Analysis of Dielectric Loss at High Frequency, for a

Nanocomposite Polymer Matrix, Based on

Polypropylene with Insertion of Multi-walled Carbon
Nanotubes (MWCNTs)

Daniel Matasaru, Vlad – Andrei Scarlatache, Andrei Pruteanu, Bogdana Florean, Georgiana Viziteu
Department of Electrical Measurements and Materials
The “Gheorghe Asachi” Technical University of Iasi
Iasi, Romania
vscarlatache@ee.tuiasi.ro

Abstract— In this paper is illustrate the dielectric characteristics
of a nanocomposite polymer matrix based on polypropylene (PP)
with insertion of multi-walled carbon nanotubes (MWCNTs).
The dielectric characteristics analyzed are the real and imaginary
part of permittivity, dielectric losses and electrical conductivity of
the sample based on PP with 5% insertion of MWCNTs. The
measurements are done in a range of frequency between 1 MHz
to 3 GHz and for a variation of temperature from 30 ºC to 120
ºC, with a step of 5 ºC. Graphical representation of dielectric
characteristics are done in 2D and 3D plans.
Keywords - permittivity; dielectric losses; polarization;
conductivity;
I. INTRODUCTION
Polypropylene is part of polyolefin's thermoplastics with a
wide spread of products that are made by injection. Is a semi-
crystalline polymer that is used extensively due to its unique
combination of properties, cost and easy to process.
Polypropylene can be processed by a variety of fabrication
techniques like film/sheet extrusion, multifilament, non-woven,
injection molding, blow molding and profile extrusion [1].
Nowadays we try to develop composite materials based on
polypropylene materials with different inserts, which could
improve certain physical, mechanical or chemical properties.
One of these materials may consist of a mixture of
polypropylene with multi-walled carbon nanotubes, which
would result in a material with better mechanical and physical
properties that can be improved by increasing or decreasing
percentage of multi-walled carbon nanotubes in polymer
matrix [2].
A lot of studies was made on this kind of nanocomposite
material in general for developing mechanical and electrical
properties.
The recent commoditization of multiwall carbon nanotubes
(CNT) in particular, as substitute for conductive carbon black
(CB) based composites has attracted immense interests from
different sector of industries. Typically, CNT can achieve
similar or greater electrical property at a fraction of CB loading
level, therefore retaining the ease of processing. It appeals
especially in applications requiring stringent cleanliness
property where contamination is detrimental to materials
performance e.g. high-end electronics. The key challenges to
successful fabrication of CNT thermoplastic nanocomposites
that combined outstanding electrical and mechanical properties
rest in understanding of its processing behavior to obtain high
degree of percolating morphology (i.e. inter-connective
network structure of CNT in polymer matrix) [3].
Because of the very low conductivity of the insulating
polymer, a model that has any conduction of charge by the
polymer would have a conductivity not very different from the
polymer conductivity; hence, nanotubes must carry all the
charge for high conductivities to be achieved. If nanotubes are
in contact, then transfer of charge from one nanotube to another
will offer much higher resistance than charge traveling along
nanotubes, even for the case of semiconducting tubes. High
resistances occur because of the limited contact area between
two tubes. This type of resistance, termed constriction
resistance, has been shown to be limiting because increasing
compression forces [4,5] or decreasing the hardness of the filler
[6] leads to higher conductivities; that is, constriction resistance
is the limiting resistance [7].
The percolation threshold of multi-walled carbon nanotubes
in polypropylene matrix depend on the processing behavior to
obtain nanocomposition of this two materials. Are papers who
related a percolation threshold of 0.22% [8] for this type of
materials. In our study will have 5% volume of MWNTs in
sample, sow more than related studies.
The PP/MWNTs nanocomposites prepared at a high shear
rate exhibit a much lower percolation threshold than
composites fabricated at a low shear rate [8].
The sample was realized by direct melt compounding and
have a diameter of 5 mm and a thickness of 2.9 mm. This
sample was cut from material with a perforating punches.
 II. MEASUREMENT SYSTEM DESCRIPTION It is very important that when starting a measurement, the
In the analyzing process of the characteristics of dielectric system to be well calibrated in order to not appear errors due to
parameters was used Agilent E4991A impedance analyzer, a line measuremet impedance. Therefore first calibrate the line
dielectric cell BDS 2200 that were connected using the and then the cell.
extension 002 of the broadband spectrometer Novocontrol,
concept 80. Also for temperature control was used the system III. EXPERIMENTAL RESULTS INTERPRETATION
Quatro Cryosystem. The measurements were performed in the frequency band:
With Agilent E4991A impedance analyzer can be measured 1 MHz ÷ 3 GHz in 20 points with a logarithmic scale. The
both the magnetic and dielectric characteristics of the materials, temperature range is the same as at low frequencies, 30 ÷ 120
but with different cell. In this paper we will focus on measuring °C, with an increment of 5 °C.
the dielectric characteristics with the system presented in Fig. Sample used for measurements in this frequency range
1. have a thickness of 2.9 mm. The Graphical representation is
The Agilent E4991A impedance analyzer has the following made in 2D and 3D form for the clarity of the rezults.
characteristics: The 2D and 3D representation of the real and imaginary
• The frequency band: 1 MHz ÷ 3 GHz; permittivity for sample PP-NTCM at HF in function of the
temperature variation are presented in Fig 2 and Fig. 3.
• The rank of the impedance: 100 mΩ ÷ 100 kΩ;
In Fig. 2 is observed a evolution of the dielectric constant in
• The accuracy: 0.3% of measured value (maximum); the same decreasing trend as in low frequency, with the remark
• The rank impedance: 100 fF ÷ 100 nF; that it is not strongly influenced by the temperature as at low
frequency.
• The rank of tan(Delta): 3m ÷ 3k;
10 0
• The accuracy of tan(Delta) 3m (max); E ps' 30 (°C )
E ps' 35 (°C )
E ps' 40 (°C )
• The rank of θ: 0 ÷ 360 degrees; E ps'
E ps'
45 (°C )
50 (°C )
E ps' 55 (°C )
• The accuracy: 0.2 degrees (maximum); E ps'
E ps'
60 (°C )
65 (°C )
E ps' 70 (°C )
• The voltage rank DC: ± 40 V; E ps'
E ps'
75 (°C )
80 (°C )
E ps' 85 (°C )
• The accuracy: 46 mV;
Eps'

E ps' 90 (°C )
E ps' 95 (°C )
E ps' 100 (°C )

• Calibration: Open, closed, full, capacitor with low loss E ps'

E ps'
105 (°C )
100 (°C )

and capacitor 50 Ω. E ps'

E ps'
115 (°C )
120 (°C )

The analyzer uses a dielectric cell BDS 2200 which has the
following characteristics: 10

• The frequency band: 1 MHz ÷ 3 GHz; 1 0 00 00 0 1E7 1E8 1E9

F re q u e n cy (H z)
• Electrodes of gold metal with 5 mm dimension that are
differentiated by a border for superior electrode;
• Calibration: Open, Closed.
100
Eps'

120
110
90 100
1000000 7080 ° C )
1E7
60 (
50 e
ur
F re 1E8 40 r at
qu
en 30 pe
cy m
(H
1E9
Te
z) 20

Figure 1. The measurement system of the dielectric characteristics at high

frequency. Figure 2. The 2D and 3D diagram of real permittivity for sample PP-NTCM
at HF in function of the temperature variation.
 A slight relaxation can be observed at around frequencies
of 500 MHz, due to ionic polarization mechanism, a
mechanism that is specific to this frequency band, but that is T a n (D e lta )
T a n (D e lta )
3 0 (°C )
3 5 (°C )

not specific to these types of materials.

T a n (D e lta ) 4 0 (°C )
T a n (D e lta ) 4 5 (°C )
T a n (D e lta ) 5 0 (°C )
T a n (D e lta ) 5 5 (°C )

Regarding the imaginary permittivity, Fig. 3, it is observed T a n (D e lta )

T a n (D e lta )
6 0 (°C )
6 5 (°C )

that decreases with increasing frequency and increased slightly T a n (D e lta )

T a n (D e lta )
T a n (D e lta )
7 0 (°C )
7 5 (°C )
8 0 (°C )
1
with increasing temperature. Is not observed a peak value for

Tan(Delta)
T a n (D e lta ) 8 5 (°C )
T a n (D e lta ) 9 0 (°C )

the loss dielectric factor, and we can say that in this band don’t T a n (D e lta )
T a n (D e lta )
9 5 (°C )
1 0 0 (° C )

have the resonance phenomena. T a n (D e lta )

T a n (D e lta )
T a n (D e lta )
1 0 5 (° C )
1 1 0 (° C )
1 1 5 (° C )
T a n (D e lta ) 1 2 0 (° C )
The evolution of the dielectric losses in 2 D and 3D
representation is shown in Fig. 4, as Tan (Delta), where a peak
is observed clearly around the frequency of a few MHz, a
phenomenon that is due to the dipolar polarization or
polarization of orientation, which was observed more clearly in 1000000 1E7 1E 8 1E9

the material analysis at low frequency [9]. This peak becomes F re q u e n c y (H z )

more pronounced with increasing the temperature and

disappears with increasing the frequency. Also a step is
observed along the reduction of Tan (Delta) around the
frequency of 500 MHz, due to the slight influence of ionic
polarization.

1
Eps" 30 (°C )

Tan(Delta)
Eps" 35 (°C )
Eps" 40 (°C )
Eps" 45 (°C )
Eps" 50 (°C )
Eps" 55 (°C )
100 Eps" 60 (°C )
Eps" 65 (°C )
Eps" 70 (°C )
Eps" 75 (°C )
Eps" 80 (°C )
Eps" 85 (°C )
140
Eps''

Eps" 90 (°C )
120
Eps" 95 (°C ) 1000000 100
Eps" 10 0 (°C ) 80 C )
Eps" 10 5 (°C ) 1E 7 60 (°
10 Eps" 11 0 (°C ) re
F re tu
Eps" 11 5 (°C )
qu 1E 8 40 ra
Eps" 12 0 (°C ) en pe
cy m
(H
z)
1E 9 Te
20

1
1000 000 1E 7 1E 8 1E 9 Figure 4. The 2D and 3D diagram of the dielectric losses for sample PP-
F re q u e n cy (H z) NTCM at HF in function of the temperature variation.

Fig. 5 presents the diagram 2D and 3D for the evolution of

conductivity at high-frequency depending on the temperature
variation. It can say that with increasing frequency the
conductivity increases. This characteristic is dependent on the
1 00
temperature, increasing with it at low frequencies in order of
MHz, but not so strong as at low frequency. Since the
frequency increases the conductivity dependence of
temperature is mitigated.
Eps''

10
IV. CONCLUSIONS
This paper presents the dielectric characteristics of a
1 21040
polymer nanocomposite material with insertion of multilayer
1 00
1 0 00 0 00
80 ) nanotubes carbon. These materials have a very interesting
1E7 60 C
(° evolution of the dielectric characteristics in frequency and
e
F re 1E8 40 t ur
qu
en ra temperature variation, due to the polarization mechanisms
cy pe
(H
z)
1E 9
20 T em present. At frequencies in order of MHz appears the
polarization of orientation that increase with increasing the
temperature. Analyzing the dielectric characteristics at high-
Figure 3. The 2D and 3D diagram of the imaginary permittivity for sample frequency, observe that mechanism of polarization is present at
PP-NTCM at HF in function of the temperature variation. all temperatures.
 an insulating character, with increasing the frequency it has a
semiconductor character.

S ig' (S /cm ) 30 (°C ) V. AKNOWLEDGMENT

S ig' (S /cm ) 30 (°C )
1 E -3
This paper was realized with the support of EURODOC
S ig' (S /cm ) 30 (°C )
S ig' (S /cm ) 30 (°C )
Sig' (S/cm)

S ig' (S /cm ) 30 (°C )

S ig'
S ig'
(S /cm )
(S /cm )
30
30
(°C )
(°C ) “Doctoral Scholarships for research performance at European
S ig'
S ig'
S ig'
(S /cm )
(S /cm )
(S /cm )
30
30
30
(°C )
(°C )
(°C )
level” project, financed by the European Social Found and
S ig'
S ig'
(S /cm )
(S /cm )
30
30
(°C )
(°C )
Romanian Government.
S ig' (S /cm ) 30 (°C )
S ig' (S /cm ) 30 (°C )
S ig' (S /cm ) 30 (°C )

REFERENCES
S ig' (S /cm ) 30 (°C )
S ig' (S /cm ) 30 (°C )
S ig' (S /cm ) 30 (°C )
S ig' (S /cm ) 30 (°C )
1 E -4
1000000 1E7 1E8 1E9
[1] “Processing Guide, Single Screw PP Sheet Extrusion,”
F re q u e n c y (H z )
http://tinyurl.com/dx8pbcw.
[2] V. A. Scarlatache, R. C. Ciobanu, M. Pasquale, A. Pruteanu, “Multi-
walled carbon nanotube effect on dielectric properties of polymer
matrices,” Buletinul AGIR nr. 4/2011, pp. 205-208, 2011.
[3] C. Y. Lew., M. Claes, F. Luizi, “The Influence of Processing Conditions
on the Electrical Properties of Polypropylene Nanocomposites
Incorporating Multiwall Carbon Nanotube,” Nanocyl, 2009.
[4] F. Carmona, R. Canet, P. Delhaes, “Piezoresistivity of heterogeneous
1 E -3 solids,” J. Appl. Phys., 61, pp. 2550–2557, 1987.
[5] S. Yoshikawa, T Ota., R. Newnham, A. Amin, “Piezoresistivity in
Sig' (S/cm)

polymer–ceramic composites,” J. Am. Ceram. Soc., 73, pp. 263–267,

1990.
114200
Te

100 [6] G. R. Ruschau, S. Yoshikawa, R. E. Newnham, “Resistivities of

mp

80
60 conductive composites,” J. Appl. Phys., 72, pp. 953–959, 1992.
er
a tu

40 [7] B. P. Grady, “Carbon nanotube-polymer composites : manufacture,

re

properties, and applications,” John Wiley & Sons, ISBN 978-0-470-

(°C

1 E -4 20 59641-8, 2011.
)

1000000 1E7 1E8 1E9

F re q u e n c y (H z ) [8] S. C. Tjong, G. D. Liang and S. P. Bao, “Electrical behavior of
polypropylene/multiwalled carbon nanotube nanocomposites with low
percolation threshold,” Scripta Materialia 57, pp. 461–464, 2007.
Figure 5. The 2D and 3D diagram of the conductivity for sample PP-NTCM [9] M. Olariu, V. A. Scarlatache, A. Niagu, S. Ursache, R. C. Ciobanu, “The
at HF in function of the temperature variation. Influence of Frequency and Temperature upon Dielectric Behavior of
Polypropylene reinforced with Multi-walled Carbon Nanotubes
From this reason we can conclude in comparison with the (MWCNTs),” Proceedings of the 13th International Conference on
Optimization of Electrical and Electronic Equipment, pp. 287 – 292,
study from low frequency [9] that with increasing the Print ISBN 978-1-4673-1653-8, 2012.
temperature, polarization for the samples PP-NTCM appears at
higher frequencies.
The electrical conduction of this material increases with
increasing the frequency. If at low frequency this material has