Composites Part B 168 (2019) 387–397

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Efficient prediction of the electrical conductivity and percolation threshold T

of nanocomposite containing spherical particles with three-dimensional
random representative volume elements by random filler removal
Do-Won Kima, Jae Hyuk Lima,∗, Jaesang Yub
a
Division of Mechanical Engineering, Chonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju-si, Jeollabuk-do, 54896, Republic of Korea
b
Composite Materials Application Research Center, Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Chudong-ro 92,
Bongdong-eup, Wanju-gun, Jeollabukdo, 55324, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: In this work, the effective electrical conductivity (EEC) and percolation threshold (PT) of a nanocomposite
Polymer-matrix composites (PMC) containing spherical particle fillers are predicted by computational homogenization schemes (CHS) with three-
Percolation threshold (PT) dimensional random representative volume elements (RVEs) by random filler removal (RFR). For this prediction,
Random filler removal (RFR) we prepare the RVE having the maximum filler volume fraction (Vf) of 52% with random particle fillers, also
Interphase modeling
termed the master model, by the discrete element method (DEM), and the corresponding finite-element (FE)
model is created. Then, 100 RVE samples for each Vf are derived by randomly replacing the material properties
of several fillers by those of the matrix from the master model with diverse Vf from 5% to 50%. In addition, the
interphase layer is employed by replacing some matrix elements with interphase elements according to the
neighboring distance of the fillers.
To demonstrate the performance of the proposed scheme, its randomness of RVEs is verified by spatial and
physical metrics in terms of autocorrelation analysis, near-neighbor analysis, and directional conductivity ratio.
The EEC prediction results with diverse Vf values are compared with those of an analytical model and test results.
As a result, the PT at which EEC of the nanocomposites suddenly increases is successfully evaluated, and the
effect of the void, interphase thickness, and conductivity, as well as the size of fillers on the EEC and PT is
investigated through a sensitivity analysis.

1. Introduction
For several decades, in sport, automobile, aerospace, construction,
and civil industry applications, composite materials have been widely
used due to their many advantages, such as specific modulus, specific
strength, low thermal expansion coefficient, and so forth. To date, state-
of-the-art transportation vehicles, such as automobiles, airplanes, and
satellites, are equipped with a variety of high-power electronics in a
very narrow internal space, which must discharge heat properly and
must meet electromagnetic interference and compatibility (EMI/EMC)
and electrostatic discharge (ESD) requirements. However, in general,
the electric and thermal conduction of most polymer-matrix composites
(PMC) is quite poor because the polymer matrix material surrounding
fillers or fibers acts as an insulator because the conductivity of the
polymer matrix is very low. Due to this problem, the application of
PMCs is limited, although industry interest in and demand for diverse
applications of composites is increasing.
To address these limitations, there have been many works on im-
proving the effective electrical conductivity (EEC) of composite mate-
rials and efforts to determine the critical point at which the EEC sud-
denly rises, termed the percolation threshold (PT) as the number of
added filler increase [1–5]. By adding highly conductive fillers, such as
carbon blacks (CBs), carbon nanotubes (CNTs), graphene nanoplatelets
(GNPs), and silver powder to PMC, and encouraging the formation of
direct networks and indirect tunneling between fillers, the EEC is dra-
matically improved with PT advancement. Networking increases the
conductivity by promoting the formation of a network through the
contact of fillers. Tunneling increases the conductivity by utilizing the
electrically conductive tunneling effect without contact between the
fillers by charge transfer according to the neighboring distance. From
the viewpoint of material designers, PT prediction is very important in
the development of polymer nanocomposites because it can maximize
EEC with the given amount of fillers. Accordingly, many studies have
been actively conducted on appropriately adding and dispersing highly

∗
Corresponding author.
E-mail address: jaehyuklim@jbnu.ac.kr (J.H. Lim).

https://doi.org/10.1016/j.compositesb.2019.03.038
Received 16 January 2019; Received in revised form 15 March 2019; Accepted 18 March 2019
Available online 22 March 2019
1359-8368/ © 2019 Elsevier Ltd. All rights reserved.
D.-W. Kim, et al. Composites Part B 168 (2019) 387–397

conductive fillers in PMCs [6–25].

Several analytical approaches have been employed [6–12]. Berhan
compared the performance of the soft-core and the hard-core ap-
proaches for modeling percolation and used Monte Carlo (MC) simu-
lation to investigate the relationship between PT and excluded volume
for both modeling approaches [6]. Modifications of existing analytical
models, such as Mori-Tanaka [7], Kovacs [8], Kirkpatrick [9,10] and
McLachlan [11], have been proposed for application to nanocomposites
considering many critical parameters, such as the aspect ratio of filler,
interphase parameter, surface energy between filler and matrix, and
remarkable successful predictions consistent with test results have been
reported. It is noteworthy that among several parameters, the inter-
phase that links fibers and the matrix plays a critical role in the tensile
modulus and strength as well as the electrical conductivity.
Furthermore, several numerical methods that combine the resistor
network model with MC simulation have been introduced to compute
the EEC [12–20]. The generation of random microstructures by the MC
method was performed, and the PT was predicted using the continuum
numerical tunneling model introduced by Lu [9]. Bartels performed a
mesoscopic simulation to predict the EEC and PT of CNT-reinforced
polymers considering the tunneling effect, and the influence of the
tunnel cutoff and polymer cutoff parameters was also examined [12].
The PT of a gold nanoparticle/polymer material was predicted using
Fig. 1. Flowchart of random RVE generation by random filler removal.
MC sampling and a numerical approach that takes into account the van
der Waals interaction effect between particles [18].
However, the aforementioned analytical models and resistor net- particles and interphase modeling due to the heavy computation cost
work models could have some limitation in describing the phenomena and complexity of FE mesh generation. However, it can be possible
associated with pre-strain or residual stress that frequently occur in efficiently by 3D RVE with the aid of the RFR technique.
practical sensor applications, although some remedies have been re- The remainder of this paper is organized as follows. In section 2, we
ported [21–23]. To overcome this issue, voxel finite-element (FE) will explain how to generate random RVEs with diverse Vf using the
models and overlapping FE models with the approximated geometry discrete-element method (DEM) and RFR. Section 3 explains the eva-
including randomly placed filler have been conducted [24–26]. Mor- luation of the EEC and PT by CHS as the number of fillers is added. The
tazaviwe et al. developed a three-dimensional (3D) FE modeling to verification on the randomness of RVE follows in Section 4. Section 5
research interphase effects on the thermal conductivity of nano- presents the prediction results and compares them with the test results
composites filled with randomly oriented fillers by the computational and those obtained by other models along with investigation of the
homogenization scheme (CHS) with RVE FE models [27] with an ac- effect of the void, interphase thickness and conductivity, as well as the
curate filler geometry. However, its Vf was quite low due to the com- size of fillers on the EEC and PT. Finally, we conclude the paper with
plexity of mesh generation of random RVEs, which is not enough to find closing remarks in Section 6.
out the PT of nanocomposites. Until now, there has been a continuing
need for the evaluation of the EEC and PT of the nanocomposite by CHS 2. Generation of RVEs having random filler positions with diverse
with FE models for a variety of applications. Recently, Park et al. [28] Vf values
developed a novel modeling scheme to generate random RVE, termed
random fiber/filler removal (RFR), which eliminates fibers from the The process of generating FE models having random filler positions
master model containing the maximum Vf for the 2D unidirectional with diverse Vf values is shown in Fig. 1. Largely, it is divided into two
composite to match the predefined Vf. The most critical contribution of steps. Once the number of particle fillers and Vf are chosen, the master
their work is that no further mesh generation is required once the FE element having the maximum Vf is determined through a three-axis
mesh of the master model is generated, which have never been attained compression simulation by DEM (see Fig. 2), and the corresponding FE
in other RVE modeling schemes [29–36]. Due to this advantage, the model of the master element is generated by ABAQUS Python script
generation of many RVEs with diverse Vf is quite straightforward. [38]. Subsequently, 100 RVEs of lower Vf are generated by the RFR
Furthermore, the application of 3D composites with spherical particles technique. It is presented in detail in the following subsections.
seems to be quite straightforward as well.
Therefore, in this work, we propose an efficient method to predict 2.1. Generation of the master RVE using DEM
the EEC and PT of nanocomposites containing spherical fillers by CHS
with 3D random RVEs of diverse Vf ranging from 5% to 50% by the RFR According to Refs. [28–36], obtaining a 3D RVE with spherical
technique, which efficiently mitigates some of the burden from the particles with high Vf over 40% is not so straightforward through
mesh generation of many RVEs with diverse Vf. To check the accuracy random sequential adsorption (RSA) that generates particle filler posi-
of the developed models, its randomness of RVEs is verified by spatial tions by MC simulation [29,30] due to the jamming limit. To overcome
and physical metrics in terms of autocorrelation analysis, near-neighbor this limitation, several algorithms have been proposed, such as nearest-
analysis, and directional conductivity ratio. The EEC prediction results neighbor algorithm (NNA) [31], modified nearest-neighbor algorithm
with diverse Vf values are compared with those of several analytical (MNNA) [32], random sequential expansion (RSE) [33], with the con-
models. As a result, the PT, at which the electrical conductivity of the strained optimization formulation [34], but they still have another
nanocomposites suddenly increases, is successfully evaluated, and we jamming limit lower than 50%. However, recently, new algorithms
investigate the effect of the void contents, interphase thickness and considering filler collision by random event-driven molecular dynamics
conductivity, as well as the size of fillers on the EEC and PT. simulation (EDMD) [35] and DEM [36] were proposed. Among those, Li
Note that, to the best of our knowledge, this kind of prediction has et al. reported the highest record in Vf higher than 60% in 3D parti-
never been conducted by CHS with RVE FE models containing spherical culate composites [35]. Accordingly, in this work, we use DEM to

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Fig. 2. Particle position determination by three-axis compression simulation by DEM.

2.2. Generation of 3D RVE FE models of diverse Vf values using random

particle filler removal

Here, the master 3D RVE FE model consisting of 1,256,737 nodes

and 7,398,389 tetrahedron elements is generated as shown in Fig. 3. To
generate random RVEs for various Vf values, 100 RVEs having a low Vf
are generated by randomly replacing the material properties of the filler
with those of the matrix from the master RVE element derived above.
This process can be easily done by reading the coordinates of fillers and
adjusting them by the ‘randperm’ MATLAB function [39]. In this work,
RVEs are generated at intervals of 5% from 50% to 5% lower than the
maximum Vf, and the number of RVEs of the sample is set to 100 for
each Vf as shown in Fig. 3. Therefore, the total number of RVEs used in
this work is 1100.

3. Prediction of the effective electrical conductivity of

nanocomposites by computational homogenization scheme

3.1. Percolation threshold theory

The variation in electrical conductivity of these nanocomposite

materials is explained in three steps, as illustrated in Fig. 4. In the first
step (A), the conductivity is still low because a small number of particle
fillers are not linked each other; rather, they are isolated particles.
Fig. 3. Generation of 3D random RVE FE models of diverse Vf by random Thus, the EEC of the composite material is almost the same as that of
particle filler removal. the polymer. In the second step (B), clusters of particle fillers are
formed, which increases the number of adjacent particle fillers. In this
state, tunneling occurs between adjacent particle fillers, although no
generate the RVE models of the maximum Vf by in-house code [36,37].
complete electrical path is formed, resulting in a gradual increase in the
In the first step, the diameter of fillers is set to 104 nm to consider the
effective diameter of carbon black (CB), and the size of RVE is set to
1000ⅹ1000ⅹ1000 nm. Then, the number of fillers in the 3D RVE is set to
1000, and it is compressed by three orthogonal rigid walls with periodic
boundary condition to the given RVE cubic, causing particle fillers to
collide until the simulation is terminated as shown in Fig. 2. The degree
of randomness of the 3D RVE is checked by spatial metrics in 3D au-
tocorrelation analysis as described in section 4.1. If it is satisfactory, the
process proceeds to the next step. If not, the three-axis compression
simulation is performed again with another initial seed. From the result,
the set of coordinates of the center of all particles is determined, and it
is converted to the corresponding FE model by using ABAQUS Python
script as shown in Fig. 3. The diameter of the particle filler is slightly
reduced to keep the minimum filler distance of 1 nm. Thus, an FE model
RVE having the maximum Vf (=52%) is obtained. At this moment, by
adjusting the diameter and the number of the spherical particles, the
maximum filler Vf can be modified. For simplicity, we term this RVE as
the master model, which will be used for sequential diverse Vf random
RVE generation as described in the following subsection.

Fig. 4. Principle of improving the effective electrical conductivity of nano-

composite [20].

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conductivity of the composite material. In the third phase (C), as the

number of particle fillers increases, a complete electrical path is formed
between the fillers due to their contact. The EEC of composite materials
at this stage increases rapidly according to the percolation power law as
expressed in Eq. (1) [2]:

σ = σf (Vf − Vc )t (1)

where σ , σf , Vf , Vc , and t denote the EEC of the composite, the electrical

conductivity of the filler, the filler volume fraction, the PT, and the
critical exponent, respectively. In the final phase (D), as more filler
particles are added to the polymer, the EEC of the composite material
gradually increases. However, since the increase at this stage is not
large compared to the increase during the percolation process, usually,
it is recommended that no more filler is added to avoid further increase
in weight.
Fig. 6. 3D RVE FE model.

3.2. Modeling of soft interphase

2 2 2
r≤d= (x i0 − x iG ) + (yi0 − yiG ) + (z i0 − z iG ) ≤ R. (2)
We adopt a soft interphase layer surrounding particles based on the
hard-core model proposed by Berhan and Sastry to consider the tun-
neling effect and electrical network [6]. The interphase layer affects the 3.3. Prediction of the effective electrical conductivity using CHS
EEC and the PT significantly in nanocomposites, because they can form
a serial electrical network between fillers by simulating the tunneling CHS is a popular method to calculate the effective properties of
effect and physical contact of the fillers [41–44]. Furthermore, it is well heterogeneous materials mixed with various constituents, such as
known that such interphase properties affect the tensile modulus and composites. An RVE representing the microstructures, as seen in Fig. 6,
strength of nanocomposites by changing stress transfer between filler is prepared, and three sets of boundary conditions are applied to the
and matrix [45–47]. In the hard-core model, the hard-cores cannot RVE along the x, y, and z directions, respectively. The FE simulation is
penetrate each other, and they are assumed to be surrounded by soft conducted considering the electrical properties of the filler, matrix, and
shells, such as interphase. If fillers are very close to each other, each interphase. The equation for the electric conduction law is given by Eq.
interphase contacts with other interphases, thus forming a network. It (3):
can simulate the tunneling effect and conductive networks in the per- Ji = −σij ∇Vj (i, j = 1,2,3), (3)
colation process. For this purpose, the FE meshes of the interphase are
formed by replacing the FE meshes around the filler with those of in- where Ji , σij , and ∇Vj denote the i-th electric flow rate, the tensor of
terphase. If an element having the distance d (see Eq. (2)) between the electrical conductivity, and the voltage gradient in the j-th direction,
center of the matrix element (x iG , yiG z iG ) and the center of the filler respectively. The effective electrical flow rate in i-th direction < Ji > is
(x i0 , yi0 z i0) is placed between the filler r and the interphase radius (R) as volume-averaged by dividing the summation of element-wise con-
shown in Fig. 5, tribution to the electrical flow by the volume of the entire RVE as ex-
pressed in Eq. (4):
nelem
1 Jikelem dΩkelem
< Ji > =
Ω
∫Ω Ji dΩ = ∑ Ω
,
k=1 (4)
where Ω, Jikelem ,
and dΩkelem
denote the total volume of RVE, the i-th
electrical flow rate, and the volume of the k-th element, respectively.
Subsequently, < Ji > is multiplied by the j-th length of RVE Xj and di-
vided by the j-th voltage difference ΔVj . Finally, the ECC tensor (σij ) is
obtained as
< Ji > Xj
σij = − .
ΔVj (5)
Among the components of σij , if the off-diagonal term is almost
negligible, typically σij replaced by σi the diagonal term of σij . This is a
typical procedure of CHS that provide a prediction with excellent ac-
curacy if a proper RVE containing the microstructures of a material is
given because there are no assumptions regarding the geometry and
arrangement of the constituents. Due to this advantage, it can be ap-
plied to any type of composite material (unidirectional, plain weave,
random composite, and so forth).

4. Verification of random RVEs

In the prediction of the effective material properties of a composite

by CHS, RVEs have to show sufficient randomness, which is checked by
Fig. 5. Schematic diagram of 3D RVEs with soft interphase for a regular array several statistical and physical metrics to ensure that a wrong predic-
and a random array of spherical particles. tion is not made with biased sample RVEs [35]. Thus, the validity of the

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Fig. 7. Radial distance (r), azimuth (θ ), and elevation (ϕ ) angles between any
point (xj) and the reference point (xi).
3D RVEs by RFR is verified by examining the randomness by auto-
correlation analysis and near neighbor analysis with spatial metrics,
such as K-, G-, and F-functions, and physical metrics, such as directional
conductivity ratio. RSA [29,30] and RSE [33] are also adopted for
comparative analysis of performance.
4.1. 3D autocorrelation analysis
Fig. 7 illustrates the definition of the azimuth angle (θ ) and the
elevation angle (ϕ ) of the arbitrary point xj with respect to the reference
point x i . Through 3D autocorrelation analysis, we analyze the relative
position of xj within the region associated with all other points as well
as the closest point. Fig. 8 shows the polar plot of the relative positions
of all the other points with respect to the reference point for Vf = 30%,
40%, and 50% by the RFR, RSE, and RSA algorithms. From all results,
all plots show almost consistent particle densities in the θ and ϕ di-
rections, indicating that all points are randomly distributed. However,
in the case of Vf = 50%, the RSA and RSE techniques fail to generate
RVE by the above-mentioned jamming limit. In the case of Vf = 40%,
the RSA technique fails to generate RVE for the same reason.
4.2. Near-neighbor analysis in 3D
Generally, 3D spatial near-neighbor analysis uses three spatial dis-
tribution functions, such as K-, F- and G-functions [35,40], based on the
near-neighbor distance. Among those, the K-function is a statistical
indicator, also termed Ripley-K function. This is defined as
n
B I (‖x i − x j ‖ ≤ r )
K (r ) = ∑∑ ,
n2 i=1 j≠i
w (i, j ) (6)
where B is the volume of the domain, n is the number of points, r is the
arbitrary radius, I (‖x i − x j ‖ ≤ r ) is 1 if the expression in parentheses is
true, and 0 otherwise. Furthermore, ‖x i − x j ‖ is the distance between
point i and j , w (i, j ) indicating the fraction of the circumference of i-th
particle with radius ‖x i − x j ‖ within the RVE cube. In the case of the
complete spatial randomness (CSR) distribution, the K-function of CSR
is 4πr 3/3.
The F-function is an empty space function that represents the
probability distribution of the distance from each grid point to the
nearest point at most r. To obtain the F-value, the fine grid on the RVE is
set, and di distance of the i-th grid point to the nearest point is used as
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Composites Part B 168 (2019) 387–397
g
1
F (r ) =
g
∑ I (di ≤ r ),
i=1 (7)
where g is the total number of grid points. For the CSR point pattern,
the F-function is 1 − exp(−4λπr 3/3) . Here, λ is the intensity (expected
number of points per unit volume) equal to n/ B . Similarly, the G-
function uses the distance of the i-th point to the nearest point di instead
of the i-th grid point to the nearest point as
n
1
G (r ) =
n
∑ I (di ≤ r ),
i=1 (8)
where n is the total number of the points. The G-function of the CSR
point pattern is 1 − exp(−4λπr 3/3) . If there is any curve showing some
deviation from the K-, G-, and F-curves of CSR, this indicates spatial
clustering or spatial regularity of the given point distribution.
Fig. 9 shows the results of the near-neighbor analysis in terms of
three spatial distribution functions (K-, F-, and G-function) for RVE with
diverse Vf of 30%, 40%, and 50%. As a result, in the case of Vf = 30%
(see Fig. 9a), it is found that all three spatial distribution functions by
RFR are almost consistent with those by RSA despite not reproducing
the CSR pattern completely. Except for the K-function, the F-functions
by RFR and RSA are slightly lower than the CSR pattern. The G-function
increases sharply at 104 nm at the diameter of the particles because the
point pattern was generated with the assumption of solid spherical
particles instead of volume-less points. However, the curves by RSE
with the minimum and maximum inter-fiber distance: lmin = 0.1 nm,
and lmax = 0.5 nm quite deviate from those of RFR and RSA. This means
that the point pattern by RSE is locally clustered or rather irregular. In
the case of Vf = 40% (see Fig. 9b), the K- and F-functions by RFR are
quite consistent with the CSR pattern, but the results by RSE are not.
Unfortunately, there is no result by RSA because it cannot construct a
point pattern due to the jamming limit. In the case of Vf = 50% (see
Fig. 9c), there is only RFR result because neither the RSE nor the RSA
can construct a point pattern due to the jamming limit, which follows
the curve of CSR in terms of the K- and F-functions as well. From the
results of the 3D near-neighbor analysis, it turns out that the proposed
RFR algorithm has sufficient randomness and generates high Vf RVE
such as 50% higher than the jamming limit of other algorithms.
4.3. Directional conductivity ratio
The physical validity of the generated 3D RVEs is checked by in-
troducing the concept of directional conductivity ratio (DCR) as
σ1 σ2 σ3
DCR = , , and ,
σmean σmean σmean (9)
where σ1, σ2 , and σ3 are the EEC of the composite in x-, y-, and z-di-
rection, and σmean is their mean value. For the evaluation of the EEC of
the composite by CHS with random RVEs, the carbon black (CB,
ENSACO 250G, TIMCAL Graphite & Carbon, Switzerland)/polymerized
cyclic butylene terephthalate (pCBT, CBT 160, Cyclics, USA) composite
whose material properties of constituents are given in Table 1 [7]. The
electrical conductivity of the polymer matrix was 8.5 × 10−14 S/m,
which is much lower than that of filler (100 S/m). We prepared five
RVE samples for each Vf = 32%, 42%, and 48%, and the EEC was
evaluated. The results of the DCR ratio are summarized in Table 2. All
values of the DCR ratio were close to unity within 3% deviation. From
the results, it is confirmed that the generated random RVEs of the filler
have the same EEC in all directions.
5. Results and discussion
To demonstrate the performance of the proposed scheme, its pre-
diction results are compared to the results of electrical conductivity
measurement of CB/pCBT composites and Raven 2000/DGEBF com-
posite in the references [7,48].
D.-W. Kim, et al.
Fig. 8. 3D autocorrelation analysis results (a) for Vf = 30% by RFR, RSE, and RSA, (b) Vf = 40% by RFR and RSE, and Vf = 50% by RFR.
5.1. Effect of interphase thickness and interphase conductivity
The result of electrical conductivity measurement consists of 6
discrete points, and its prediction by CHS of CB/pCBT composites for
each Vf are plotted in Fig. 10a according to Vf. Furthermore, Fig. 10
shows the prediction results with various interphase sizes and inter-
phase conductivity. The electric conductivity of the interphase σi was
assumed to be 100 S/m, the same as the electric conductivity of CB.
While the inner radius r was maintained at 52 nm, the outer radius R
was gradually increased from 52 nm to 60 nm to realize the interphase.
At this time, the size of FE meshes of the matrix was 0.5–1.0 nm around
CB particles, sufficiently small to consider the interphase layer as shown
in Fig. 11. Blue (in web version) indicates the interphase FE meshes,
and red (in web version) indicates those of the filler. Furthermore, it
can be found that the conductive network region expands as the in-
terphase layer thickness increases such as R/r = 1.0, 1.015, 1.038, and
1.154 (See Fig. 11), and as the Vf increases such as 10%, 20%, 30%, and
40% (see Fig. 12).
In the case of RVE without interphase (R/r = 1.0, see Figs. 10a and
11a), the EEC of the RVEs did not show any remarkable increase be-
cause all particles are isolated due to the minimum filler distance
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Composites Part B 168 (2019) 387–397
between particles that are adopted for efficient FE mesh generation. As
the interphase radius become larger, they start to link with each other,
and the enhancement of EEC and PT can be observed at R/r = 1.013,
and PT is advanced up to 15% as the interphase radius increases. When
the interphase radius is between 52.7 nm (R/r = 1.013, see Fig. 11c),
the ECC is rapidly increased at Vf = 28% like the PT (=Vc) of the test
results. It is also verified by the McLachlan model [11,48] that explains
the macroscopic characteristics of media according to the character-
istics and volume ratios of the matrix and filler as
Vf (σ 1/
f
h
− σ 1/ h (1 − Vf )(σm1/ h − σ 1/ h)
+ = 0,
σ 1/ h
+ Aσ 1/ h
σm1/ h + Aσ 1/ h
f (10)
where A = (1 − Vc )/ Vc , σf , σm , and σ are the electrical conductivity of
the filler and polymer matrix, and the composite, respectively. Here, h
is the critical exponent defined by the coefficient of demagnetization
and depolarization between filler and matrix. We use the parameters of
the McLachlan model in Table 3.
Fig. 10a shows the comparison result of the EEC by CHS with the
relative ratio of radius R/r=1.013. As a result, it is found that the re-
sults by the proposed CHS are consistent with those of the McLachlan
D.-W. Kim, et al. Composites Part B 168 (2019) 387–397

Fig. 9. Near-neighbor analysis results in terms of K-, F-, and G-functions of (a) Vf = 30%, (b) Vf = 40%, (c) Vf = 50%.

Table 1 electrical conductivity on interphase on the PT is considered very

Material property of constituents of CB/pCBT composite. minimal. However, there is significant change in the plateau values of
Matrix (pCBT) [7] Filler (Carbon Black) [7] the EEC.
From a comparative study of EEC prediction by CHS and the
−14
Electrical conductivity (σ ) [S/m] 8.5 × 10 100 McLachlan model, it is noted that the prediction by the proposed CHS
Density ( ρ ) [kg/m3] 1300 170
do not need several critical parameters in contrast to the analytical
model, such as Vc , t , and h that are obtained by the curve fitting of many
coupon test results in the analytical model. Instead of this, we have to
Table 2
update the size of the interphase and the electrical conductivity of the
Directional conductivity ratio of RVE with diverse Vf.
interphase to fit the simulation data with the test results.
Vf σ1 (S/m) σ2 (S/m) σ3 (S/m) σmean
(σ1/ σmean) (σ2/ σmean) (σ3/ σmean) (S/m)
5.2. Effect of void contents and the size of particles
32% 23.2412 23.7132 24.4904 23.8149
(0.9859) (0.9957) (1.0284)
In addition, the effect of void contents and the size of particles on
42% 42.2893 44.4791 43.7084 43.4923
(0.9823) (1.0227) (1.0050) the prediction results is investigated to check their sensitivity on the
48% 55.3859 55.7618 56.6933 55.9470 EEC evaluation. Voids, which are one of the most common types of
(0.9910) (0.9967) (1.0133) defects in the manufacturing of composite materials due to improper
curing and moisture of the prepreg, may lead to degradation of the
physical properties. To consider voids in the nanocomposite, matrix and
model as shown in Fig. 10a. interphase elements were removed randomly from 1% to 3% as shown
Fig. 10b shows a rising trend in the ECC according to the con- in Fig. 13. Fig. 14a shows the predicted EEC with the variation of the
ductivity of the interphase: 0.1, 1.0, 10, and 100 S/m at the interphase void content with a 60 nm (R/r = 1.154) interphase radius. It is con-
radius of 60 nm (R/r = 1.154). From the results, its influence of the firmed that the PT and EEC are slightly lowered as the void content is

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Fig. 10. Prediction of ECC with diverse Vf according to (a) interphase thickness
and (b) interphase conductivity.

increased, but its effect on the PT is not critical. Fig. 14b presents the
variation of EEC according to the size of particles. This is a comparison
with the variation of the size of particles at a 52 nm, 60 nm, and 90 nm
while keeping the relative radius ratio of R/r = 1.154. As the diameter
of particles increases from 52 nm to 90 nm, there is significant ad-
vancement of the EEC and PT, which is consistent with the findings of
other works [17].
Fig. 11. Morphology of particle fillers at Vf = 0.3 with the interphase layers of
5.3. The application for a different set of test data (a) R/r = 1.0, (b) R/r = 1.015, (c) R/r = 1.038, and (d) R/r = 1.154.

To check the applicability of the proposed scheme, we adopt a

different set of test data as a reference for additional validation [48].
The matrix is diglycidylic ether of bisphenol f epoxy (DGEBF, CibaGeigy
Company, Switzerland), and the filler is the carbon black (CB, Raven
2000, Cabot Corporation, USA) as summarized in Table 4.
To make the prediction by CHS, we repeat the same process as in
Section 2 and 3, Fig. 15 shows the comparison result of the EEC ac-
cording to R/r: 1.479, 1.667, and 1.791, and σi : 6.56 × 10−2,
6.56 × 10−3, and 6.56 × 10−4 S/m. The prediction results of the
McLachlan model and the test results are plotted together. The para-
meters of the McLachlan model are presented in Table 5. The prediction
results produced by the CHS with R/r of 1.667 and σi of 6.56 × 10−4 S/
m are consistent with the McLachlan model and the test results as
shown in Fig. 15. As with previous results, to match the prediction
results with test results, we only update the size and the electrical
conductivity of the interphase. It is confirmed that as the size of the
interphase increases, the PT value increases, and the plateau value is
adjusted by the electrical conductivity of the interphase.
6. Conclusion
In this paper, we proposed efficient 3D random RVEs by RFR al-
gorithm showing spatial and physical randomness with emphasis on the
prediction of the ECC and PT of a nanocomposite. The EEC and PT are
evaluated by CHS as a function of Vf from 5% to 50% in the presence of
a soft interphase to consider the electrical networks and the tunneling
effect. To achieve this goal efficiently, 3D random RVEs with diverse Vf
that randomly replace the material properties of particle fillers with
those of the matrix from the master model are generated. Thus, the ECC
is obtained with diverse Vf . Finally, the PT is successfully found without
any experimental observation. To the best of our knowledge, this kind

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D.-W. Kim, et al. Composites Part B 168 (2019) 387–397

Fig. 13. Generation of 3D RVE FE model with voids.

Fig. 12. Morphology of particle fillers with the interphase layer of R/r = 1.154
and (a) Vf = 0.1, (b) Vf = 0.2, (c) Vf = 0.3, and (d) Vf = 0.4. Fig. 14. Prediction of EEC with diverse Vf according to (a) void contents and
(b) the size of the filler.
Table 3
Input parameters of prediction model. Table 4
Composite Model Parameter
Material properties of constituents of Raven 2000/DGEBF composite.
Matrix (DGEBF) [48] Filler (Raven 2000)
CB/pCBT McLachlan model Vc = 0.28, h = 2.7 [48]

Electrical conductivity (σ ) [S/m] 1.4ⅹ10−14 0.0656

of prediction has never been conducted by CHS with random RVEs
containing spherical particles and interphase modeling due to the heavy
computation cost and complexity of FE mesh generation.
To demonstrate the performance of the proposed method, the ECC
of CB/pCBT and CB/DGEBF was compared with analytical models and
the test results, which are in good agreement with each other. In ad-
dition, a sensitivity analysis of the thickness and conductivity values of
the interphase, void contents, and the size of particles was conducted.
Particle size [nm] – 9.6
The results demonstrated that the thickness and electrical conductivity
of the interphase and the size of particles are the influential parameters
in determining the ECC and PT of the nanocomposites. Based on all of
the prediction results, we believe that the proposed scheme can rapidly
generate random RVEs with a diverse range of Vf values and that it can

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Fig. 15. Comparison of the results produced by the proposed CHS, test results
and MacLachlan model for EEC with diverse Vf according to interphase thick-
ness and interphase conductivity.
Table 5
Input parameters of prediction models.
Composite Model Parameter
CB/DGEBF McLachlan model Vc = 0.036, h = 2.2
accurately predict the ECC considering the geometry of fillers and the
interaction between constituents. This general modeling framework is
not limited in the prediction of ECC of the nanocomposite containing
spherical particulates, and it has great potential to predict the effective
properties, such as the elastic properties and strength, as well as the
thermal conductivity of composites with complex-shaped constituents
such as cylindrical carbon nanotubes, circular-disk-shaped graphene
nanoplatelets, and their mixture. Furthermore, it can provide a solu-
tion, when the nanocomposite is subjected to mechanical strain and
residual stress, which are inevitable in practical sensor applications and
are hardly tractable in conventional analytical models. Research on
these issues is currently ongoing, and the results will be reported when
it is completed.
Acknowledgements
This study was supported by Space Core Technology Development
Program through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science and ICT (Korea, No. 2019001872).
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