ISSN 1995-4212, Polymer Science, Series D, 2016, Vol. 9, No. 4, pp. 377–381. © Pleiades Publishing, Ltd., 2016.

Original Russian Text © I.A. Aleksandrov, P.V. Prosuntsov, 2016, published in Klei, Germetiki, Tekhnologii, 2016, No. 5, pp. 17–21.

Determination of the Effect of Carbon Nanosized Particles

on Thermophysical Characteristics of Polymer Composite Materials
I. A. Aleksandrova and P. V. Prosuntsovb, *
aInstitute
of Engineering and Technological Informatics, Russian Academy of Sciences,
per. Vadkovskii 18–1A, Moscow, 127055 Russia
b
Bauman State Technical University, ul. Vtoraya Baumanskaya 5, Moscow, 105005 Russia
*e-mail: iaa@emtc.ru
Received January 26, 2016

Abstract—Models are developed for calculation of the thermal conductivity of a polymer binder modified
with different contents of carbon nanotubes (CNTs). Comparison of the computation data with the experi-
mental results shows that the introduction of CNTs cannot significantly increase the thermal conductivity of
the binder due to the presence of air cavities around CNTs.

Keywords: polymer composite materials, carbon nanotubes, thermal conductivity, size stability
DOI: 10.1134/S199542121604002X

INTRODUCTION The goals of the present work are to calculate the

Owing to a complex of high stress-strain [1], ther-
mophysical [2] and other properties, polymer com-
posite materials find increasing application. Tradi-
tionally the key problems for constructions made of
polymer composite materials are believed to be their
strength and stability. Nevertheless, in recent years,
growing attention has been drawn to constructions
with size stability [3]. “Size stability” in this case
means the ability of a material to retain its size and
shape to the greatest extent under the effect of variable
power and thermal loads.
An efficient technique for creation of thermally
stable constructions seems to be the use of polymer
composite materials with low values of linear thermal
expansion coefficient and high thermal conductivity.
An increase in the material thermal conductivity yields
a reduction in the temperature drops and, thereby, a
decrease in the temperature deformations [4].
The thermophysical characteristics of a reinforcing
filler usually significantly exceed the properties of a
binder. The appearance of nanosized fillers enabled
improvement of the mechanical and thermophysical
properties of matrix materials to values comparable
with the properties of reinforcing fillers. Today, grow-
ing attention is being drawn to the development of
polymer composite materials (PCMs) based on fillers
made of carbon nanomaterials—carbon nanotubes
(CNTs) and carbon nanofibers.
Therefore, increasing the thermal conductivity of a
binder via development and approbation of the meth-
ods for introduction of nanomodifiers into matrix
materials is an urgent task.
thermal conductivity of a matrix material based on
modeling of heat transfer in the binder with variable
content of CNTs and compare the data obtained with
the results of experimental studies.
EXPERIMENTAL
To determine thermal conductivity, the principle
of selecting an elementary cell of nanomodified binder
and calculation of the coefficient of its generalized
conductivity was used [5]. To study the effect of a
modifier made of carbon nanotubes on the thermo-
physical characteristics of the epoxy binder, three-
dimensional geometrical models of elementary cells
were developed that reflect the main geometrical prop-
erties of a CNT–binder system and take into account
the key factors for the transfer process (Fig. 1).
Upon modeling of CNT distribution in the binder
medium in the form of cylindrical bodies, a series of
assumptions are made. The first is that CNTs are rep-
resented as a hexagonal network of carbon atoms
rolled into a jointless cylinder, which is sealed from the
butt end with a half of a fullerene molecule.
At the present time, the process of CNT prepara-
tion does not allow their production in the form of
fullerenes from hexahedral networks: defective
penta- and tetrahedral cells of carbon atoms are pres-
ent, and it is difficult to determine the content of
defective tubes due to the labor-intensiveness and
cost of such an assessment. Therefore, it is assumed
that the tubes considered in modeling do not ref lect
possible ornateness.

377
378 ALEKSANDROV, PROSUNTSOV
Fig. 1. Geometrical model of the elementary cell.
During distribution of CNTs over the binder vol-
ume, some of the dispersed CNTs join into agglomer-
ates. This is caused by the fact that each particular
concentration of nanotubes requires a choice of
modes for introduction depending on the rheological
properties of a medium into which they are introduced.
The choice of introduction mode must include the step
of binder curing, since the formation of agglomerates is
possible up to completion of the gel formation stage.
Determination of the volume content of agglomerates
in the binder and their effect on nanocomposite charac-
teristics does not seem to be possible. Therefore, it was
assumed that the distribution of nanotubes over the
whole volume of the binder is uniform.
To calculate the thermal conductivity of the binder
with the nanomodifier, the model of heat transfer was
used, which entails that, on two opposite walls of the
elementary cell, there are given magnitudes of tem-
perature that are constant over the surface but differ-
ent (the drop is no more than 5°C). The other facets of
the elementary cells are considered to be thermally
isolated. Modeling of heat transfer was carried out
using Ansys Workbench finite-element analysis [6].
The temperature field of the elementary cell was
obtained (Fig. 2), and the heat flow through a side wall
of the cell was determined.
To determine the thermal conductivity, the Fourier
law was used:
q mentary cells with randomly oriented inclusions (with
λ= ,
l ΔT
where λ is the thermal conductivity coefficient of the
binder with the nanomodifier, W/(m K); q is the heat
flow through the side cell wall, W/m2; l is the length of
POLYMER SCIENCE, SERIES D
B: 05
Temperature
Type: Temperature
Unit: °C
Time: 1
26.05.2014 10:25
25.003 Max
24.47
23.891
23.334
22.778
22.222
21.666
21.110
20.554
19.998 Min
0.000 0.800 m
Z X
0.200 0.600
Fig. 2. Temperature field of the elementary cell.
the elementary cell edge, m; and ΔT is the difference
between the initial temperatures of opposite cell walls, K.
To carry out experimental studies, a series of sam-
ples of the nanomodified binder were prepared based
on Araldite CY 179 epoxy resin, HY 917 curing agent,
and DY 070 catalyst. The modifier used was Baytubes
C150 P CNTs.
Introduction of carbon nanotubes into the binder
was performed via ultrasonic treatment with an
LUZD-1,5/21-3,0 ultrasonic dispersion system. Sam-
ples were prepared with a weight fraction of nanotubes
of from 0 to 0.5% with a 0.1% step.
After curing of the half-finished samples, they were
mechanically treated, proceeding from the require-
ments for carrying out measurements. The experi-
mental investigation of the temperature conductivity
was carried out by the laser flash method using a
NETZSCH LFA 427 unit [5]. The thermal capacity
was determined with a DSC 204 F1 Phoenix LFA 427
highly sensitive differential scanning calorimeter man-
ufactured by NETZSCH [7]. Densities of the samples
were determined by gyroscopic weighing.
The thermal conductivity of the material was deter-
mined from the following expression:
λ = aC pρ,
where a is temperature conductivity, m2/s; Cp is ther-
mal conductivity, J/(kg K); and ρ is density, kg/m3.
RESULTS AND DISCUSSION
To analyze the effect of CNT concentration on the
thermal conductivity of the nanomodified binder, ele-
a weight fraction from 0.1 to 0.5%, with a 0.1% step)
were constructed.
The initial data used for modeling are presented in
Table 1.
Vol. 9 No. 4 2016
 DETERMINATION OF THE EFFECT OF CARBON NANOSIZED PARTICLES 379

(a) (b)

Y Y

0.000 0.700 0.000 0.700

Z X Z X
0.350 0.350

Fig. 3. Three-dimensional model of the elementary cell at CNT wt content (a) 0.1 and (b) 0.5%.

0.8
Thermal conductivity, λ, W/(m K)

0.7 1
0.6

0.5

0.4

0.3
2
0.2

0.1

0 0.1 0.2 0.3 0.4 0.5

Weight fraction of CNT, %

Fig. 4. Dependence of the thermal conductivity of the

nanomodified epoxy binder on CNT weight fraction:
(1) calculation data (finite-element analysis); (2) experi- Fig. 5. Model of the elementary cells with an air shell
mental data. around cylindrical CNTs.

Figure 3 presents the models of elementary cells natural to think that the presence of such a structure
that contain 0.1 and 0.5 wt % of cylindrical inclusions does not allow the binder to come into contact with
of CNTs. the nanotube surface.
Figure 4 shows the results of calculation and exper-
To determine the effect of possible air inclusions
imental definition of the thermal conductivity of the
nanomodified binder randomly reinforced with CNTs on the thermal conductivity of nanomodified binder,
in amounts of from 0 to 0.5 wt %. models of elementary cells with an air shell around
As can be seen from Fig. 4, the deviation of the cal-
culated values of thermal conductivity from the exper- Table 1. Properties of the components used for modeling of
imental data lies in the range of from 104 to 257%. the elementary cell
Structural analysis of Baytubes C 150 P CNTs per- Cell component
formed earlier using scanning electron microscopy [8] Parameter
CNT binder
showed that the actual diameter of nanotubes exceeds
the nominal data in by two or three times. An increase Length, nm 1000
in the diameter of nanotubes can be caused by the Diameter, nm 13
presence of an ornate structure at the atomic level Density, kg/m3 130 1200
formed on the tube surface during preparation. It is Thermal conductivity, W/(m K) 100 0.23

POLYMER SCIENCE, SERIES D Vol. 9 No. 4 2016

380 ALEKSANDROV, PROSUNTSOV

(a) (b)

Fig. 6. Models of the elementary cells with an air shell at CNT weight fraction of (a) 0.1 and (b) 0.5%.

(a) (b)

Fig. 7. Models of the elementary cells with an air shell around CNTs. The value of the shell relative to the CNT diameter is (a) 10
and (b) 50%.

0.8 cylindrical CNTs were constructed (Fig. 5). The air

shells were constructed for all the previously consid-
Thermal conductivity, W/(m K)

0.7 1 ered models of elementary cells of the binder ran-

0.6 domly reinforced with CNTs in the amount of from
0.1 to 0.5 wt % with a 0.1% step (Fig. 6). The value of
0.5 2 air shells around CNTs varied from 10 to 50% of the
nanotube diameter (Fig. 7).
0.4 3
The results of calculation of the thermal conductiv-
0.3 ity of the nanomodified epoxy binder depending on
4
7 the value of air inclusions around CNTs are presented
0.2
5 in Table 2.
0.1
6 The dependence of thermal conductivity of the
nanomodified epoxy binder on CNT concentration at
0 0.1 0.2 0.3 0.4 0.5 different values of air inclusions is presented graphi-
Filler weight fraction, % cally in Fig. 8.
Fig. 8. Dependence of thermal conductivity of the nano- As can be seen from Fig. 8, the model of an ele-
modified binder on the CNT weight fraction at different mentary cell of the binder with the content of air
values of air inclusions around CNTs, % relative to the
CNT diameter: (1) 0, (2) 10, (3) 20, (4) 30, (5) 40, (6) 50, inclusions equal to 30% of the nanotube diameter cor-
and (7) experimental data. responds to the experimental data best of all.

POLYMER SCIENCE, SERIES D Vol. 9 No. 4 2016

 DETERMINATION OF THE EFFECT OF CARBON NANOSIZED PARTICLES 381

Table 2. Calculated thermal conductivity of the nanomodified epoxy binder depending on the weight fraction and value of
air shells around CNTs
Thickness of air inclusions, % relative to the CNT diameter
CNT
concentration, 0 10 20 30 40 50
wt %
thermal conductivity, W/(m K)
0.0 0.23 0.23 0.23 0.23 0.23 0.23
0.1 0.45 0.32 0.31 0.25 0.15 0.11
0.2 0.61 0.40 0.35 0.24 0.12 0.06
0.3 0.65 0.46 0.37 0.22 0.12 0.04
0.4 0.65 0.47 0.34 0.20 0.10 0.01
0.5 0.75 0.53 0.32 0.14 0.06 0.02

CONCLUSIONS polysulfone modified epoxy binders,” Glass Physics

Comparison of the results of modeling and experi-
mental investigations on thermal conductivity of the
nanomodified binder samples showed that the appli-
cation of existing technologies for introduction of the
modifier into the binder volume does not allow one to
realize the potential of CNTs: the presence of air
inclusions in nanotube cavities not only does not
improve the thermal conductivity of the nanomodi-
fied binder, but can even reduce it.
ACKNOWLEDGMENTS
This work was supported in part by the Ministry of
Education and Science of the Russian Federation,
subsidy agreement no. 14.577.21.0095 of August 25,
2014, unique identifier of applied research investiga-
tions no. RFMEFI57714X0095.
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Translated by K. Aleksanyan

POLYMER SCIENCE, SERIES D Vol. 9 No. 4 2016