CHARACTERISATION AND OPTIMISATION OF THE ELECTROMAGNETIC

PROPERTIES OF CONDUCTING POLYMER COMPOSITES

IN THE MICROWAVE BAND
HOANG NGOC NHAN
Electric Power Univeristy, Hanoi, Vietnam

ABSTRACT
In this paper, the Genetic Algorithm (AG) is used to conceive an optimized multilayer electromagnetic shielding
of polyaniline-polyurethane (PAni/PU) conducting composites in the microwave band. Electrique and electromagnetic
properties of freestanding and three-layered PAni/PU films are presented in X and Ku bands. The electromagnetic
shielding performances of three-layered PAni/PU composite are investigated in the microwave with the object if to obtain
an attenuation of 40 or 80 dB depending on the applications. The optimisations results show that a 262m or 400m total
thickness can answer to many industrial (from 50MHz) or military (from 8GHz) shielding applications. The shielding
effectiveness of the optimized three-layered PAni/PU composite is measured and shown a good agreement with the values
optimized by the GA. Moreover, the AG is used to conceive absorbing materials at a chosen frequency. For two-layered
structure with a metal backing, it is observed an attenuation of 30 dB of the main peak at 10GHz for just 1.175 mm total
thickness.
KEYWORDS: Polyaniline-Polyurethane (PAni/PU), Genetic Algorithm (AG), X and Ku Bands
INTRODUCTION
Nowadays, with the proliferation of commercial, military, scientific electrical divices and equipement in high
frequencies, so the electromagnetic interference (EMI) becomes more of problem. To protect against the incoming and
potentially disturbing radiation from penetrating into the equipment, electronic divices must be shielded.
The interactions mechanisms of an electromagnetic wave with a material can be divided in three mechanisms:
reflection, absorption and multiple reflections inside the material [3]. The first mechanism, reflection, depends on the
permittivity and conductivity of the sample. The reflection increases with increasing permittivity and conductivity of
shield. The second mechanism of EMI shielding, absorption, requires the existence of mobile charge carriers (electrons or
holes), which interact with the electromagnetic radiation. The third mechanism of EMI attenuation is multiple reflections.
This mechanism depends on physical properties and geometric structure of shielding material.
With highly conducting property, metals are usually used as the shielding material [6]. In the recent years, new
materials as intrinsically conducting polymers (ICP), show high conductivities, lightweight and then appear as an
alternative to metals Among the ICP, Polyaniline (PAni) has a lot of potential applications in electronic and micro-
electronic industry such as opto-electronic devices, sensors [1], electrostatic discharge layers, printed circuit board [2] and
electromagnetic interference shielding [3,4,5]because of good environmental stability.
C.Y. Lee and al. [7] presented the EMI shielding effectiveness of the mixtures of PAni and conducting powders
such as silver, graphite and carbon black in the frequency range from 10 MHz to 1 GHz. The SE of the mixture of doped
International Journal of Electrical and Electronics
Engineering Research (IJEEER)
ISSN 2250-155X
Vol. 3, Issue 1, Mar 2013, 209-220
TJPRC Pvt. Ltd.
210 Hoang Ngoc Nhan
PAni and Ag powder is about 46 dB at temperature room. Those authors shown theoretically that the SE could be
ameliorated with the three-layered structure. Makela and al. [8] measured the SE for two-layered structure of PAni-CSA,
the SE found to be 39 dB at 1 GHz in the far field. A three-layered structure of PAni/PU was optimized by the Nelder-
Mead simplex method in our precedent work [9]. This is the local search method so the optimized results depend to the
starting point. In this work we present a global optimization method, Genetic Algorithm (GA), based on randomized
operations to optimize a three-layered structure (PAni-CSA/PU | Kapton | PAni-CSA/PU) for a fixed SE. Preparations
methods of freestanding films or three-layered PAni-CSA/PU films are presented. The electric and electromagnetic
properties of those films are measured and modelized in X and Ku bands. Finally, the comparison between the modelized
value and measured SE of three-layered film with optimized parameters is presented for two objectives SE>40 dB and
SE>80dB. Moreover, RF screen absorber with optimized structure is presented for frequency specified performance.
EXPERIMENTAL
Material
In the non-conducting form, Emeraldine Base (EB) is a type of polyaniline and the general structure is presented
in figure 1
N N
y

H H
N N

n

1-y

Figure 1: Schematic Representation of Emeraldine Base Y=0.5
The conducting polyaniline is obtained by oxidation with camphor sulphonic acid (CSA) as described in literature
[10]. EB was fully protonated by CSA with the 0.5 molecular radio (H
+
/PhN=0.5), it can be easily dissolved in
dichloroacetic acid (DCAA) to concentrations of 2.85% w/w. Protonation reaction lasted minimum 3 days at room
temperature. Finally, we have a 1.2g PAni in 100g PAni- (CSA)
0.5
/DCAA solutions.
Among the thermoplastics, the Polyurethane (PU) is flexible, has good mechanical properties and is easily soluble
in DCAA. First, PU was dissolved in the DCAA solution in the mass ratio of 1 to 10 % and then blended with PAni-
(CSA)
0.5
solution with different mass fraction of PAni in the PU and CSA. The mixture was carefully homogenized by a
magnetic agitator for 10 minute. Finnaly, the PAni-CSA
05
/PU solution was spread out on a glass container (for the
freestanding films) or on a Kapton slide (for the three-layered films). The solvents were evaporated under an infra lamp
for a period minimum of 48h and then 6 h in a vacuum oven at 60C. The obtained films have a specific mass about 1g.cm
-
3
. The freestanding films and a three-layered PAni/PU film are presented in the table 1 and table 2 respectively.
Table 1: Parameters of Freestanding PAni/PU Films

Sample PAni0.2/PU PAni0.5/PU PAni1/PU PAni4.7/PU PAni8.8/PU PAni16/PU PAni44/PU
Mass fraction
of PAni
0.2 0.5 1 4.7 8.8 16 43.86
Thickness
(m)
150 150 150 160 155 145 50

Table 2: Parameters of Three-Layered PAni/PU Films

Sample 1
st
Layer 2
nd
Layer 3
rd
Layer
TS8
PAni8.8/PU Kapton PAni8.8/PU
d=93m 125m 360m
Characterisation and Optimisation of the Electromagnetic Properties of 211
Conducting Polymer Composites in the Microwave Band
Theoretical Model of Shielding Effectiveness of Multilayered Structure
The electromagnetic shielding effectiveness SE of a material is defined by the ratio of the transmitted power (Pt)
through the material to the incident power (Pi) of an electromagnetic wave [3]. In general SE is given in decibel (dB):
|
|

\
|
=
|
|

\
|
=
i
t
i
t
E
E
P
P
SE log . 20 log 10
(1)
where E
i
and E
t
are the incident and transmitted field strengths. (comment : il faut mettre module du rapport des
champs, ici je ne peux pas corriger la formule)
A theoretical model of shielding effectiveness of multilayered structure is based on transmitted wave matrix in the
far field [4]. The reflection and the transmission of a normal EM wave on the N-layer structure are presented in the figure
2. Consider that each layer is homogeneous and isotropic, the physical parameters of i-layer are noted:
i
-permeability,
i
-
conductivity,
i
- permittivity and di- thickness. The intrinsic impedance of i
th
-layer (Z
i
)

depend on the frequency of incident
wave is given by:
2 / 1
/
(

+
=

j
Z
i i
i
i
(2)







The characteristic matrix of i
th
-layer is presented:
[ ]
(
(

=
) cos( ) sin(
) sin( ) cos(
i i i i
i
i i i i i
i
d k d k
Z
j
d k jZ d k
M
(3)
where: k
i
=
2

i
'
+
i
/( j
0
)
( )
(
0
/
c
)
2
[ ]
1/ 2
and
0
is the wavelength in the air and
c
is the cut-off
wavelength of the TE
01
mode in the waveguide, and
i
the relative permittivity.
The characteristic matrix of the whole structure presented:
[ ]
(

= =
22 21
12 11
2 1
] ]....[ ].[ [
M M
M M
M M M M
N
(4)
N-layers structure is in contact with two semi-infinite air media, so Z
0
=Z
N
=377 ().
According to K. Naishadham [4], the coefficients of reflection R and transmission T are represented:
E
I

1

1

2

2


nc

n

d
1
d
2
d
N

Figure 2 : The Reflection and the Transmission of a Normal EM Wave on the N-Layer Structure


x
y z
E
T
E
R
212 Hoang Ngoc Nhan
R =
M
11
Z
0
M
12
( ) Z
1
M
22
M
21
Z
0
( )
M
11
Z
0
M
12
( )+ Z
1
M
22
M
21
Z
0
( )
(5)
( ) ( ) [ ]
( ) ( )
0 21 22 1 12 0 11
0 21 22 12 12 0 11 22
2
Z M M Z M Z M
Z M M M M Z M M
T
+
+
=
(6)
Conception of a Multilayered Structure Shield
Multilayered Model
For the Electromagnetic Shielding
To improve the shielding efficiency and the mechanical properties of shielding material, the three-layer structure
was studied (figure 3), the physical parameters of each layer is presented in table 3.
Table 3: Rang of Physical Parameters of Three-Layered Material

Material (S/m) d (m)
1
st
layer: PAni/PU - From 30 to 10
4
From 0 to 300
2
nd
layer: Kapton 3.1 0 125
3
rd
layer: PAni/PU - From 30 to 10
4
From 0 to 300








For the Absorbing Material
We work with two-layered structure of PAni/PU deposited on a metallic plan as shown in the figure 4





Figure 4: Two-Layered Structure Deposited on a Metallic Plan
Objective Function
For the Electromagnetic Shielding
The objective is to obtain a fixed attenuation (SE
fix
) in the microwave band depending on the applications for the
three-layered material. The objective function is calculed according to:
d1 d2 d3
Kapton
PAni/PU
Film
PAni/PU
Film
Figure 3: Three-Layered Material
PAni%/PU (B)
PAni%/PU (A)
d1

d2
Metallic Plan
Characterisation and Optimisation of the Electromagnetic Properties of 213
Conducting Polymer Composites in the Microwave Band
=

) 10 ( ) (
20
1
T x f
Fix
SE
Minimum (7)
or : =

) 10 log( 20 ) (
20
1
T x f
Fix
SE
Maximum (8)
where T is the transmitted coefficient presented in the equation 6. (comment : mettre module de T)
For the Absorbing Material
For the two-layered structure deposited on a metallic plan, the objective is here to obtain minimum possible the
reflection at a chosen frequency. So the objective function is now:
= ) log( 20 ) ( R x f
R
Maximum (9)
where R is the reflected coefficient presented in the equation 5.
Genetic Algorithm
The genetic algorithm (AG) is a stochastic method of researcThh and optimization which mimic natural selection
and genetic [12]. The AG starts with the random creation of a first population of individuals.
Then the algorithm will pass from a generation to others by applying the mechanisms of evaluation, selection,
crossing, and mutation until obtaining a termination conditions (iteration count N, better fitness.). The genetic algorithm is
represented in figure 5.From N random individuals of population in binary code, N/2 pairs of parents are chosen. The
crossover operator produces a pair of children with probability P
c
. Following crossover, mutation operator is applied to all
individuals with probability P
m
, at mutations position, each bit on every binary individual is inverted. Now, there are N

individuals, that is greater than N individuals in the population parent. It has to select N individuals from N

individuals by
roulette wheel selection. The new population then becomes the current population and the cycle is repeated until some
termination criteria are satisfied (fixed number of iterations or until convergence is detected). We use 0.9 for P
c
and 0.01
for P
m
.












Verify the Termination Condictions?
Initialize N Random Individuals of
Population
Selection N/2 pairs of parents
Crossover
Mutation
Selecte a new population to
becomes the current population
No
Yes
Stop
Figure 5: Genetic Algorithm
214 Hoang Ngoc Nhan
RESULTS AND DISCUSSIONS
The Conductivity Measurements and the Morphology
The static conductivity of PAni/PU films was measured by the Van der Pauw or four probes techniques. The DC
conductivity and the uncertainty of PAni/PU films are presented in the table 3. The figure 6 shows the percolation curve.
The conductivity varies with the mass fraction of the PAni in the blend from the conducting states (10
4
S/m) to insulation
states (10
-5
S/m).
Table 3: Conductivity and Uncertanity of PAni/PU Film

Sample PAni0.2/PU PAni0.5/PU PAni1/PU PAni4.7/PU PAni8.8/PU PAni16/PU PAni44/PU
(S/m) 10
-4
0.1 2.44 235 792 2456 11500
(S/m) - - - 5.4 15.6 234 10
3







Figure 6: The Conductivity of the PAni/PU Films as a Function of PAni Concentration






Figure 7: Fit of Data Presented in Figure 8 to the Scaling Law of the Percolation
The conductivities of the PAni/PU films follow scaling law of the percolation. From the percolation threshold, we
have:
t
c
p p p ) ( ) (
0
= where
0,
p, p
c
and t are respectively a constant, the concentration of the PAni in the blends, the
percolation threshold, and the critical exponent. In our calculations, the best fit of the date is shown in figure 7 with p
c
=
0.188 wt% and t= 2.3. The obtained critical exponent t is near with the theoretical value (t=2.0) [13]. The very low
percolation threshold shows that the PAni/PU films have a good inter-chain interaction between PAni, acid dopant and PU.
The use of the Scanning Electron Microscope (SEM) technique permits to analyse the morphology of freestanding and
thee-layered PAni/PU films in profile section. In the figure 8, it cant distinguish the PAni, CSA and PU phases. It shows
that the film is homogeneous at micrometric scale. The figure 9 shows a good interaction between the PAni/PU and the
Kapton films.

Characterisation and Optimisation of the Electromagnetic Properties of
Conducting Polymer Composites in the Microwave







Figure 8: Scanning Electron Microscope








Figure 9: Scanning Electron Microscope of
SE Measurement
The figure 10 shows the SEs evolution of the 1, 5, 8.8 and 16 % of freestanding PAni films in X and Ku bands.
The shielding level depends on the conductivity and the thickness of material. For the freestanding PAni/PU films, the
thickness is smaller than its skin depth (
behaviour of PAni/PU films are flat in this band (8.2
1.75dB and the SEs increase with increasing of the conduct
PAni5/PU, PAni8.8/PU and PAni16/PU films respectively. It can also be observed that the three
an attenuation about 41dB corresponding to 99.1% of incident radiation (figur
intermediary layer has a significant role in resonant media to improve the SE level as well as very good mechanical
properties.
Here, the modelling results are in good agreement with measurements values as we have
measurements uncertainty induced by the calibration kit, the conductivity and the thickness measurementsof each film.
This modelling method permit to calculate the shielding behaviour of material in other band as well as it can be used in
objective function for shielding optimisation problem.


Pani 8.8/PU
Pani 8.8/PU
Kapton
Characterisation and Optimisation of the Electromagnetic Properties of
Conducting Polymer Composites in the Microwave Band
Scanning Electron Microscope of PAni0.5/PU in Profil Section
Scanning Electron Microscope of Three-Layered PAni 8.8/PU Film in Profil Section
the SEs evolution of the 1, 5, 8.8 and 16 % of freestanding PAni films in X and Ku bands.
The shielding level depends on the conductivity and the thickness of material. For the freestanding PAni/PU films, the
) /( 2
0
= ) (see the table 4) so the reflection SE is dominant and the SE
behaviour of PAni/PU films are flat in this band (8.2 18GHz). For the PAni 1/PU film, the achieved attenuation was
1.75dB and the SEs increase with increasing of the conductivity following the algorithm law: 21dB, 30dB and 38dB for
PAni5/PU, PAni8.8/PU and PAni16/PU films respectively. It can also be observed that the three-layered ST8 film presents
an attenuation about 41dB corresponding to 99.1% of incident radiation (figure 11). In the multilayered material, the
intermediary layer has a significant role in resonant media to improve the SE level as well as very good mechanical
Here, the modelling results are in good agreement with measurements values as we have
measurements uncertainty induced by the calibration kit, the conductivity and the thickness measurementsof each film.
This modelling method permit to calculate the shielding behaviour of material in other band as well as it can be used in
jective function for shielding optimisation problem.
Pani 8.8/PU
Pani 8.8/PU
Kapton
Interface
215
Profil Section
Profil Section
the SEs evolution of the 1, 5, 8.8 and 16 % of freestanding PAni films in X and Ku bands.
The shielding level depends on the conductivity and the thickness of material. For the freestanding PAni/PU films, the
) (see the table 4) so the reflection SE is dominant and the SE
18GHz). For the PAni 1/PU film, the achieved attenuation was
ivity following the algorithm law: 21dB, 30dB and 38dB for
layered ST8 film presents
e 11). In the multilayered material, the
intermediary layer has a significant role in resonant media to improve the SE level as well as very good mechanical
Here, the modelling results are in good agreement with measurements values as we have 5dB of the
measurements uncertainty induced by the calibration kit, the conductivity and the thickness measurementsof each film.
This modelling method permit to calculate the shielding behaviour of material in other band as well as it can be used in
216 Hoang Ngoc Nhan
Table 4: Skin Depth of PAni/PU Films at 10GHz
Sample PAni1/PU PAni5/PU PAni8.8/PU PAni16/PU
Skin depth (m) 3.2.10
3
3.2.10
2
1.8.10
2
102
d(m) 150 160 155 145
0
5
10
15
20
25
30
35
40
45
8.0E+09 1.0E+10 1.2E+10 1.4E+10 1.6E+10 1.8E+10
S
E
(
d
B
)
F(Hz)
PAni 1/PU
PAni 5/PU
PAni 8,8/PU
PAni 16/PU
Modelling Measurements

Figure 10: Shielding Effectiveness of the Freestanding PAni/PU Films in X and Ku Bands
0
5
10
15
20
25
30
35
40
45
50
8,0E+09 1,0E+10 1,2E+10 1,4E+10 1,6E+10 1,8E+10
F(Hz)
S
E
(
d
B
)
Modelling Measurement

Figure 11: Shielding Effectiveness of TS8 Film in X and Ku Bands
Optimisation Results
The shielding effectiveness of three-layered material (described in 2.3.1) was calculated form a combination of
four parameters: the conductivity and the thickness of the first and the third layers. The optimisation purpose is to find four
parameters that define a SE best suited for the specific application with least weight of PAni and the thinnest total
thickness. For many commercial shielding applications, the SE is greater than 40dB and for many military shielding
applications, the SE are significantly higher than 80dB [3].
For Commercial Applications from 50MHz
The GA started with the randomly generated initial population. By using the objective function for the maximum
function-equation 9, the fitness evaluations were increased and stabilized at 250dB after 400 iterations i.e. the transmitted
coefficient error between T desired and T calculated is about 3.7 10
-6
. After 400 generations, the best solution was found in
the table 5:
Characterisation and Optimisation of the Electromagnetic Properties of 217
Conducting Polymer Composites in the Microwave Band
Table 5: The Optimized Parameters for Many Commercial Applications from 50MHz

Material (S/m) d (m)
1
st
-layer: PAni /PU - 2215.3 78.4
2
nd
-layer: Kapton 3.1 0 125
3
rd
-layer: PAni /PU - 5888.7 59.6

Table 6: Film Carried Out from the Optimized Parameters in the Table 5

Material (S/m) d (m)
1
st
-layer:PAni16% /PU - 2450 80
2
nd
-layer: Kapton 3.1 0 125
3
rd
-layer: PAni 30% /PU - 5700 55

From the calculated conductivities, we can find the concentration of PAni in the blends by using the conductivity
model presented in 3.1. We decided to carry out to the first layer with 16% of PAni and 80m of thickness, the third layer
with 30% of PAni and 55m of thickness. So the three-layered film with the optimized parameters in the table 5 was
carried out (figure 6).
The SE of this film was measured in X and Ku band. It is observed that the measured SE is good agreement with
the calculated SE (figure 12).
For many Military Shielding Applications at 8GHz
By using the objective function (for maximum), the fitness evaluations were increased and stabilized at 300dB, i.e. the
transmitted coefficient error (T desired T calculated) is about 3 10
-7
. After 200 generations, the best solution was found in the
table 7:
Table 7: Optimized Parameters for many Military Applications from 8 GHz
Material (S/m) d (m)
1
st
-layer: PAni /PU - 5803.7 196
2
nd
-layer: Kapton 3.1 0 125
3
rd
-layer: PAni /PU - 5972.7 180.1

Table 8: Film Carried Out from the Optimized Parameters in the Table 7

Material (S/m) d (m)
1
st
-layer:PAni 30% /PU - 5700 210
2
nd
-layer: Kapton 3.1 0 125
3
rd
-layer: PAni 30% /PU - 5700 180

A three-layered film with the optimized parameters in the table 7 was carried out. The first and the third layer are the 30%
of PAni/PU with the physical parameters shown in figure 8. A better precision of conductivity and thickness between the optimized
parameters and the real parameters show a close agreement between measured SE and calculated SE (figure 13).
218 Hoang Ngoc Nhan
0
10
20
30
40
50
60
70
80
1,0E+06 1,0E+07 1,0E+08 1,0E+09 1,0E+10 1,0E+11
F( Hz)
S
E

(
d
B
)
Measurement
Modelling

Figure 12: Shielding Effectiveness Modelization as a Function of Frequency with the Optimized Parameters in the
Table 6
0
20
40
60
80
100
120
140
160
180
200
1,0E+09 1,0E+10 1,0E+11
F(Hz)
S
E

(
d
B
)

Figure 13: Shielding Effectiveness Modelization as a Function of Frequency with the Optimized Parameters in the
Table 8
For the Absorbing Material at 10GHz
For the two-layered structure of PAni/PU deposited on a metallic plan, the optimized parameters of each layer
were found and presented in the table 9 after 300 generations. From the figure 14, we obseve that an attenuation of 30dB of
the main peak at 10GHz for just 1.175 mm total thickness (0.812 mm for the first layer made of PAni (1.1%)/PU and 0.363
mm for the second layer of PAni (0.6%)/PU. This absorbing characteristic comes from the ohmic losses and multiple
reflections in each layer of PAni/PU.

Table 9: The Optimized Parameters
Material (S/m) d (m)
1
st
-layer:PAni (1.1%) /PU 41.97 4.68 812.5
2
nd
-layer:PAni(0.6%)/PU 5.91 0.9 363.4


Modelling
Measurement
Characterisation and Optimisation of the Electromagnetic Properties of 219
Conducting Polymer Composites in the Microwave Band


Figure 14: Reflectivity Modelization of Two-Layered Structure (Table 9) as a Function of Frequency
CONCLUSIONS
A high level of electromagnetic shielding performance was achieved by using the Polyaniline blends with
Polyurethane and the composites with Kapton film. The physical properties of the PAni/PU blends were tailored from
insulating (10
-11
S/m) to conducting (11500 S/m) states, showing a very low percolation threshold (0.188%). Those blends
could be replaced corrosive metals and carbon to control electromagnetic radiations. The PAni16/PU film with just 145 m
of thickness have 38dB attenuation radiation in X and Ku bands. It was still observed better attenuation (41dB) on the
same bands for three-layer composite of Polyaniline with only 570m of the total thickness. The shieldings optimization
was performed by using the genetic algorithm to conceive multilayer composites with the wished SE level. SE higher
than 40dB from 50MHz and 80dB from 8GHz were found with a total thickness below 1mm, compatible with many
commercial and military shielding applications. The permittivities of these blends particularly for the high conducting
films will be characterized to ameliorate the precision of the modelling and optimization methods.
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