Thermal Percolation Behavior of Graphene

Nanoplatelets/Polyphenylene Sulfide Thermal

Conductivity Composites

Junwei Gu,1 Chao Xie,2 Hailin Li,1 Jing Dang,1,3 Wangchang Geng,1 Qiuyu Zhang1
1
Department of Chemistry, Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education,
School of Science, Northwestern Polytechnical University, Xi’an 710072, People’s Republic of China

2
Department of Oral Implantology, Stamotological Hospital, Fourth Military Medical University, Xi’an
710032, China

3
Division of Standards and Materials, AVIC the First Aircraft Institute, Yanliang, Shaan xi 710089, China

The volume fraction of functionalized graphene nano-
platelets (GNPs) influencing on the thermal conductiv-
ities of GNPs/polyphenylene sulfide (GNPs/PPS)
composites are investigated. Results reveal that a
great improvement of the thermal conductivities with
the addition of functionalized GNPs, and the thermal
conductivity of the GNPs/PPS composite is 4.414
W/mK with 29.3 vol% functionalized GNPs, 19 times
higher than that of the pure PPS matrix. The signifi-
cantly high improvement of the thermal conductivities
is ascribed to good thermal transmission through
GNPs networks in the PPS matrix, following a thermal
percolation behavior. Meantime, the GNPs have strong
ability to generate continuous thermally conductive
chains, and the formation of thermally conductive net-
works becomes much easier. POLYM. COMPOS.,
35:1087–1092, 2014. V C 2013 Society of Plastics
Engineers
INTRODUCTION
The continuing miniaturization of microelectronic
devices is setting higher requirements for performance,
reliability, and processing techniques for advanced pack-
Correspondence to: J.W.G.; e-mail: gjw@nwpu.edu.cn (or) Q.Y.Z.;
e-mail: qyzhang1803@gmail.com
Contract grant sponsor: Northwestern Polytechnical University; contract
grant number: JCY20130143; contract grant sponsor: Higher School the
Special Research Fund; contract grant number: 20116102120044; con-
tract grant sponsor: Open Fund from National Defense Science and
Technology Key Laboratory; contract grant number: 2013AFDL007;
contract grant sponsor: National Natural Science Foundation of China;
contract grant number: 81100783.
The author Chao Xie contributed equally to this work and should be
considered co-first author.
DOI 10.1002/pc.22756
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2013 Society of Plastics Engineers
V thermal percolation behavior of GNPS/polymer
aging materials [1–8]. Highly thermal conductivity poly-
mers are promising candidates to address heat dissipation
problems in microelectronic packaging, printed circuit
boards, and flexible displays [9, 10]. However, the ther-
mal conductivity coefficient of most polymers is rela-
tively low.
Recent studies have shown that by incorporation ther-
mal conductivity fillers, such as carbon nanotube [11–14],
boron nitride nanotube [15], silicon nitride [16, 17], sili-
con carbide [18, 19], graphite [20–22], and carbon black
[23, 24], etc., into polymers can improve the thermal con-
ductivities. In our previous work [25–28], various thermal
conductivity composites have been fabricated by adding
different thermally conductive fillers. Unfortunately, the
improvement of thermal conductivities of the composites
is often less than expected from previous theory design.
To the best knowledge of us, the thermal percolation
behavior plays a major role in the great improvement of
the thermal conductivities of the polymeric composites.
However, the physics of thermal percolation behavior is
still a worthy discussed issue [29, 30]. The recognized
thermal conductivity mechanism is that the thermal trans-
port through not only thermally conductive fillers networks
but also the polymer matrix. For this reason, it is difficult
to see clear evidence on the thermal percolation behavior,
especially at low volume fraction of thermally conductive
fillers. Owing to high aspect ratio, outstanding physical
properties, and cost efficiency, graphene nanoplatelets
(GNPs) are considered to be effective fillers for thermally
conductive enhancement in polymeric matrix [31, 32].
At present, some researchers have adopted thermal per-
colation behavior to explain the thermally conductive
behavior of CNT/polymer composites [33–35]. However,

POLYMER COMPOSITES—2014
 FIG. 1. Schematic illustrating a process of as-grown GNPs transformation to MSA/NaOH/NDZ-105 func-
tionalized pristine GNPs (NDZ-105-g-GNPs).
composites has not been observed and reported. Further-
more, thermal percolation transport of the GNPs/polymer
composites can be a promising mechanism for developing
polymeric composites with high thermal conductivity for
various electronic packaging applications.
In this work, the volume fraction of GNPs influencing
on the thermal conductivities of GNPs/polyphenylene sulfide
(GNPs/PPS) composites is investigated. And the method of
methanesulfonic acid (MSA)/sodium hydroxide (NaOH)/iso-
propyltrioleictitanate (MSA/NaOH/NDZ-105) are performed
to functionalize the pristine GNPs, to further improve the
thermal conductivities of the GNPs/PPS composites by min-
imizing the interfacial thermal resistance. The corresponding
thermal percolation behavior of GNPs/PPS thermal conduc-
tivity composite is described and discussed.
EXPERIMENTAL
Materials
Graphene nanosheets (GNPs), KNG-180, with diameter
of 40 mm, super diameter/thickness ratio of 250, are
received from Xiamen Knano Graphene Technology
(Fujian, China); PPS, 1.43 g/cm3, is supplied by Nanjing
Deyuan Science and Technology (Jiangsu, China); MSA
is received from Chengdu Kelong Chemical (Sichuan,
China); Titanate coupling reagent of isopropyltrioleictita-
nate (NDZ-105), is supplied by Nanjing Shuguang Chem-
ical Group (Jiangsu, China); NaOH, isopropyl alcohol,
tetrahydrofuran, and absolute ethanol are all purchased
from Tianjin Ganglong Chemical Group (Tianjin, China).
Surface Functionalization of Pristine GNPs
The surface functionalization of pristine GNPs will
hopefully ensure better dispersion of GNPs in PPS matrix,
FIG. 2. Chemical reactions between functionalized GNPs and PPS matrix.
1088 POLYMER COMPOSITES—2014
to improve the interfacial compatibility of GNPs/PPS.
The proposed method of MSA/NaOH/NDZ-105 hardly
decreases the intrinsic thermal conductivity of GNPs. Fig-
ure 1 shows the general process of MSA/NaOH/NDZ-105
functionalized pristine GNPs. Herein, strong interfacial
adhesion and chemical reaction are guessed to occur
between functionalized GNPs and PPS molecular chains,
as illustrated in Fig. 2.
Fabrication of the GNPs/PPS Composites
The GNPs/PPS composites are prepared according to
the following procedures: (i) Mixing GNPs and PPS using
ball mill machine for 24 h at room temperature, to embed
the GNPs onto the surface of PPS matrix; (ii) Compres-
sion molding (295 C, 10 MPa) to fabricate the GNPs/PPS
composites with segregated structures.
Characterization
The thermal conductivities of samples are measured
using a Hot Disk instrument (AB Corporation, Sweden)
according to standard ISO 22007-2: 2008; The electrical
conductivities of samples are measured using a 4-probe
Agilent 34410A 6.5 digit multimeter. Scanning electric
microscope (SEM) morphologies of samples are analyzed
by VEGA3-LMH (TESCAN Corporation, Czech Republic).
RESULTS AND DISCUSSION
Thermal Conductivities of the GNPs/PPS Composites
Considering relatively high interfacial thermal resist-
ance between rigid GNPs and soft PPS matrix, the pris-
tine GNPs are first functionalized by our proposed
method of MSA/NaOH/NDZ-105, to reduce interfacial
DOI 10.1002/pc

FIG. 3. The volume fraction of GNPs influencing on the thermal con-
ductivities of the GNPs/PPS composites.
thermal resistance effectively and generate the multidi-
mensional thermally conductive networks easily.
The volume fraction of GNPs influencing on the ther-
mal conductivities of the GNPs/PPS composites is shown
in Fig. 3. The GNPs/PPS composites exhibit a rapid
improvement of the thermal conductivities in the range of
6.5–21.0 vol%. The thermal conductivity is 4.414 W/mK
with 29.3 vol% functionalized GNPs, 19 times higher
than that of the pure PPS matrix (0.226 W/mK). When
the volume fraction of GNPs is over 21.0 vol%, the val-
ues of thermal conductivities are increased slowly, which
are ascribed to the formed voids in the GNPs/PPS compo-
sites possibly.
The high intrinsic thermal conductivity of GNPs can
offer reasonable explanations for the higher improvement
of thermal conductivities of GNP/PPS composites than that
of traditional thermally conductive fillers. Additionally, the
super diameter/thickness ratio of GNPs can achieve a rela-
tively lower percolation threshold (Schematic in Fig. 4),
resulting in the higher improving thermal conductivities. It
can be deduced that the thermal conductivities of the
FIG. 4. Schematic of interconnected function between GNPs-GNPs
exceeding thermally conductive percolation threshold.
DOI 10.1002/pc
GNPs/PPS composites are strongly depended on the vol-
ume fraction of the GNPs in the PPS matrix.
Thermal Percolation Behavior
Figure 5 shows the log-log plot of thermal conductiv-
ities of the GNPs/PPS composites as a function of GNPs
volume fraction. Compared with the improving orders of
magnitude in electrical conductivities at low volume fac-
tion of GNPs, the values of thermal conductivities of the
GNPs/PPS composites reveal a more moderate growth. It
is interesting to note that the thermal conductivities of the
GNPs/PPS composites show the similar percolation
behavior to that of electrical conductivities.
Figure 6 shows the SEM morphologies of the function-
alized GNPs/PPS composites. It can be seen that the func-
tionalized GNPs are dispersed uniformly in the PPS matrix
and the thermally conductive networks are formed (also
known as thermal percolation networks). With the increas-
ing addition of functionalized GNPs, GNPs can contact
each other to generate the thermally conductive networks
(c–f). In addition, functionalized GNPs have good interfa-
cial compatibility with PPS matrix. It can decrease the
interfacial thermal resistance between GNPs and PPS
matrix, in favor of the phonon transport, finally to increase
the thermal conductivities of the GNPs/PPS composites.
The Thermally Conductive Coefficient Model Fitting
of the GNPs/PPS Composites
Many theoretical and empirical models have been pro-
posed to predict the effective thermal conductivities of
two-phase composites [36–39]. Maxwell obtained an
exact solution for the conductivity of randomly distrib-
uted and noninteracting homogeneous spheres in a homo-
geneous medium. According to the different dispersion
phase and continuous phase, Hashin-Shtrlkman
determined the values of the lower and upper bounds of
Maxwell equation [40].
FIG. 5. The log-log plot of thermal conductivity of the GNPs/PPS
composites as a function of GNPs volume fraction.
POLYMER COMPOSITES—2014 1089
 FIG. 6. SEM morphologies of the functionalized GNPs/PPS composites. (a) original PPS matrix; (b) 3.2
vol GNPs/PPS composites; (c) 6.5 vol GNPs/PPS composites; (d) 13.5 vol GNPs/PPS composites; (e) 21.0
vol GNPs/PPS composites; (f) 29.3 vol GNPs/PPS composites.

1. kcont < kdisp, the lower bound of Maxwell-Eueken: The prediction of Maxwell-Eucken model has a big devi-
ation, and the thermal conductivity of heterogeneous
2km 1kf 22Vf ðkm 2kf Þ phase materials can be simulated by “Effective Medium
Kc HS- 5km
2km 1kf 1Vf ðkm 2kf Þ Theory” (EMT), the formula of EMT model shown as
follows [41].
1
2. kcont > kdisp, the upper bound of Maxwell-Eneken: Kc 5 ½kf ð3Vf 21Þ1km ð3Vm 21Þ
q4 ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 ½kf ð3Vf 21Þ1km ð3Vm 21Þ2 18km kf 
2kf 1km 22ð12Vf Þðkf 2km Þ
Kc HS1 5kf For GNPs/PPS composites, experimentally determined
2kf 1km 1ð12Vf Þðkf 2km Þ
thermal conductivity values and those predicted from the

TABLE 1. The experimentally determined thermal conductivity values and those predicted from models.

Lower bound of Upper bound of

Volume fraction Experimental Maxwell-Eueken Maxwell-Eueken Values from EMT
of GNPs (vol%) values (W/mK) model (W/mK) (W/mK) model (W/mK)

0 0.226 0.226 0.226 0.226

3.2 0.475 0.248 21.787 0.250
6.5 0.944 0.273 44.514 0.281
13.5 1.856 0.332 94.455 0.379
21.0 3.578 0.406 150.744 0.609
29.3 4.414 0.507 216.672 1.817

1090 POLYMER COMPOSITES—2014 DOI 10.1002/pc


FIG. 7. The logarithmic values of thermal conductivity values as a
function of the GNPs volume fraction.
lower bound of Maxwell-Eueken, the upper bound of
Maxwell-Eueken and EMT models are shown in Table 1.
The experimental thermal conductivity values are smaller
than the theory values predicted from the upper bound of
Maxwell-Eueken model, but are larger than those theory
values predicted by the lower bound of Maxwell-Eueken
and EMT models. The reason is that the predicted models
above do not consider the factors such as particle shape
and content and size, surface performance and interfacial
thermal barrier resistance. Therefore, the models above
have certain limitations and errors, and the corresponding
model equations remain to be further improved and per-
fected. Agari’s semiempirical model can yield better
results than the theoretical ones. The logarithmic equation
of Agari is shown as follows [42, 43]:
lg kc 5Vf  Cf  lg kf 1ð12Vf Þlg ðCp kp Þ
where Cp represents the effect of GNPs on the PPS
structure, that is, Cp is related to the change of thermal
conductivity of PPS matrix, as a consequence of a change
of its crystallinity; Cf represents the ability of GNPs to
continuous chains, 0 < Cf < 1.
The logarithmic values of thermal conductivity values
as a function of the GNPs volume fraction is presented in
the Fig. 7. From Fig. 7, the parameters of Cp and Cf are
calculated to be 1.585 and 20.134. The high value of Cp
suggests that the GNPs can affect the crystallinity of the
PPS matrix obviously. The low value of Cf suggests that
the GNPs have strong ability to generate continuous ther-
mally conductive chains, and the formation of thermally
conductive networks becomes much easier with the incor-
poration of GNPs [44].
CONCLUSIONS
The GNPs prove a remarkable improvement of the
thermal conductivities at low volume fraction loading,
much better than that of traditional thermally conductive
DOI 10.1002/pc
fillers. The thermal conductivity of the GNPs/PPS compo-
sites is 4.414 W/mK with 29.3 vol% functionalized
GNPs, 19 times higher than that of the pure PPS matrix.
The significantly high improvement of the thermal con-
ductivity is ascribed to good thermal transmission through
GNPs networks in the PPS matrix, following a thermal
percolation behavior.
The functionalization of pristine GNPs by MSA/
NaOH/NDZ-105 method can further improve the thermal
conductivities of the GNPs/PPS composites by minimiz-
ing the interfacial thermal resistance. GNPs can affect the
crystallinity of the PPS matrix obviously. Additionally,
the GNPs have strong ability to generate continuous ther-
mally conductive chains, and the formation of thermally
conductive networks becomes much easier.
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DOI 10.1002/pc