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ISSN 1811-2382, Polymer Science, Series C, 2016, Vol. 58, No. 1, pp. 85–92. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © E.A. Karpushkin, A.K. Berkovich, V.G. Sergeyev, 2016, published in Vysokomolekulyarnye Soedineniya, Ser. C, 2016, Vol. 58, No. 1, pp. 93–101.
Composites Based on Acrylic Polymers and Carbon Nanotubes as
Precursors of Carbon Materials
E. A. Karpushkin
a, b
*, A. K. Berkovich
a
, and V. G. Sergeyev
a
a
Faculty of Chemistry, Moscow State University, Moscow, 119899 Russia
b
Bauman Moscow State Technical University, ul. Vtoraya Baumanskaya 5, str. 1, Moscow, 105005 Russia
*е-mail: eukarr@gmail.com
Received November 12, 2015
Abstract—The effect of carbon nanotubes on the properties of composite fibers and films based on polyacry-
lonitrile is analyzed. It is shown that the introduction of carbon nanotubes makes it possible to improve the
mechanical characteristics of the composite material. Data on the effect of carbon nanotubes on chemical
reactions occurring during the thermal stabilization and carbonization of these materials are cited.
DOI: 10.1134/S1811238216010057
INTRODUCTION
Since their discovery in 1991 [1], carbon nanotubes
(СNTs) have attracted the attention of researchers
because of their unique set of mechanical (rigidity,
strength, and record values of elastic modulus), elec-
tric, and optical properties [2]. Depending on their
structural features, СNTs are divided into single-wall
and multiwall (composed of several embedded single-
wall СNTs) as well as chiral and achiral. The amount
of layers constituting СNTs largely determines their
mechanical properties, whereas chirality, structural
imperfection, and the presence of amorphous carbon
on the surfaces of nanotubes primarily affect their
chemical and electronic properties [2].
Recent studies have shown that the use of СNTs as
a filler of polymeric materials allows efficient control
over the mechanical [3] and electric [4] properties of
these materials because СNTs are characterized by
high length-to-diameter ratios (1000 or greater). Spe-
cifically, СNTs have been employed as an additive to
polyacrylonitrile for the creation of new-generation
carbon fibers [5]. As precursors of carbon fibers,
copolymers of acrylonitrile with small amounts of
methyl acrylate and itaconic or acrylic acid are used.
At present, exactly these copolymers are applied to
produce carbon fibers with record values of strength
(6.37 GPa [6]) and elastic modulus (up to 294 GPa
[6]) that are employed as reinforcing components of
modern composite materials [7]. The mechanical
properties of СNTs are almost an order of magnitude
higher than those of carbon fibers; therefore, СNTs
hold much promise for the design new-generation
composite materials.
The extensive studies of СNT-containing spin
dopes of PAN and composite fibers formed on their
basis commenced not long ago [8–10]. It has been
found that the addition of carbon nanotubes to a spin
dope considerably simplifies heat treatment of the
PAN fiber and improves the quality of the final carbon
fiber [11–13]. However, as has been mentioned in [14,
15], the introduction of СNTs into a PAN fiber insig-
nificantly affects the heat treatment of the fiber and
does not improve the properties of the final product.
In other words, the introduction of СNTs only unrea-
sonably complicates the technological scheme of car-
bon fiber production and does not provide any advan-
tages.
The seeming inconsistency may be due to the fact
that the advantageous effect of СNTs on the process of
heat treatment of the PAN fiber and properties of the
final product is related not directly to the properties of
СNTs but to change in the structure and properties of
the polymer solution caused by the introduction of the
anisotropic filler into it and/or the effect of this filer
on chemical processes occurring during the heat treat-
ment of composite PAN-based materials. This review
will address some factors that, in our opinion, are the
most important in explaining the inconsistency of the
published data.
DISPERSION OF СARBON NANOTUBES
IN A PAN SOLUTION: PREPARATION,
STRUCTURE, AND RHEOLOGICAL
BEHAVIOR
The dispersions of СNTs in PAN solutions were
apparently first described in [16]. Already at that point
it was indicated that the associates of CNTs (Fig. 1a)
should be destroyed to obtain stable homogeneous
dispersions. Otherwise, the sedimentation-unstable
dispersion with separated microphases is formed.