1 Abstract

Polyphenylene Sulphide and Multi-Walled Carbon Nano Tubes composite was prepared using
melt blending procedure [1]i. And the same method was used for PPS/GNPs composites prepared
by melt intercalation by shearing action [2]ii. MWCNTs uniformly distributed within the matrix of
PPS in a 5 wt % in case of PPS/MWCNTs and 7 wt % in case of PPS/GNPs and it is confirmed
through Scanning Electron Microscopy (SEM) and there seemed a little aggregation in both
PPS/CNTs and PPS/GNPs nanocomposites [2]. Thermal properties were determined using
Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry and studied by three
models: Maxwell Theoretical Model, Hamilton Cross Model and Russel Cross Model. The thermal
conductivity of PPS/GNPs is improved and thermal conductivity used for GNPs as 5000 w/mk
according to ____________. And 2586 w/mk for PPS/ MWCNTs according to__________. An
increase of thermal conductivity of PPS is observed by the order of ________as compared to the
unfilled thermoplastic. the reduction in thermal boundary resistance was observed by increasing
GNPs and MWCNTs content.

1. Introduction
Poly phenylene sulfide is an excellent high-performance thermoplastic and has broad range of
applications from consumer products to aerospace sector due to its superior chemical resistance,
thermal stability, high stiffness and considered to be a metal alternativeiii. Despite of high melting
point up to 285oC PPS have low glass transition temperature (Tg) due to flexible sulfide linkages
in the chemical structure and brittleness.
Thermal conductivity is widely investigated during due to the large dissipation of energy. Modern
studies revealed that thermal conductivities of many composites can be improved by the
fabrication of conductive or hybrid fillersiv. Graphenes, CNTs, Graphite, Carbon Black were
considered to be thermally conductive fillersv. This research mainly focuses thermal conductivities
of PPS/MWCNTs and PPS/GNPs composites. The addition of CNTs and GNPs forms some
agglomerates during fabrication of compositets that can be minimized by two methods. One by
the fictionalizing the CNTs and Graphenes and other by applying high shear rate to equally
distribute the filler content. Thermal conductivity of the nanocomposites is smaller than the
particle size and it shows ballistic transport than diffusive.vi Pak et al. investigated the thermal
conductivity of MWCNTs with powder of boron nitride. With 50% BN thermal conductivity of
PPS observed was 1 W/mk. while on the other hand with 50% BN powder and 1 wt% MWCNTs
the thermal conductivity was recorder 1.45 W/mk [5]. MWCNTs are cylindrical structures and
more phonons transport tthrough interface because of the higher aspect ratio and high surface area
to volume ratio. The addition of MWCNTs into the polymer matrix have remarkably improved the
thermal conductivityvii. However thermal conductivity of CNTs show linear enhancement but lack
of percolationviii. CNTs are proved to show possess more thermal conductivity as compared to the
metals. That’s why carbon nano-tube based composites are suitable for high temperature
conductivities. But due its costly production other conducting fillers are being usedix.
Graphenes are carbon-based honey comb structured nano-fillers with 2 dimensional structure in
which carbon atoms are (Sp2) bonded. A single layer graphene can exhibit thermal conductivity
up to 5000 W/mk [7]. Having high aspect ratio, cost effectiveness and good physical properties
graphenes are encouraged to use with polymeric matrix [8]. Single Graphene nanoplatelets show
a contribution for polymer matrix. GNPs allow phonon transport through the matrix and filler
interface as a result PPS/GNPs exhibits an increased order of thermally conductive composite upto
5000 W/mk. [8]. This article focused on the thermal conductivity of PPS/MWCNTs at different
concentrations of MWCNTs of 1,3 & 5 wt%. while PPS/GNPs’ thermal conductivity studies by
varying GNPs concentration w.r.t 3,5 & 7 wt%. The results obtained are subjected to quote an
increased temperature conductance of the nanocomposites.

2 Experimentation
2.1 Materials
Polymers usually show lower temperature conductance and it is of quite interest to increase their
thermal conductivity so that can be easily used as heat sinks in electronic systems. There are some
conventional ways to increase the thermal conductivity by addition of conductive filler. Thermal
conductivities of some of the conductive fillers is given belowx

Table 1: Thermal Conductivities of some Conductive Fillers[9]

Material Thermal Conductivities at 25oC W/(mk)

Graphite 100-400 (On Plan)
CNTs 2000-6000
Diamond 2000
Coper 483
Silver 450
Aluminium 204
Nickal 158

Some of the physical properties of Fillers are given in table 2.

Table 2: Physical Properties of fillersxi
2.1.1 PPS
Poly phenylene sulfide is considered to be a thermosetting-thermoplasticxii [3] due to its excellent
properties of heat and chemical resistance, high mechanical properties, oxidative, hot water
resistancexiii [4], high creep resistant, stiffnessxiv [5]. Now a days PPS is widely being used in
engineering application such as automotive and industrial applications as well as for consumer
goods. Due to completely recyclable and lower carbon emissions than other epoxies and
engineering plastics is increasing its demand for automotive and other electronics applications [5].
One of the expected increase in demand rate is shown in Fig 1. Instead of all its demand in
automotive PPS is now a major concern in aerospace sector [5]. PPS possesses low thermal
conductivity and to make it high thermal conductor composites are prepared using conductive
fillers as given in above table 1. Physical properties of PPS are given in the table 3.
Table 3: Physical Properties of Polymers

Figure 1: expected increase of demand for PPS in USA 2014-2017

2.1.2 CNTs
Carbon Nanotubes are the hollow cylindrical structures and thought an ideal candidate in
reinforcing the polymers due to low density high electrical and thermal conductivityxv. CNTs are
of two types
I. Single-Walled Carbon Nano-tube
II. Multi-Walled Carbon Nano-tube
PPS/MWCNTs composites were produced via melt blending procedure in which polymer matrix
and CNTs are both subjected to an extruder under centrifugal action resulting a homogeneous
nanocomposite shown in fig 2. Though the filler doesn’t homogeneously dispersed so the
agglomerates can be minimized by functionalizing the CNTsxvi.

Figure 2: Polymer matrix/CNTs composites formation via blending procedure

Multiwalled Carbon nanotubes were produced through catalytic deposition method on an industrial
scale assuring the following properties
Carbon purity 90%, diameter 10nm, length 1.3𝜇𝑚, surface area 250-300 m2/g and density of 1.75
g/cm3.xvii Thermal conductivity of 3000 W/mk is reported for MWCNTs and 2000 W/mk for
SWCNTs. Thermal conductance depends upon number of phonons to transport energy and their
scattering along the interface and also on the path length [9].

Figure 3: Effect of interface thermal resistance on thermal conductivity enhancement in CNTs

Composites
Owing a larger diameter of MWCNTs the temperatue effects should be small for quantum effects
and with linear acoustic phonons their thermal conductivity should be of that a 2-D structure. The
thermal conductivity of a 2-sheet follows T2 temperature dependence. Ye et al. measured thermal
conductivity of the MWCNTs samples and found a T2 temperature dependence up to 100K, and at
room temperature due to tube to contact or incomplete graphitization MWCNTs thermal
conductivity of these samples found to be approximately 25K/mk.
Microfabricated structure is used to directly measure the thermal conductivity Kim et al. Thermal
conductivity of a single MWCNTs is measured and it showed a same temperature dependence
discussed above and an increased thermal conductivity up to 100K and peaks at 300K. The room
temperature value of thermal conductivity is upto 3000 W/mkxviii.

Figure 4: thermal conductivity of a single MWCNT

2.1.3 Graphenes
A monolayer of sp2 bonded carbon atoms arranged in a honeycombed structure having one atom
thickness. Graphite nanoplatelets are two-dimensional crystal lattice enriched with distinct
properties of high aspect ratio, high surface area and superior thermal conductivityxix. The
graphene can be subdivided in one layer, bilayer and multi-layer graphene. However, the
production of multi-layer graphene is effective and low cost and have the thermal conductivity of
about 3000-5000 W/mk. Having same characteristics as of single layer. Thus, can be used to make
high performance composites. PPS/GNPs nanocomposites are prepared through melt blending as
discussed above in CNTs section. The homogeneous dispersion of GNPs throughout the polymer
matrix is confirmed by scanning electron microscopy. The thermal behavior of PPS/GNPs can be
studied by the differential scanning electron calorimeter. As shown in fig 4 below

Figure 5: DSC for PPS/GNPs (a) heating (b) cooling

2.2 Theoretical models of thermal Conductivity

Enhancement of thermal conductivity has been reported over one and half decades. A wide
difference in the literature values of thermal conductivity to the observed values is reported. There
are some mean field models used to predict the thermal conductivity values of the binary
component mixturesxx.
Maxwell Garnett Model
The first theoretical model used to predict thermal conductivity of the binary component
mixturesxxi having negligible interfacial resistance. This model predicts thermal conductivity of
linear, isotropic, non-parametric mixturesxviii. the randomly distributed spherical inclusions
considered to be small as compared to the total volume.

Kp according to Chen et al.

Whereas, Keff, Kp and Kf are thermal conductivities of the nanocomposites, inclusions and the
matrix. And ∅v is the volume fraction of nanoparticles xviii.
2.2.1 Hamilton-Crosser Model
Later Hamilton and Crosser modified the Maxwell model for non-spherical inclusions. The
effective thermal conductivity described by Hamilton-Crosser model by the following expression

3
Whereas, 𝑛 = Ѱ , empirical shape factor

Ѱ = dispersed particle sphericity

2.2.2 Russel Model
Using electrical analogy Russell developed a model which assumes that discrete phase is an
isolated cube and isothermal lines are plans. using a series parallel network, he derived an
equation to measure the thermal conductivity of the composites xxii.

3 Results
4 Conclusion
5 References
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polyphenylene sulfide/multi-walled carbon nanotube composites. United Kingdom: Engineering
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[2] Xing, J., Deng, B. and Liu, Q. (2017). Effect of graphene nanoplatelets on the performance of
polyphenylene sulfide composites produced by melt intercalation. SAGE Publication, page 1-2
[3] Hiroi, R. and Tanaka, H. (2010). Preparation of PPS-based nanocomposites and delamination of
layered titanate fillers . Japan: Journal, page 1
[4] Gu, J., Du, J., Dang, J., Geng, W., Hu, S. and Zhang, Q. (2014). Thermal conductivities, mechanical
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[5] Eksik, O., Bartolucci, S., Gupta, T., Fard, H.,Tasciuc, T. and Karotkar, N. (2016). A novel approach to
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[6] Horiuchi, S., Yamamoto, D., Kaiho, S., Yamashita, K., Yokoe, M., Osato, K. and Yamauchi, K.
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Journal, page
[7] Wu, D., Wu, L., Zhou, W.,Yang , T. and Zhang ,M. Study on Physical Properties of Multi-walled
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[8]
i
Mechanical and thermal properties of polyphenylene
sulphide/multi-walled carbon nanotube composites by Zhenyu Jiang, Peter Hornsby, Rauri McCool, Adrian Murph
ii
Effect of graphene nanoplatelets on the performance of polyphenylene sulfide composites produced by melt
intercalation by Jian Xing, Bingyao Deng and Qingsheng Liu
iii
Preparation of PPS-Based Nanocomposites and Delamination of Layered Titanate Fillers by Ryoichi Hiroia,∗ and
Hitoshi Tanakab
iv
THERMAL CONDUCTIVITIES, MECHANICAL AND THERMAL PROPERTIES OF GRAPHENE NANOPLATELETS/
POLYSULFIDE JUNWEI GU JUNJI DU
v
A novel approach to enhance the thermal conductivity of epoxy nano composites using graphene core-shell
additives by Osman Eksik, Stephen F. Bartolucci
vi
Well-Controlled Synthesis of Poly (phenylene sulfide) (PPS) Starting from Cyclic Oligomers by Syunsuke Horiuchi,1
Daisuke Yamamoto,2 Shu Kaiho,1 Kohei Yamashita,2 Makito Yokoe,2 Keiko Osato,2 Koji Yamauchi
vii
StHoriuchiudy on Physical Properties of Multiwalled Carbon Nanotube/Poly(phenylene sulfide) Composites by
Defeng Wu,1 Lanfeng Wu,1 Weidong Zhou,2 Tao Yang,1 Ming
viii
Thermal conductivity of carbon nanotubes and graphene in epoxy nanofluids and nanocomposites by
Mario Martin-Gallego,1 Raquel Verdejo,1 Mohamed Khayet,2 Jose Maria Ortiz de Zarate,2 Mohamed
Essalhi,2 andMiguel Angel Lopez-Manchado 1
ix
Thermal Percolation Behavior of Graphene Nanoplatelets/Polyphenylene Sulfide Thermal Conductivity
Composites by Junwei Gu,1 Chao Xie,2 Hailin Li,1 Jing Dang,1,3 Wangchang Geng,1 Qiuyu Zhang
x
Thermal Conductivity of Carbon Nanotubes and their Polymer Nanocomposites: A Review by Zhidong Han 1,* ,
Alberto Fina 2,
xi
Development of Novel Graphene and Carbon Nanotubes Based Multifunctional Polymer Matrix Composites
byS.N. Leung, M.O. Khan and H.E. Naguib
xii
Study on Physical Properties of Multiwalled Carbon Nanotube/Poly(phenylene sulfide) Composites byDefeng
Wu,1 Lanfeng Wu,1 Weidong Zhou,2 Tao Yang,1 Ming Zhang1
xiii
Well-Controlled Synthesis of Poly (phenylene sulfide) (PPS) Starting from Cyclic Oligomers by Syunsuke
Horiuchi,1 Daisuke Yamamoto,2 Shu Kaiho,1 Kohei Yamashita,2 Makito Yokoe,2 Keiko Osato,2 Koji Yamauchi
xiv
Poly phenylene sulfide market size by application( automotive, electricacl and electronics, industrial and
coatings) by region and segment forecasts 2014-2025
xv
Electrical and mechanical properties of Carbon nanotube/polyphenyle sulfide composite incorporating
poyetherimide and inorganic fullerenes like nano particles by ana m.daiz pascaul
xvi
Mechanical and Thermal Properties of Polyphenylene Sulfide/Multiwalled Carbon Nanotube Composites by
Zhenyu Jiang, Peter Hornsby, Rauri McCool, Adrian Murphy
xvii
Electrical And Thermal Conductivity Of Polypropylene Filled With Combinations Of Carbon Fillers byBeate
Krausea), Petra Pötschkeb)
xviii
Carbon Nanotubes: Thermal Properties by J. Hone
xix
Effect of graphene nanoplatelets on the performance of polyphenylene sulfide composites produced by melt
intercalation by Jian Xing, Bingyao Deng and Qingsheng Liu
xx
Thermal conduction in polymeric nanofluids and nanosolids controlled by interfacial scattering solutions to some
selected problems by Nisha M. R.
xxi
Theoretical Models for Thermal Conduction in Polymeric nanofluids and nanosolids department of
instrumentation CUAST
xxii
A Numerical Study on the effective thermal conductivity of the Composite material by Serhat DUMRAZ , January
2004