Effect of Filler Treatment and Crosslinking on Mechanical
and Dynamic Mechanical Properties and Electrical
Conductivity of Carbon Black-Filled Ethylene–Vinyl
Acetate Copolymer Composites
N. C. Das, T. K. Chaki, D. Khastgir
Rubber Technology Centre, Indian Institute of Technology, Kharagpur-721302, India
Received 29 July 2002; accepted 23 January 2003
ABSTRACT: Mechanical, dynamic mechanical, and elec-
trical conductivity of conductive carbon black-filled ethyl-
ene–vinyl acetate (EVA; 28% VA) composites were investi-
gated. The above-mentioned properties were also measured
when carbon black was treated with nitric acid before addi-
tion to the EVA matrix. It was found that acid-treated carbon
black exhibits a higher filler–polymer interaction and this
was reflected in the improvement of the mechanical prop-
erties and the modification of electrical conductivity of these
composites, especially when measured against the temper-
ature. The effect of curing of the polymer matrix on the
mechanical properties and electrical conductivity was also
investigated. It was found that the introduction of crosslinks
in the polymer matrix improves its mechanical properties as
well as the thermal stability of its electrical conductivity. The
electrical conductivity of ethylene propylene diene (EPDM)
and an EVA–EPDM (50/50) blend filled with carbon black
were also studied for comparison. © 2003 Wiley Periodicals, Inc.
J Appl Polym Sci 90: 2073–2082, 2003
Key words: crosslinking; conductive composite; filler treat-
ment; electron beam radiation
INTRODUCTION
Conductive polymer composites made by incorpora-
tion of different volume fractions of conductive fillers
like carbon black (CB), carbon fiber, and metal powder
into a polymer matrix have found many applications
in the field of electronics and in electrical industries
such as for electrostatic charge dissipation and elec-
tromagnetic interference shielding.
1–3
Positive temper-
ature coefficient of resistance (PTC) composites are
commonly employed in a wide range of uses, includ-
ing in temperature sensors, protection circuitry, mi-
croswitches, flow meters, self-regulating heating ele-
ments, and self-resetting over current protection ele-
ments. However, the range of their technical
application is restricted because most of the conduc-
tive particulate-filled polymer composites are electri-
cally and/or dielectrically unstable with respect to
thermal cycling (rise and fall in temperature) in tech-
nically useful temperature intervals. Therefore, it is
necessary to determine the sources of the instability of
the electrical properties filled to minimize this defect.
Composite thermistors composed of highly conduct-
ing CB-filled polyethylene having room-temperature
resistivity in the order of 1–100 ohm cm exhibit a PTC
effect of six to eight orders of magnitude (at about
130°C, T
m
for PE). These materials can easily be fabri-
cated and are intrinsically cost-effective.
4–7
Thermal recycling (heating– cooling cycle) of CB-
filed polymer composites has been studied extensively
because a large number of industrial applications are
based on either their electrical properties or mechan-
ical properties. It was found that the conductivity, in
particular, changes during thermal cycling, and there
is a hysteresis-type loop in the conductivity versus
temperature plots during the heating– cooling cycle
with some electrical set, that is, there is a permanent
change in the starting value of the conductivity at
room temperature after the heating– cooling cycle.
Further, the conductivity versus temperature plot also
changes during a repeated heating– cooling cycle. This
is due mainly to the breakdown and formation of a
conductive network due to CB aggregates present in
the insulating rubber materials.
The PTC and negative temperature coefficient
(NTC) phenomena of filled polymer composites were
studied by number of authors.
8 –12
In our previous
work,
13
we studied the NTC and PTC effects of ethyl-
ene–vinyl acetate (EVA)-based flexible composites
filled with conductive CB and carbon fiber. It is pre-
dicted that the conductive filler network undergoes
two processes during an increase in temperature: One
is breakdown and the other is reformation through
reagglomeration of a conductive filler, especially par-
ticulate fillers. The ultimate PTC/NTC behavior of the
Correspondence to: D. Khastgir (khasdi@rtc.iitkgp.ernet.in).
Journal of Applied Polymer Science, Vol. 90, 2073–2082 (2003)
© 2003 Wiley Periodicals, Inc.