IEEE Transactions on Dielectrics and Electrical Insulation Vol. 21, No.

3; June 2014 929

Electric Modulus
Powerful Tool for Analyzing Dielectric Behavior
Fuqiang Tian
School of Electrical Engineering, Beijing Jiaotong University, Beijing 100044, China

and Yoshimichi Ohki

Department of Electrical Engineering and Bioscience, Waseda University, Tokyo 169-8555, Japan

ABSTRACT
Complex electric modulus, defined as the inverse of complex relative permittivity, can be a
significantly powerful tool for analyzing dielectric behavior of a polymeric insulating material,
especially at relatively high temperatures, where complex permittivity usually becomes very
high due to electrode polarization and carrier transport. In this paper, a typical example of
the above is clearly shown by referring to an experimental result obtained for epoxy resin.
Index Terms — Electric modulus, dielectric property, dielectric relaxation.

1 INTRODUCTION Table 1. Comparison of Mechanical and Electric Moduli.

FOR electrical insulation, charge transport and accumu- Mechanical Dielectric

lation are matters of serious concern. Especially, for organic stress  electric field E
polymer dielectrics like epoxy resin, space charge accumu- strain  displacement D
lation enhances local electric field, which eventually leads elastic compliance J permittivity 
to partial discharges or dielectric breakdown. Moreover, =J D=E
elastic modulus G electric modulus M
charge accumulation near the electrode, which is often
=G E=MD
called electrode polarization (EP), would induce a huge
G=1/J M=1/
permittivity. Such EP obscures the bulk relaxation process
and makes it very difficult to examine its behavior. On such
For a Cole-Cole type relaxation, can be expressed as
occasions, use of complex electric modulus, which is
defined as the inverse of the complex relative permittivity,

. 2 
provides a significantly powerful tool. 1
Here, and are respectively the relative permittivity
2 THEORY OF ELECTRIC MODULUS values at infinite and near-zero frequencies, while is the
Complex electric modulus M* is defined as the inverse of relaxation time in the form of complex permittivity and  (0
the complex relative permittivity r*. Namely, for < < 1) is the shape parameter of the Cole-Cole arc. If
as a function of angular frequency  where satisfies equation 2, can be expressed as [4]
and are respectively the real permittivity and
dielectric loss factor, M* is expressed by the equation, 1 1 1 1
·
1 1
. 1 1 
1 
Electric modulus was first proposed in 1967 by McCrum 1
⁄ 1 ⁄ 1
et al. [1], to the authors’ knowledge, as an analogy to the 1
1 1  1 
mechanical modulus in the viscoelastic relaxation of
polymers as shown in Table 1. Macedo et al. were the first ⁄ 1
1 
to exploit the electric modulus for the investigation of 1
electrical relaxation phenomena in vitreous ionic conduc- 1 ⁄ 1
1 
tors [2]. Electric modulus has also been proved to be useful 1 ⁄ 1
to provide information about charge transport and dielectric 1 1 1
polarization in polymer electrolytes [3]. However, it has 1 1
been rarely exploited to study the dielectric behavior of ⁄  
1 ·
insulating polymers.
1 1
1
Manuscript received on 17 January 2014, in final form 2 February 2014,

3
accepted 3 February 2014. 1 M 1 M

DOI 10.1109/TDEI.2014.004561
930 F. Tian and Y. Ohki: Electric Modulus Powerful Tool for Analyzing Dielectric Behavior
6060
Here, 1/ and 1/ . Furthermore, the 20℃ 20℃
40℃ 40℃
relaxation time M is given by 5050 60℃ 60℃

D ielectric C onstant  r '

80℃ 80℃

Dielectric Constant  r '

100℃ 100℃
  4040 120℃
120℃
M · M , (4) 140℃
160℃ 140℃
30 180℃ 160℃
30
200℃ 180℃
200℃
⁄ 20
where M . Since is always larger than 20
, M or M is always smaller than . This means that the 10
relaxation moves to a high frequency in the modulus 10
spectrum compared to the permittivity spectrum. In -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10
addition, since both and now appear in the 10
-2 -1
10 10 Frequency
10
10 (Hz)
10
2
10
3
10
4
10
5

denominators, and become small if and (a) Frequency (Hz)

become large. Therefore, the tendency that large values of 10
5 (a)
5 20℃
and overwhelm relaxation peaks is completely 10 40℃ 20℃
4
10 60℃ 40℃
eliminated in the electric modulus spectrum. As shown 10
4
80℃ 60℃

D ielectric L oss Factor  r ''

above,  remains unchanged regardless of the arc whether it
3
10 100℃ 80℃

Dielectric Loss Factor  r ''

3 120℃ 100℃
is drawn in the permittivity mode or electric modulus mode. 10 2 140℃
10 160℃
120℃
Namely, in both Cole-Cole arcs of r* and M*, a smaller  10
2
1
180℃
140℃
means a wider distribution of relaxation time around , M 10 200℃ 160℃
1
180℃
or M at each respective center. 10 0 200℃
10
Moreover, the contribution of charge transport to 1010-1
0

appears in the form of -1

/ , (5)
where is the dc conductivity and is the permittivity of
vacuum. This means that becomes higher if becomes
lower for given . Charge accumulation near the electrodes
is also enhanced at low frequencies. Therefore, especially at
high temperatures at low frequencies, the dielectric
behavior of the bulk would be obscured. In this regard,
especially for the analysis of dielectric relaxation process or
its time constant at relatively low frequencies, M* can be a
significantly powerful tool.
3 A TYPICAL EXAMPLE
The sample we used to demonstrate the usefulness of M*
is epoxy resin. The base resin is diglycidyl ether of
bisphenol-A (816B, Mitsubishi Chemical), while a hardener
(113, Mitsubishi Chemical) used as a curing agent was
added to the base resin with a weight ratio of 10 (resin) : 3
(hardener). Complex permittivity was measured by an
impedance analyzer (126096, Solartron) at temperatures
from 20 to 200 °C at intervals of 20 °C in a frequency range
from 10-2 to 105 Hz by applying an ac voltage of 3 Vrms to
the sample of 200 μm thick, with vacuum-evaporated
aluminum electrodes with a diameter of 20 mm on both
sides.
Figure 1 shows r* spectra obtained experimentally. As a
significant feature, εr’ and εr’’ increase rapidly with an
increase in temperature. This indicates that dc conduction
exerts strong influences on r* at low frequencies at high
temperatures.
It has been known that ions, more specifically sodium
and chloride ions remaining from the synthesis procedure,
i.e. the condensation of epichlorohydrin with bisphenol-A
1010-2
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10
10
-2
Frequency (Hz) 2
-2 -1 0 1 3 4 5
10 (b) 10 10 1010 10 10 10
Frequency (Hz)
Figure 1 Real (εr’) and imaginary (εr’’) parts of the
(b)
complex permittivity as a function of frequency
Figure 1. Real (εr’) and imaginary (εr’’) parts of the complex
measured at different temperatures.
permittivity of epoxy resin as a function of frequency measured at
different temperatures.
in the presence of alkali, are present in epoxy resin [5]. In
addition, the unreacted hardener and nonreactive polar
impurities in the hardener would be ionized at elevated
temperatures [6]. Therefore, such ions are likely to be
responsible for the significantly large values of εr’ and εr’’.
Although not shown, thermal analysis indicates that the
glass transition temperature Tg of this sample is about
110 °C. Therefore, it is reasonable that both εr’ and εr’’
become larger when the temperature exceeds 110 °C [7].
Figure 2 shows complex electric modulus spectra
obtained by re-plotting the complex permittivity data shown
in Figure 1. Very clear relaxation peaks are seen in the M’’
spectra at temperatures between 120 and 200 °C,
accompanied by a stepwise transition from low to high
values in M’. The relaxation peak, which appears at
temperatures above Tg and moves to higher frequencies
with an increase in temperature, seems to be ascribable to
hopping of ions [8]. The charge carriers are mobile over
long distances at frequencies below the peak frequency,
while they are confined to potential wells and can hop only
a short distance at frequencies above the peak frequency [9].
Figure 3 shows fitting results of complex electric
modulus to the Cole-Cole equation 3 at temperatures
between 120 and 200 °C. The result indicates that the
relaxation process is close to a simple Debye single
relaxation, since  (= 0.92) is close to 1.0.
Figure 4 shows the reciprocal temperature dependence of
the peak frequency fm of the relaxation in the form of
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 21, No. 3; June 2014 931

Arrhenius plot obtained from M’’ spectra at temperatures

0.35
between 120 and 200 °C and a similar Arrhenius plot of
0.30 conductivity estimated from at 0.01 Hz using equation
0.25
5. The two activation energies are very close.
Real Modulus M'

0.20

0.15
20℃
40℃ 4 CONCLUSION
60℃
0.10
80℃
100℃
Complex permittivity of epoxy resin was measured at
120℃
140℃
various temperatures. Complex permittivity above the glass
0.05
160℃
180℃
transition temperature at low frequencies is dominated by
0.00
-3 -2 -1 0 1 2 3 4 5
200℃
6
the transport of ions. Complex electric modulus is a
10 10 10 10 10 10 10 10 10 10 powerful tool to reveal the dielectric relaxation and charge
Frequency (Hz)  
(a)  transport in dielectric materials.
20℃
0.10 40℃
60℃
0.08
80℃ REFERENCES
100℃
Imaginary Modulus M''

120℃ [1] N. G. McCrum, B. E. Read and G. Williams, Anelastic and

140℃ Dielectric Effects in Polymeric Solids, NewYork: Wiley, pp. 108-111,
0.06 160℃
180℃ 1967.
0.04 200℃ [2] P. B. Macedo, C. T. Moynihan and R. Bose, “The role of ionic
diffusion in polarization in vitreous ionic conductors,” Phys. Chem.
0.02 Glasses, Vol. 13, pp. 171-179, 1972.
[3] I. M. Hodge, M. D. Ingram and A. R. West, “Impedance and
modulus spectroscopy of polycrystalline solid electrolytes,” J.
0.00
Electroanal. Chem., Vol. 74, pp. 125-143, 1976.
10
-3
10
-2
10
-1
10
0 1
10 10 10
2 3
10
4
10
5
10
6 [4] F. Kremer and A. Schönhals, Broadband Dielectric Spectroscopy,
Frequency (Hz)   Berlin: Springer, pp. 71-98, 2003.
(b) [5] J. Ulański, K. Friedrich, G. Boiteux and G. Seytre, “Evolution of ion
Figure 2. Real (M’) and imaginary (M’’) parts of the complex mobility in cured epoxy-amine system as determined by time-of-
electric modulus as a function of frequency measured at different flight method,” J. Appl. Polym. Sci., Vol. 65, pp. 1143-1150, 1997.
temperatures. [6] M. Cohen, L. S. Kohn and D. I. MacDonald, “Dielectric loss features
of some epoxy resins,” J. Appl. Polym. Sci., Vol. 7, pp. 2003-2023,
1963.
0.16 120℃ [7] N. Fuse, H. Sato, Y. Ohki and T. Tanaka, “Effects of nanofiller
140℃ loading on the molecular motion and carrier transport in polyamide,”
160℃ IEEE Trans. Dielectr. Electr. Insul., Vol. 16, pp. 524-530, 2009.
Imaginary Modulus M''

0.12 180℃
200℃ [8] I. M. Hodge, K. L. Ngai and C. T. Moynihan, “Comments on the
electric modulus function,” J. Non-Cryst. Solids, Vol. 351, pp. 104-
0.08 115, 2005.
[9] A. A. Saif and P. Poopalan, “AC conductivity and dielectric
relaxation behavior of sol-gel BaxSr1-xTiO3 thin films,” Mater. Sci.
0.04 Technol., Vol. 27, pp. 802-808, 2011.

0.00
0.00 0.04 0.08 0.12 0.16 0.20 0.24
Real Modulus M'
Figure 3. Cole-Cole plots of electric moduli at different Tian Fuqiang was born in Gansu, China in 1983. He
temperatures. received his Bachelor and Doctor degrees in Electrical
Engineering from Beijing Jiaotong University in 2006
4 and 2012, respectively. At present, he is an Associate
log  Professor in the School of Electrical Engineering,
2 log fm Beijing Jiaotong University.
log ó(S/m) and log fm(Hz)

0
EA= 1.2 eV
-2

-4

-6
EA= 1.2 eV Yoshimichi Ohki (M’76-SM’98-F’00) received the
-8 B.Eng., M.Eng. and Dr. Eng. degrees in 1973, 1975
and 1978, respectively, all from Waseda University,
-10
Japan. He joined the teaching staff of the Department
-12 of EE, Waseda University in 1976 and is presently a
2.0 2.1 2.2 2.3 2.4 2.5 2.6 Professor.
1000/T (1/K)
Figure 4. Arrhenius fitting of relaxation frequency (fm) and conductivity
(σ) evaluated. EA: activation energy.