MULTI-

MULTI-WALLED CARBON NANOTUBE EFFECT ON

DIELECTRIC PROPERTIES OF POLYMER
MATRICES

Vlad-Andrei SCARLATACHE Romeo Cristian CIOBANU

Gheorghe Asachi Technical University Gheorghe Asachi Technical University
of Iaşi of Iaşi

Massimo PASQUALE Andrei PRUTEANU

Institutul Naţional de Cercetare Gheorghe Asachi Technical University
Metrologică (INRIM), Torino, Italia of Iaşi

REZUMAT. Această lucrare prezintă analiza dieletrică a unei mostre de material compozit pe bază de polipropilenă (PP) cu
inserţ
inserţii de fibre de nanotuburi de carbon multistrat (MWNT). Cu ajutorul analizorului de impedanţimpedanţă 4294A furnizat de către
Agilent şi a fixturii 16451B pentru teste dielectrice asupra materialelor, au fost măsurate permitivitatea reală, permitivitatea
imaginară,
imaginară, factorul de pierderi dielectrice şi conductivitatea materialului compozit pe bază de PP cu insertii de MWNT cu un
procent de 5% din totalul volumului. S- S-a urmărit în principal efectul polarizării electrice asupra proprietăţ
proprietăţilor dielectrice ale
materialului
materialului şi asupra conductivităţ
conductivităţii acestuia în funcţ
funcţie de evoluţ
evoluţia frecvenţ
frecvenţei în domeniul 40 Hz ÷ 15 MHz. În procesul de
măsurare s-s-au utilizat două metode, şi anume metoda prin contact direct şi metoda fără contact.

Cuvinte cheie:
cheie analiza dielectrică, polarizare electrică.

ABSTRACT. This paper presents dielectric analysis of a composites material sample, based on polipropilen (PP) with insertion
filers of multi-
multi-walled carbon nanotube (MWNT). Using impedance analyzer Agilent 4294A
4294A and dielectric test fixture 16451B,
16451B,
were measured real and imaginary permittivity, dielectric loss factor and conductivity of composite material based on PP
inserts MWNT with a rate of 5 % of total volume. The aim was mainly the effect of electric polarization on the dielectric
properties
properties of the material and its conductivity to a change in frequency of 40 Hz to 15 MHz. In the measurement proces we
used two methods, namely Contacting Electrode Method and Non- Non-contacting Electrode Method (Air Gap Method).
Method).
.
Keywords:
Keywords dielectric analysis, electric polarization.

1. CHARACTERISTICS OF THE MATERIALS Polypropylene can be processed by a variety of

USED IN MIXTURE fabrication techniques like film/sheet extrusion,
multifilament, non-woven, injection molding, blow
molding and profile extrusion [1].
Polypropylene is part of polyolefin's, It’s used in a wide variety of applications
thermoplastics with a wide spread of products that including packaging, textiles (e.g., ropes, thermal
are made by injection. Is a semi-crystalline polymer underwear and carpets), stationery, plastic parts and
that is used extensively due to its unique combination reusable containers of various types, laboratory
of properties, cost and easy to process.

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Buletinul AGIR nr. 4/2011 ● octombrie-decembrie 205
equipment, loudspeakers, automotive components,
and polymer banknotes.
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.
One of the most important utility of this composite
material is in the field of electromagnetic shielding.
Electrical properties of carbon nanotubes can be
improved by changing the chirality of their structure.
Formula for conductance of carbon nanotubes is given
by :
 2
G = G0 M =  2e  M (1)
 h 
Where G0=(2e2/h)=12.9(kΩ)-1 is the quantum unit of
the conductance, e is electron charge, h is Planck's
constant, M is an apparent number of conducting
channels including electron-electron coupling and
intertube coupling effects in addition to intrinsic
channels. In general, MWNT are quite often found to be
one-dimensional conductors with a high electrical
conductivity. The metallic properties of the MWNT are
due to their multiple-shell structure consisting of tubes
with various electrical properties, where additional
electronic coupling between shells takes place.
Moreover, MWNT are predicted to have ballistic
electron transport at room temperature (it refers to
conduction where Ohm’s law does not apply; the
resistance is not dependent on the CNT’s length). The
electrical current that could be passed through a
multiwall nanotube corresponds to a current density in
excess of 107 A/cm2. If nanotubes were classical
resistors, the power dissipated by such a current would
heat the nanotube so much that it would vaporize. The
fact that this does not happen suggests that the electrons
in nanotubes are strongly decoupled from the lattice [2].
Multi-walled nanotubes (MWNT) consist of
multiple rolled layers (concentric tubes) of graphite and
can exhibit superconductivity if it have optimal
numbers of electrically activated shells, which are
realized by end bonding.
A number of recent studies have shown the
usefulness of polymer-grafted CNTs as reinforcing
fillers for polymers. A better dispersion of multiwalled
carbon nanotubes (MWNTs) in PP matrix could be
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206 Buletinul AGIR nr. 4/2011 ● octombrie-decembrie
achieved by strong shearing force using a dynamic
packing injection molding process.
2. EXPERIMENTAL PROCEDURES
In the measurement proces we used an impedance
analyzer Agilent 4294A and dielectric test fixture
16451B. Were measured real and imaginary
permittivity, dielectric loss factor and conductivity in a
range of frequency 40 Hz ÷ 15 MHz. In our study, some
methods are tried to measure the spectroscopy for
polymer matrix, including contact method and non-
contact method (Air Gap Method) [3].
The measuring principle of contact method consist
in to let the measuring electrode to contact with the
sample and then measure the paralel capacitance (Cm)
of the sample directly. Dielectric constant (ε’) of
sample can be expressed as:
ε ' = C m d / ε 0πR 2 (2)
Where d is the thickness of sample, R is the radius of
the measuring electrode.
For the measuring principle of non-contact method
we must consider the air-gap between the measuring
electrode and sample . Dielectric constant of a test
material can be obtained with the following equations:
1
ε' = (3)
C s1 tg
1 − (1 − )×
C s2 ta
Parameters Needed:
Cs1 - Series capacitance when the test material is not
inserted [F]
tg - Gap between Guarded/Guard electrode and
Unguarded electrode [m]
Cs2 - Series capacitance when the test material is
inserted [F]
ta - Average thickness of test material [m]
The imaginary part of permittivity is give by equation:
ε"= ε ' × D (4)
Where D is the dissipation factor and it’s recommended
to be measure just for first method because the air-gap
method gives big erors for imaginary part [5].

Fig. 1. Frequency response of electric polarization [4]
slightly decreasing. This phenomen can be understand
from figure 4 where we have the real and imaginary
permittivity of PP-MWNT measured by contact
method. Note very clearly that around the frequency of
1.5 MHz we have transition from interfacial
polarization in the ionic and electrical resonance
phenomenon occurs or dielectric relaxation.
For our materials we have a high interfacial
polarization at low frequencies when the relaxation time
of polarization dipoles is much less than the half -
period of the field, the molecular dipole is perfectly
oriented, and the polarization material (respectively,
permittivity) is practically independent of frequency.
This polarization is typical of solid dielectric with
different filling materials respectively in this case we
have polipropilene like dielectric and MWNT like
fillers.
200

E ps'

150
Permittivity (F/m)

Fig. 2. Time Response of Dielectric Polarization [4]

100

3. DESCRIPTION OF ELECTRIC 50

POLARIZATION PRINCIPLE
0
0 2000 000 400 0000 1 000000 0 120 00000 140 00000

The real and imaginary part of permittivity can F requen cy (H z)

describe very easy the evolution of polarization of a Fig. 3. Real Permittivity of PP-MWNT in range of frequency 40 Hz
÷ 15 MHz using non contact measurement method
material subjected to an electric field.
We have four basic mechanisms of electric
When the frequency increases to a value where the
polarization: Electronic, Ionic, Rotational or Dipolar
relaxation time of polarization dipoles becomes larger
and Space Charge or interfacial.
than a half - period of the field applied, the molecular
This four types of polarization have a diferrent
dipole orientation can not be fully achieved, and that
frequency response, how we can see from figure 1,
polarization permittivity goes down, where we have the
but when we have an answer like in figure 2 we can
electronic polarization.
say that we have an resonance of the signal. In
general we can make a prelyminary prediction of a
Eps'
material polarity if we now the chemical structure of 100
Eps"
that material.
Permittivity (F/m)

4. EXPERIMENTAL RESULTS

Agilent 16451B electrodes system and Agilent

10
4294A Precision Impedance Analyzer is used to
measure dielectric properties of sample. The scanning
frequency covers from 40Hz to 15 MHz. 100000 1000000 1E7

As shown in figure 3, the real permittivity measured Frequency (Hz)

by non contact method increases and decreases abruptly Fig. 4. Real pemittivity, imaginary permittivity of PP-MWNT in
around the frequency of 1.5 MHz, after this value range of frequency 40 Hz ÷ 15 MHz using contact measurement
method

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Buletinul AGIR nr. 4/2011 ● octombrie-decembrie 207
 Relaxation time in our case is very large because we
can’t distinguish just one type of polarization from a
range of frequency, but we can say that is around 1.5
MHz when it’s observ a small pick of ε”.
Maximum ε” corresponds to maximum conversion
from EM energy to thermal energy, but in our case we
don’t have a clear peack of dissipation factor sow we
can’t assume a prognosis.
0.01
Conductivity (S/m)
1E-3
1E-4
100000 1000000
Frequency (Hz)
Fig. 5. Conductivity of PP-MWNT in range of frequency 40 Hz ÷
15 MHz using contact measurement method
To have peaks of imaginary permittivity,
temperature should be increased which will increase the
thermal agitation and will obtain more eloquent answer
for the charge carriers.
For the PP-MWNT nanocomposites with filler
content, the conductivity has a plateau in the low-
frequency regime but rises at 105 Hz.
The frequency dependency of the dielectric constant
and the conductivity of disordered solids generally
results from the polarization between clusters and
anomalous diffusion within each cluster.
The evolution of permittivity and conductivity can
be describe like a function of x and y folow next
principle. Permittivity can be wrote by the ε ≈ f-y
relation (f is frequency) for frquency > 105 Hz. The
critical exponent, y, is determined to be about 0.4. And
for conductivity σ ≈ fx for f > 105 Hz. The critical
exponent, x, is determined to be 0.53. Therefore, the x +
y = 1 relation can be approximately met for PP-MWNT
nanocomposites with a filler content above percolation
threshold [6].
When the MWNT content exceeds the percolation
threshold, the conductivity is mainly determined by the
paths of the percolating clusters in the low-frequency
regime, independent of frequency how we can see from
figure 5. The capacitative effect between clusters on the
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208 Buletinul AGIR nr. 4/2011 ● octombrie-decembrie
conductivity and dielectric constant becomes significant
only at high frequencies. As a result, conductivity
increases but dielectric constant drops with frequency in
the high frequency regime.
5. CONCLUSION
Composite material based on polypropylene with
insertion of multi-walled carbon nanotubes has a
conductivity that would allow use of this material in the
electromagnetic shielding.
Relatively high permittivity and dielectric loss peak
Sig
of around 1.5 MHz frequency could also help to shape
the material using an electromagnetic induction, that
can be useful in adhesives industry.
As a final conclusion we can say that by changing
the content of MWNT in polymer matrix can alter the
electrical properties of the material depending on the
desired use.
1E7
ACKNOWLEDGEMENT
This paper was realised with the support of
EURODOC “Doctoral Scholarships for research
performance at European level” project, financed by the
European Social Found and Romanian Government.
I would also like to thank S.R. Massimo Pasquale
and INRIM (Istituto Nazionale di Ricerca Metrologica,
Turin, Italy) research center for their support in carrying
tests.
REFERENCE
[1] http://www.fpcusa.com/products/PP/pdf/SingleScrew_BLAC
K.pdf
[2] Sid Senadheera, Electro-mechanical properties of Carbon
Nanotubes, Ryerson University, Toronto, Canada.
[3] AGILENT TECHNOLOGIES, Agilent 16451B dielectric
material test fixture Operation Manual.
[4] S.O. Kasap, Principles of Electronic Materials and Devices,
Third Edition, McGraw-Hill, 2005.
[5] Hairu Xu, Yewen Zhang, Feihu Zheng, Study on Measuring
Method of Dielectric Spectroscopy for Polymer Dielectrics,
Proceedings of the 9th International Conference on Properties
and Applications of Dielectric Materials, July 19-23,2009,
Harbin, China, ISBN 978-1-4244-4368-0.
[6] 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 (2007) 461–464.