Effect of heating rate on positive-temperature-coefficient-of-resistivity behavior of

conductive composite thin films

S. Hirano and A. Kishimoto

Citation: Applied Physics Letters 73, 3742 (1998); doi: 10.1063/1.122880

View online: http://dx.doi.org/10.1063/1.122880
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 APPLIED PHYSICS LETTERS VOLUME 73, NUMBER 25 21 DECEMBER 1998

Effect of heating rate on positive-temperature-coefficient-of-resistivity

behavior of conductive composite thin films
S. Hiranoa) and A. Kishimoto
Institute of Industrial Science, University of Tokyo, 7-22-1 Roppongi, Minato-ku, Tokyo 106-5885, Japan
~Received 20 July 1998; accepted for publication 16 October 1998!
A phenomenon was discovered that leads to the selective detection of abrupt increases in the
temperature of conductive composite thin films consisting of conductive ceramic fillers and an
insulating polymer matrix. Examining the heating rate dependence of the positive-temperature–
coefficient-of-resistivity ~PTCR! effect provided information about this intelligent phenomenon.
The anomalous PTCR effect was observed above 0.3 °C min21 for all the prepared films. However,
the magnitude of the anomaly decreased when the heating rate decreased below 0.1 °C min21, and
when the heating rate further decreased below 0.04 °C min21, the anomalous resistivity–
temperature relationship disappeared. The results suggest that these thin films can selectively detect
abrupt increases in temperature, which could lead to an intelligent mechanism. Our results also
suggest a PTCR mechanism, in which the expansion of crosslinked polymers in the thermodynamic
nonequilibrium state essentially produces the anomaly. © 1998 American Institute of Physics.
@S0003-6951~98!03251-3#

Heterogeneous composites of various combinations of
materials sometimes show new mechanical and electrical ef-
fects. As one example of the latter, an anomalous positive-
temperature-coefficient-of-resistivity ~PTCR! effect is
known in disordered insulator–conductor composites.1–8
This effect can be applied to various industrial devices in-
cluding thermal detectors, self-regulating heaters, current
limiting devices in circuit protection,7,8 etc.
Although various experimental and theoretical investiga-
tions of the anomaly in disordered composites have been
made,1–6 the basic mechanism is still in dispute because of
the complicated nature of the composites. Previously, many
researchers studied the geometric factors derived from the
relative differences in the expansion coefficients of the com-
ponents as well as electron tunneling across interparticle
gaps. However, the microstructure of disordered conductor–
insulator polymer composites is closely related to the ther-
modynamic factors reflecting the interfacial properties. Also,
because the PTCR transition is generally observed above the
transition point in the specific volume of the matrix, attention
must be paid to the thermomechanical property described by
the nature of a viscoelastic body. However, to the best of our
knowledge, there have been no experimental studies of the
anomaly from this perspective. This is believed to be one
reason why the detailed mechanism of the anomaly has re-
mained unknown for the past few decades.
From the practical aspect of temperature control, there
are many examples in which it is a rapid temperature change
rather than the temperature itself that significantly affects
various properties of a substance. In these cases, the use of
conventional PTCR devices, such as BaTiO3 ceramics,9
leads to overshooting. Overshooting can be prevented using
proportional-integral-derivative ~PID! control, but this re-
a!
Electronic mail: hirano-s@ceram.iis.u-tokyo.ac.jp
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quires both temperature sensing and calculation, resulting in
a larger, more complicated system. Until recently, self-
regulating heaters based on the PTCR effect have generally
involved BaTiO3 ceramics. Since the PTCR effect in BaTiO3
ceramics is independent of the heating rate, its use is limited
to maintaining a constant temperature. However, if PTCR
materials can be designed that respond to environmental
temperature changes, then these materials might be substi-
tuted in the PID controller and revolutionize the temperature
control industry.
In this letter, we describe a thin-film-type PTCR ther-
mistor that responds to the heating rate. This material can
selectively detect an abrupt temperature increase. The micro-
structure of our thin films is based on a conventional digly-
cidyl ether of bisphenol A epoxy resin @Epikote 828 and
B-002W ~100:53! supplied by Yuka Shell Epoxy K. K., To-
kyo, Japan#, which is an insulator, and conductive ceramic
whiskers with a 0.2 mm average diameter and an average
initial length of 5.1 mm @SnO2~Sb!-coated TiO2 , FT-3000,
supplied by Ishihara Sangyo Kaisha, Ltd., Mie, Japan#.
These starting materials were mixed in methylethylketone
and a well-dispersed precursor solution was obtained. To
control the thickness of the film, the viscosity of the solu-
tions was controlled by adjusting the amount of solvent. A
thin film was fabricated by spin casting, which involves
dropping the solution on a flat glass plate, which is then
rotated at 1600 rpm. The resulting films were annealed at
130 °C for 2 h for curing and to remove any residual solvent.
The resulting thin films were approximately 7 mm thick. Sil-
ver paste painted on both ends of the film surface was used
for the electrodes. The surface resistivity ( r s ) was measured
by the two-probe direct current method using a digital elec-
trometer ~model TR8652, Advantest Co., Ltd., Tokyo, Japan!
in dry air when the heating rate was changed from 0.04 to
1 °C min21.
3742 © 1998 American Institute of Physics
 Appl. Phys. Lett., Vol. 73, No. 25, 21 December 1998
FIG. 1. Surface resistivity as a function of temperature for epoxy composite
thin films containing 12.8 vol % filler at various heating rates.
As with lattice percolation, it is well known that the
electrical resistivity ~r! of the conducting composites10,11 fol-
lows a power law of the form r ;(V2V c ) 2t near the tran-
sition, where V is the volume fraction of the conductive
phase, V c is the critical volume fraction, and t is the expo-
nent for each system. For our thin films, the V c is approxi-
mately 6 vol % whiskers at room temperature, and the sur-
face resistivity r s decreases with increasing whisker
fractions above V c due to the formation of continuous con-
duction pathways. The dependence of the heating rate on the
PTCR effects for the conductive thin film containing 12.8
vol % filler is shown in Fig. 1. For heating rates above
0.3 °C min21, the surface resistivity increases by more than
six orders of magnitude at around 130 °C and is stable at this
high level after the conductor-to-insulator transition, show-
ing the anomalous PTCR effect. In this case, the resistivity
jump is quite sharp. This result suggests that the epoxy com-
posite films can serve as a thin-film-type thermal detector.
Strümpler reported that for crosslinked epoxy matrix com-
posites the transition temperature is correlated with the cur-
ing temperature.2 For the present composite, the transition
occurs exactly at the curing temperature (130 °C).
Further decreases in the heating rate below 0.3 °C min21
decrease the height of the anomaly observed around 130 °C.
Eventually, the anomaly disappears from the r s – T curves
when the heating rate is below 0.04 °C min21. In other
words, as the heating rate decreases, the anomaly fades
away. These results suggest that the anomaly only occurs in
the thermodynamic nonequilibrium state of the matrix, and
that the thin film can also selectively detect an abrupt in-
crease in temperature. The thin film has the potential to re-
place conventional BaTiO3 ceramic PTCR thermistors, in
which the same level of anomaly is generally observed at
any heating rate. This function can be used for abrupt heat-
ing self-regulating heaters. This thin film might also be sub-
stituted for the PID controller in a temperature control sys-
tem.
Meanwhile, macroscopic dilatometry between 0.1 and
21
2 °C min revealed that there is no heating rate dependence
for the coefficient of thermal expansion ~CTE! of the epoxy
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resin in dry air below and above its glass transition tempera-
On: Sat, 20 Dec 2014 18:41:22
S. Hirano and A. Kishimoto 3743
ture (T g ), '77 °C. The CTE in dry air for the epoxy resin
below and above T g are 5.431025 and 15.531025 K21,
respectively. This suggests that the relative differences in the
CTE of the components are not always related to the occur-
rence of the anomaly. These results are considered to be
quite surprising and important.
Our results cannot be easily interpreted by any previous
mechanism for a thermoplastic matrix4,5 that expands discon-
tinuously at the melting point, because in contrast to thermo-
plastics there is no discontinuity in the specific volume of the
crosslinked polymers.2,3 In addition, although several recent
studies1–3 have suggested a correlation between the expan-
sion and the anomaly, at present the qualitative model for the
crosslinked composites is insufficient for a complete discus-
sion, due to their complex nature.
We speculate that the heating rate dependence of the
anomaly in the present system is strongly related to the ther-
mal strain rate of the matrix. With a fast heating rate, the
conductor that adheres to the polymer starts moving rapidly
with the expansion of the polymer. In contrast, with a de-
creasing rate, most conductors remain in their initial position
in spite of the expansion of the polymer. It is thought that
this is the qualitative reason why the heating rate dependence
of the anomaly is observed.
However, we do not know why the continuous conduc-
tion pathways are not broken with slow heating. We also
speculate that the following supplementary mechanism is in-
volved. Generally, as the temperature increases above T g ,
the stiffness of the matrix rapidly decreases and the matrix
then becomes rubbery. The viscoelastic property of the
crosslinked matrix above T g is typically explained by a unit
that consists of a Hookean spring and a Newtonian
dashpot.12 Even if the matrix has viscoelastic properties un-
der normal conditions, at a certain temperature above T g the
unit should not work as a simple viscoelastic body, espe-
cially with a fast thermal strain rate. For the fast rate, all of
the initial deformation of the matrix caused by the thermal
expansion takes place in the spring, not in the dashpot. In
other words, the mechanical response of the matrix at a cer-
tain temperature during the fast heating rate is approximately
described by the Hookean spring, suggesting that the stiff-
ness of the matrix is apparently enhanced. Hence, due to the
dynamic effect of the action and reaction, the greater the
stiffness, the greater the expansion stress of the matrix at the
filler/matrix interface. As a consequence, because the con-
ductive fillers are strongly restrained by the matrix, rapid
expansion with a large expansion stress causes complete geo-
metrical separation of the contact between the fillers below
the percolation threshold.
Meanwhile, the expansion stress decreases due to stress
relaxation, which is derived from the Newtonian dashpot
when the thermal strain rate is slow. Hence, little breaking of
the continuous paths occurs with a slow heating rate. In ad-
dition, because the breaking of the continuous pathways or
contact opening among the conductive fillers might obey
some statistical distribution,6 most paths are disrupted at a
point prescribed by a critical temperature. Hence, the electri-
cal resistivity rapidly increases at the transition temperature.
Finally, if the viscoelastic response of the matrix can be
controlled, then PTCR materials that respond to a more rapid
 3744 Appl. Phys. Lett., Vol. 73, No. 25, 21 December 1998 S. Hirano and A. Kishimoto

temperature increase might be made. Our results are thought 1

to disprove several established theories that hold that the
anomaly is simply derived from the thermal expansion of the
polymers. Based on these observations, we believe that the
phenomenon described in this letter should occur in any
crosslinked polymer composite showing anomalous PTCR
effects.
The authors wish to thank Ishihara Sangyo Kaisha, Ltd.
and Yuka Shell Epoxy K. K. for providing the initial mate- 10
11
rials and all members of our laboratory for help with the
experiments. Special thanks also go to Professor M. 12
Miyayama ~University of Tokyo! for the experimental facil-
ity support.
M. B. Heaney, Appl. Phys. Lett. 69, 2602 ~1996!.
2
R. Strümpler, J. Appl. Phys. 80, 6091 ~1996!.
3
D. M. Moffatt, J. P. Runt, A. Halliyal, and R. E. Newnham, J. Mater. Sci.
24, 609 ~1989!.
4
K. Ohe and Y. Naito, Jpn. J. Appl. Phys. 10, 99 ~1971!.
5
J. Meyer, Polym. Eng. Sci. 13, 462 ~1973!.
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F. Carmona, E. Valot, L. Servant, and M. Ricci, J. Phys. ~France! 2, 503
~1992!.
7
A. R. Duggal and L. M. Levinson, Appl. Phys. Lett. 71, 1939 ~1997!.
8
R. Strümpler, G. Maidorn, and J. Rhyner, J. Appl. Phys. 81, 6786 ~1997!.
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W. Heywang, J. Am. Ceram. Soc. 47, 484 ~1964!.
S. Kirkpatrick, Rev. Mod. Phys. 45, 574 ~1973!.
D. S. McLachlan, M. Blaszkiewicz, and R. E. Newnham, J. Am. Ceram.
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See, for example, L. E. Nielsen and R. F. Landel, Mechanical Properties
of Polymers and Composites, 2nd ed., Revised and Expanded ~Marcel
Dekker, New York, 1994!.

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