used for electromagnetic characterization with schematic representation.

Present address: AGC glass Europe, 15 rue Bleriot, Gosselies, Belgium.

Electronic mail: christian.bailly@uclouvain.be

b)

0003-6951/2014/105(10)/103105/4/$30.00

105, 103105-1

C 2014 AIP Publishing LLC

V

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Appl. Phys. Lett. 105, 103105 (2014)

FIG. 2. SEM micrographs of polycarbonate expanded graphite nanocomposites at concentrations of (a) 25 wt. %,
(b) 20 wt. %, (c)17.5 wt. %, (d) 15 wt.
%, (e) 10 wt. %, (f) 1 wt. %, arrow
indicate the squeezing direction.

analyzer was used to measure the reflection and transmission

scattering parameters, S11 and S12, in the frequency range
from 10 MHz to 67 GHz. From those parameters, the constitutive electromagnetic parameters of the substrate, i.e., its
conductivity, were extracted, according to the method
explained in Ref. 12.
From SEM micrographs, it is observed that samples
ranging from 15 to 25 wt. % show nanoplatelets orientation
in a plane perpendicular to the squeezing direction (see
Figures 2(a)2(d)). Further, the spacing between nanoplatelets is related to their concentration, at least up to 20 wt. %.
The observed orientation is clearly due to a confinement
effect at high concentration, which is forcing the nanoplatelets to align in the biaxial flow direction during hot pressing.
On the other hand, for concentrations below 10 wt. %, the
nanoplatelets are randomly dispersed with no clear orientation as shown in Figures 2(e) and 2(f).
Electromagnetic characterization was conducted in
order to assess the effect of the nanocomposites morphology.
The transmission scattering parameter (S12) shows a
resonant-like minimum for samples with high GNP concentrations, i.e., 1525 wt. %. In addition, the position of the
minimum is shifted to lower frequency with increasing nanoplatelets concentration (see Figure 3).
As shown in Figure 3, samples with oriented platelets
have a cut-off frequency above which the transmission of

FIG. 3. Measured transmission scattering parameter (S12) versus frequency,

the number in the legend gives the graphite nanoplatelets wt. % and PC
stands for polycarbonate.

electromagnetic waves is significantly reduced, which suggests that most of the power is absorbed inside the polymer
nano-composite, making it attractive for microwave absorbers. Figure 4 confirms this hypothesis: whatever the wt. %,
the reflection coefficient S11 is kept lower than 10 dB over
the whole frequency range, without noticeable increase
above corresponding cut-off frequencies. This confirms that
reflection plays no significant role in the strong reduction of
power transmission observed in Figure 3.
The conductivity was extracted from the measured scattering parameters, as described in Ref. 12. The conductivity
shows a resonant-like strong jump (see Figure 5), at a frequency correlated with the position of the S12 scattering minima in Figure 3. At higher frequencies, the conductivity
either increases as in the case of 25 and 20 wt. % GNP or
stays relatively constant as in the case of 17.5 and 15 wt. %
GNP.
The observed electromagnetic properties can be directly
correlated to the morphology of the samples. We can assume
that strong capacitive coupling occurs between well oriented/stacked conductive nanoplatelets and microstrip mode
of propagation in the plane of the polymer substrate, yielding
a resonance at a certain frequency. Above it, wave transmission through the network of platelets dominates, with strong
absorption resulting from their conductive nature. The nanoplatelets concentration and orientation affects their spacing,
which directly controls the coupling capacitance and the
position of the resonance frequency.

FIG. 4. Measured reflection scattering parameter (S11) versus frequency for

the same samples as in Fig. 3.

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Appl. Phys. Lett. 105, 103105 (2014)

FIG. 5. Conductivity versus frequency for the same samples as in Figs. 3

and 4.

An equivalent circuit comprised of capacitors, resistors,

and inductors validates this explanation. Components of the
equivalent circuit have been arranged in such a way that it
mimics the SEM micrographs and the microstrip configuration used for the measurements. Resistors model the conductive nature of the platelets, while LM and CM are the per unit
length inductance and capacitance associated to the transverse electromagnetic (TEM) mode of propagation along the
microstrip line. The gap capacitance Cgap between stacked
nanoplatelets and the lateral capacitance Clateral between adjacent platelets couples the conductive platelets to the microstrip mode of propagation. The value of the coupling
capacitance is varied by changing the gap and lateral distance between nanoplatelets (Figure 6(a)). At low frequencies, capacitances connected to the resistors block the signal
path which flows consequently through the inductance and
capacitance of the line. At higher frequencies, the capacitances act as short-circuit so that the conductive path dominates
over the inductive path: the wave is trapped by resistorcapacitor (RC) conductive network and is strongly attenuated while its propagation is cut off.
Based on this circuit, conductivity is found to be resonant and the position of the resonance peak is indeed shifted
to lower frequency with decreasing nanoplatelets gap and
lateral distance (Figure 6(a)). The predictions shown in
Figure 6(b) mimic the experimental observations in Figure 5.
As shown in Figure 6(b), the model nicely matches the location of the resonance versus frequency and also qualitatively
shows the unsymmetrical nature of the conductivity below
and above the resonant frequency: the propagation occurs
through the lossless LM CM network below resonance, so
that transmission is preserved (Figure 3) while extracted conductivity is insignificant (Figure 5). Above resonance, the
RC conductive network dominates, inducing cut-off of the
propagation with strong absorption and high conductivity.
The model in Figure 6(a) however overestimates the amplitude of the conductivity at the resonance point. The mismatch may have arisen from the coarse nature of the model,
which assumes defect free graphene like structures, which is
different from reality. Further, the model assumes no connection between neighboring nanoplatelets. From Figure 5
and 6(b), it can be concluded that the resonant property

FIG. 6. (a) Equivalent circuit including capacitance between parallel platelets (Cgap is the equivalent capacitance of a stack of platelets), capacitance
between lateral platelets (Clateral), and capacitance between the strip line and
the ground (CM) assumed to be constant. (b) Conductivity versus frequency
from equivalent circuit.

emerges from the capacitive coupling induced by aligned

nanoplatelets with microstrip mode propagating in the polymer film. The resonant-like/cut-off frequency is proven to
depend on the gap between platelets, which itself depends on
concentration.
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