Kurdistan Regional Government

Ministry of Higher Education and Scientific Research

Soran University Faculty of Engineering
Chemical Engineering Department

Thermal Conductivity of Polymeric Nanocomposite

Prepared by:

Hadi Haji Hussein

Supervised by:

Dr. Arkan Jasim Hadi

Jan.- 2024
Table of Contents
Abstract ......................................................................................................................................................... 1

1.Introduction ................................................................................................................................................ 1

2.Thermal stability of polymer nanocomposites ........................................................................................... 3

3.Synthesis of polymeric Nanocomposite ..................................................................................................... 7

4.Thermal conductivity of polymeric Nanocomposite.................................................................................. 8

4.1. Physical mechanisms affecting the thermal conductivity of polymeric nanocomposites ................. 9

4.1.1.Polymeric Nanocomposite with inter-filler network .................................................................. 10

4.1.2.Polymeric Nanocomposite without inter-filler network............................................................. 10

5.Conclusion ............................................................................................................................................... 12

References ................................................................................................................................................... 13

Table of Figures
Figure 1/ structure of a polymer chain. ......................................................................................................... 2

Figure 2/ Schematic illustration of a) top-down and b) bottom-up processes. ............................................. 7

Figure 3/ Schematic diagrams of polymer nanocomposites: (a) without inter-filler network; (b) with inter-
filler networks. Thermally conductive pathway is identified with sprint traces. ........................................ 12

List of abbreviations
Abbreviation Definition
TC Thermal conductivity
CNT Carbon nanotubes
GOs Graphene oxides
POSS Polyhedral Oligomeric Silsesquioxane
CVD Chemical vapor deposition
3D Three-dimensional
Abstract
Polymers and polymer composites are widely used in various industrial applications, but their
low thermal conductivity restricts their performance in applications requiring efficient heat
dissipation. Enhancing the thermal conductivity of polymers has been a challenging research
topic. This report discusses the factors influencing the thermal conductivity of polymers,
including morphology, inter-chain coupling, and the use of nanofillers such as nanoparticles,
nanotubes, and nanorods. The synthesis of polymeric nanocomposites and their thermal
stability are explored, highlighting the role of nanofillers in improving heat conduction. The
study also investigates the physical mechanisms affecting the thermal conductivity of polymeric
nanocomposites.

1.Introduction
Polymers and polymer composites are widely used as structural materials for industrial
applications in such fields of science as electronics, energy studies, and biomedicine.
Nevertheless, their low thermal conductivity of about 0.1–0.5 W·m−1 K−1 restricts their
performance and reliability in applications where efficient heat dissipation is required,
including flexible electronics. Increasing the thermal conductivity of these materials has been
a long-standing challenge that is considered to be an emerging hot research topic in recent years.

The thermal conductivity of polymers and polymer composites is governed by a number of

variables, including the morphology structure and inter-chain coupling holding polymer chains,
as well as sort shape dimension, concentration dispersion, and nanofillers. Also, interfacial heat
resistance (Fig. 1) shows the typical structure of a polymer. Any materials with a minimum size
in the nanometer range are referred to as nanofillers, which include nanoparticles, nanotubes,
and nanoroads. These nanofillers increase the thermal conductivity of polymers and polymer
composites through mechanisms such as providing high-level pathways, increasing phonon
scattering, and altering chain conformation or orientation. Factors including material
composition, structure, temperature, and pressure affect thermal conductivity. The different
materials have diverse thermal conductivities, ranging from too poor (air 0.26 W m-1 K-1) to
very good ones (diamond approximately 200W m-1 K-1). Metals possess superior thermal

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conductivities than those of non-metals, and crystalline materials have better thermal properties
compared to amorphous ones. Since polymers are commonly termed thermal insulators and
their limited nature is caused by low thermal conductivity, a number of recent studies have
revealed shockingly excellent thermal conductivities possessed by some polymers that are
comparable to those in poor metals or even silicon.

Polymer composites are materials made up of a polymer matrix and one or more fillers that
exhibit different characteristics as compared to the substrate. Polymer composites can be
classified into

two main categories based on the size of the fillers: microcomposites and nanocomposites. Of
special interest are the nanocomposites that may demonstrate novel and improved properties
that cannot be observed in individual components or microcomposites. The main objective of
polymer nanocomposites is to increase the thermal conductivity of polymers by adding high-
TC fillers such as carbon nanotubes (CNT), graphene oxides (GOs), boron nitrides, and metal
nanoparticles. These additives can serve as thermal conductors, enabling heat conduction
throughout the polymer matrix.

Figure 1/ structure of a polymer chain.

The thermal conductivity enhancement of polymer nanocomposites is not only influenced by

the type of filler used but also by its shape, size distribution, and concentration in terms of
dispersion and interfacial heat resistance. Such factors include phonon-phonon coupling and
phonon electron scattering; they also include boundary and interface contributions.[3,5]

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2.Thermal stability of polymer nanocomposites
1. Polymer/nano-oxide nanocomposites
Polymer/metal or metal oxide nanocomposites enhance thermal stability by establishing
a polymer-nanoparticle network by physical cross-linking of polymer chains with metal
particles. Some examples of nanocomposites include polyacrylate/ZnO and
polyurethane/TiO2. Hybrid materials often undergo reduced thermal stability as a result
of metal-catalyzed oxidative breakdown mechanisms. Utilizing ceramic nanofiller may
enhance the rigidity and heat resistance of a pliable polymer matrix. Polymer matrices
may readily integrate nano-sized silica or alumina particles without requiring any
chemical alteration. The increase of thermal stability involves the manipulation of
molecular dynamics, the formation of physical cross-links, and the establishment of
particular interactions between the components. Experimental findings demonstrate that
the incorporation of colloidal silica nanoparticles into poly maleimide matrices results
in the formation of inorganic networks that are chemically bonded to the poly
maleimides. This bonding enhances the heat resistance of the nanocomposites. The
addition of nanoparticles to a polymer matrix might enhance the initial decomposition
temperature by means of physical or chemical cross-linking. [2]

2. Nanocomposites consisting of polymers and carbon nanotubes.

Functionalizing the surface of nanofiller with carbon nanotubes may boost interfacial
interactions with the polymer matrix, hence improving its dispersion. Functionalization
may be achieved by three methods: chemical functionalization, physical
functionalization, and surface deposition. The mechanisms that promote the thermal
stability of carbon nanotubes and nanofibers include two processes. The first process is
the decrease of mass loss in inert atmospheres, which occurs owing to the physical
adsorption effects of macromolecules on the surfaces of the nanotubes. The second
process is the reduction of mobility in the presence of carbon nanotubes.
The thermal stabilization effect of carbon nanotubes is comparable to that of layered
silicates and is observable in inert atmospheres via the alteration of the temperature at
which deterioration begins. The Marosfői research group discovered that the thermal
stabilization effect of carbon nanotubes is due to enhanced interfacial contacts between
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 the nano additive and polymer matrix, resulting in an elevation of the activation energy
of degradation. The introduction of multi-walled carbon nanotubes caused a little delay
in the process of thermal volatilization, without altering the underlying mechanism of
thermal degradation. However, the degradation process in the presence of air was
delayed by around 100°C, regardless of the concentration of multi-walled nanotubes.
Research conducted by Chipolata has shown that the thermal stability of
polymer/carbon nanotube nanocomposites is directly influenced by the amount of nano
additives present. The improved thermal stability is attributed to the interactions
between the macromolecular chains and carbon nanotubes. Nevertheless, carbon
nanoparticles may also expedite the breakdown of polymers in the presence of oxygen,
often because of residual amounts of inorganic components. The degrading
characteristics of polymer/carbon nanotube nanocomposites are contingent upon the
specific alteration undergone by the carbon nanotubes. Reactive chemical changes have
the capacity to substantially alter the degradation route and enhance thermal stability by
achieving a more uniform dispersion of nanoparticles. [2]

3. Nanoclays
The existing body of work on the thermal stability of polymer/clay nanocomposites
presents inconclusive findings on the efficacy of clay in enhancing thermal stability.
Vaia's experimental findings demonstrated that the inclusion of clay in the polymer
matrix led to a noteworthy reduction in the rate of mass loss. This effect was seen even
when as little as 2 weight percent of exfoliated layered silicate was added. Nevertheless,
the inclusion of clay in poly(propylene-graft-maleic anhydride)/layered silicate
nanocomposites had a negligible impact on thermal degradation and did not result in
any significant increase in residue.
The influence of the scattered nano clay on thermal degradation is contingent upon the
particular processes linked to the degradation response of the polymer and the chemical
characteristics of the nano additive. Systematic investigations have shown that the clay
has an impact on both the quantity and quality of polymer breakdown. The impact of
clay on enhancing the thermal stability of different polymeric matrices has been
analyzed based on the intricacy of degradation pathways or radical stability.

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 Recent study has verified that alterations in the movement of large molecules adhere to
the surface of the filler, leading to an elevation in the glass transition temperature. These
nanoparticles may exhibit reduced reactivity and enhanced chemical and thermal
stability compared to unmodified polymers. Montmorillonite, obtained from bentonite
by the process of settling in water and then treated with sodium cations, has excellent
resistance to changes in temperature within the range of 20–500 °C.
The distribution of nano additives and their interaction with the matrix are crucial factors
in determining the thermal stability of polymer nanoparticles. Enhancing the
intercalation of polymer chains between the layers is achieved by improving the
incorporation of suitable organic linkages between the matrix and filler by
functionalization. These positively charged ions decrease the amount of energy on the
surface of organoclay and make it easier for large molecules to enter the spaces between
the clay layers.
At the nanometric scale, the interaction between the nanofiller and the matrix can result
in three different scenarios, each of which has an impact on the properties of the polymer
composite material. These scenarios include: the nanofillers being unevenly mixed in
the matrix and forming distinct regions, macromolecules entering between the plates of
the nanofillers, or the nanofillers being completely separated and dispersed.
Clays in polymer nanocomposites have a dual catalytic influence on the heat breakdown
of organic compounds. Under elevated temperatures in an inert environment, the clay
promotes the breaking of carbon-carbon bonds, causing the release of volatile
substances and the formation of thermally stable charred nanoparticles by a process
called thermo-oxidative dehydrogenation. The enhancement in thermal stability is
proposed to be a result of the production of char due to the presence of distributed
montmorillonite layers. Exfoliated clay nanoparticles have the ability to catalyze the
breakdown of hydroperoxide under circumstances that include the presence of oxygen.
Nano additives initiate degradation processes before to the initiation of thermal
breakdown of the pure polymer, resulting in a reduction in the rate of mass loss during
later degradation phases. The catalytic activity of organoclay in polymer degradation is
demonstrated throughout the process of nanocomposite compounding and as the

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 material ages in a heat oxidative environment. Quaternary alkyl ammonium organoclays
undergo decomposition at temperatures ranging from 200 to 300 °C, resulting in the
formation of α-olefins and amines. This decomposition process aligns with the Hofmann
elimination mechanism. This phenomenon often occurs when a quaternary ammonium
hydroxide or chloride undergoes conversion into an alkene and an amine at elevated
temperatures.
The accelerated deterioration of polymer in the presence of organoclay is often
attributed to the catalytic effect of acidic sites generated as a result of the Hofmann
degradation of onium compound. The presence of both organic modifiers and their
degradation products, as well as the naturally occurring acidic sites on the mineral
surface, contribute to the catalytic effects on polymer breakdown. The presence of metal
ions, such as Fe 3+ or Cu 2+, in clay minerals serves as catalytic sites, so enhancing the
degrading processes. Alkylammonium salts with catalytic activity for degrading
reactions may give rise to several following processes, including the creation of
unsaturated and conjugated bonds, cyclization, aromatization, fusion of aromatic rings,
subrostrate carbon formation, and graphitization. The development of char during the
thermal degradation of polymer nanocomposites demonstrates improved resistance to
flames, leading to the investigation of the thermo-oxidative stability of these materials
in connection to fire retardancy. [2]

4. Other Nanofillers
Studies suggest that gold nanoparticles possess catalytic properties that may augment
the heat decomposition of polymers. Nanocomposites that include metal are more
resilient to pyrolytic breakdown, although they may experience mass reductions in the
presence of oxidative atmospheres. Graphite has an anisometric shape and exhibits heat
resistance, enabling it to form physical barriers against heat and dispersing gasses.
Unaltered graphite does not impede polymer degradation but functions in a physical
manner. The oxidation process of graphite increases the presence of polar groups on the
graphite layers, resulting in enhanced thermal characteristics. Polyhedral oligomeric
silsesquioxane nano additives have a wide range of uses, such as modifying surfaces,
strengthening coatings, supporting catalysts, and creating membrane materials.

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 Poly(phenyl) silsesquioxane (POSS) inorganic-organic hybrid materials provide
enhanced flame and heat resistance, increased glass transition temperature, and
improved thermal stability and melt strengths. POSS molecules have the capacity to
undergo reactions with diepoxides or dianhydrides, resulting in the formation of
materials with a high density of cross-links. These materials exhibit excellent resistance
to thermal oxidation and show enhanced compressive strengths. [2]

3.Synthesis of polymeric Nanocomposite

In-situ synthesis of the inorganic particles or dispersion of fillers can be commonly used to
prepare nanocomposites. The right selection of preparation technology is crucial for the
achievement of nanomaterials with the appropriate properties. The synthesis of polymeric
nanocomposites often involves bottom-up or top-down methodologies (Fig. 2).

Figure 2/ Schematic illustration of a) top-down and b) bottom-up processes.

In the case
Figureof3/Bottom Furthermore,
Schematic block-assembly
diagrams of polymer or building
nanocomposites: (a) withoutblock approaches
inter-filler network; (b)can
withbe used
inter-filler networks. Thermally conductive pathway is identified with sprint traces.Figure 4/
whereinSchematic
preformed units are
illustration of a)hierarchically assembled
top-down and b) bottom-up to create the desired material. Compared
processes.

to in-situ nanoparticle formation, an advantage of the building block approach is that at least
one structural unit has a well-defined structure and seldom takes significant changes during
Figure 5/ Schematic diagrams of polymer nanocomposites: (a) without inter-filler network; (b) with
matrix inter-filler
formations. As mentioned
networks. above, the
Thermally conductive bottom-up
pathway methodologies
is identified include chemical
with sprint traces.Figure 6/
Schematic illustration of a) top-down and b) bottom-up processes.

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Figure 7/ Schematic diagrams of polymer nanocomposites: (a) without inter-filler network; (b) with
inter-filler networks. Thermally conductive pathway is identified with sprint traces.Figure 8/
Schematic illustration of a) top-down and b) bottom-up processes.
processes such as sol-gel, CVD, template synthesis, or spray pyrolysis. On the other hand, the
bottom-up approach breaks down the bulk material into smaller pieces or patterns using mostly
physical techniques with top dispersions of layered silicates in polymer matrices. Inorganic
nanoparticles are usually dispersed into the polymer matrices by referring to the three
approaches. The first employs the bottom-up approach, whereby there is a direct impregnation
of a polymeric matrix by means of solution or melt. The second process involves the in-situ
polymerization of the nanoparticles prepared prior to or with the simultaneous synthesis of
organic and inorganic species for particle formation and subsequent suspensions. The final one
involves the in-situ formation of both organic and inorganic components. These two latter
approaches are called bottom-up methodologies.[4]

4.Thermal conductivity of polymeric Nanocomposite

Advances in nanocomposites based on graphene and CNTs have displayed notable mechanical
as well as thermal properties. Generally, the thermal conductivity of a suspended single-layer
graphene is about 5300 W m−1 K −1, and it decreases for multiple layers approaching that of
graphite. Nevertheless, the thermal conductivity of these carbon-based nanocomposites is
smaller than predicted due to problems associated with increasing filler volume fractions. Size
effects on heat conduction by each component and very weak coupling lead to disordered
thermoreflectance between the fillers and their boundary swarms (polymer).The graphene-
based polymer nanocomposite may achieve a thermal conductivity of up to This level is attained
when the volume fraction reaches 25%. There is a slow increase in the thermal conductivity
with small volume fractions, then there is a sudden turning point at 15 to 20% of the filling
fraction. This percolation-like behavior is due to an additional pathway between the connecting
graphene nanoplatelets when the volume fraction increases from 13% to 19%. The coupling
between CNTs and polymers can be greatly enhanced by functionalizing the surface, which
leads to a decrease in the ITR, but it also potentially increases secondary damage that reduces
the intrinsic thermal conductivity. Moreover, improving the contact area between the fillers and
polymers by modifying the aspect ratio of the filler can also lower ITR. The largest thermal
conductivity achieved was 6.44 W m−1 K −1 (25% loading), which translates into a ratio 30
times larger than the applicable matrix polymers and is superior to conventional fillers at about
70 vol%.[5]

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 4.1. Physical mechanisms affecting the thermal conductivity of polymeric
nanocomposites
The thermal conductivity of polymer nanocomposites is influenced by several physical
mechanisms [3], including:

1. Filler Type: To a great extent, the thermal conductivity of the nanocomposite is

determined by that of the filler material. Highly thermally conductive fillers, such as
CNTs, graphene, and metal nanoparticles, can enhance the thermal performance of a
given nanocomposite.
2. Filler Size and Shape: Thermal conductivity can be influenced by the dimensions and
shape of the filler in a nanocomposite. Big fillers increase the thermal conductivity of
the volume, while small ones possess a huge interfacial temperature resistance that
cancels out its high mean. Additionally, the filler’s ratio, such as CNT length-to-
diameter, can also affect the thermal conductivity of nanocomposite.
3. Filler Concentration and Arrangement: Secondly, the amount of filler and its orientation
in the polymer matrix can additionally affect thermal conductivity. However, the fillers
behave as individual entities and exhibit a linear increase in conductivity with increasing
solute concentrations at low concentrations. However, as the concentrations increase,
fillers tend to agglomerate, and due to this, their thermal conductivity decreases.
4. Interfacial Thermal Resistance: However, one of the main challenges concerning high
thermal conductivity nanocomposite is the interfacial resistance between filler and
polymer matrix. The nanofiller’s surface-to-volume ratio may cause a lot of significant
interfacial conductivity resistance that could counterbalance the overall thermal
resistance of a nanocomposite.

5. Polymer Matrix: The thermal conductivity of the nanocomposite may be impacted by

the crystallinity and molecular orientation of the polymer matrix.

We discuss about the polymer nanocomposites as well. Without any inter-filler network and with
an inter-filler network. The present knowledge on the thermal conductivity of the polymer
nanocomposites.

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4.1.1.Polymeric Nanocomposite with inter-filler network

The conductivity of polymeric nanocomposites with an inter-filler network is the case when
filler concentration in a nanocomposite exceeds the critical value, at which continuous network
occurs. This may significantly improve the thermal conductivity of nanocomposites since heat
can pass through fillers, and matrixes or interfaces do not retard it fig(3-b)shows thermal
conductivity pathway and filler distribution. But even this case is not free from challenges, like
keeping a favorable heat conduction pathway, preventing filler agglomeration, and decreasing
inter-filler thermal contact resistance.

Classes of fillers that can create an inter-filler network are single, hybrid, and 3D foam fillers.
One-filler fillers are the same kind of fillers as carbon nanotubes, graphene, and metal
nanoparticles. The combination of hybrid fillers is diverse, like carbon nanotubes and graphene
or CNTs with metal nanoparticles. The porous foam fillers include a naturally 3D network
structure of intrinsic carbon foam or graphene.

Each category of filler has its strengths and weaknesses in improving the thermal conductivity
of nanocomposites. For instance, single-fillers can form a percolated network at low filler
concentrations; however, these networks might possess high inter-filler thermal contact
resistance and voids in the structure. However, they have complex interfacial interactions and
compatibility problems. The use of 3D foam fillers can help overcome the inter-filler thermal
contact resistance and improve their contact area with a matrix, but these foams have low
mechanical strength at a high cost.[1,3]

4.1.2.Polymeric Nanocomposite without inter-filler network

In a situation where an inter-filler network is not formed in one nanocomposite, the thermal
conductivity of that composite will be due to the limitations of the polymer matrix and the
interface resistance between fillers and matrices fig(3-a)shows thermal conductivity pathway
and filler distribution. The resistance to heat transfer across the boundary between two given
materials is referred to as interface thermal resistance. It is determined by several parameters,
namely the phonon wavelength, the incidence angle impact of interface roughness, and the
acoustic impedance mismatch. Sound, or heat, is the form of mechanical vibrational energy

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whose quanta are called phonons. For nanocomposites without an inter-filler network, the
thermal conductivity increases continuously with the increasing filler concentration and lacks
percolation behavior. The behavior referred to as percolation is the substantial increase in
thermal conductivity when filler concentration reaches a critical value that will form a
continuous network of particles. The concentration-dependent thermal conductivity of
nanocomposites without an inter-filler network can be separated into three regimes:

• In the case of low concentration filler regime, they are independent from one another
and as such thermal conductivity will increase with the increasing amount of
• fillers ( first rise )
• As the concentration continue to increase, the fillers are prone to aggregate as a result
of insufficient volume at high concentrations. Unlike the monomer phase, when fillers
agglutinate the contact area between the filler and polymer matrix reduces significantly
ad also thermal conductivity sharply drops. In addition to the interface thermal
resistance, variations of filler shapes (such as bending or twisting) also lead to a decrease
in heat transmission.
• With further increase in the filler concentration, a second rise of thermal conductivity
may take place due to the aggregation between clusters and contact with each other for
heat transport pathway formation.

There are several ways to increase the interface conductance and make filler distribution better
in nanocomposites without inter-filler networks, such as surface modification,
functionalization, hybridization, etc. These methods can change the morphology of
nanoparticles and homogenize defects. density chemisorbed bonds The compatibility of the
matrix includes effects on the thermal transfer rate within the nanocomposite. [3]

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 Figure 9/ Schematic diagrams of polymer nanocomposites: (a) without inter-filler network; (b) with inter-filler networks.
Thermally conductive pathway is identified with sprint traces.

5.Conclusion
In conclusion, improving the thermal conductivity of polymers and polymer composites is
crucial for enhancing their performance in various applications. The incorporation of
nanofillers, such as carbon nanotubes, graphene oxides, and nano clays, has shown promising
results in increasing thermal conductivity by providing high-level pathways and altering chain
conformation. The thermal stability of polymer nanocomposites can be enhanced through the
establishment of polymer-nanoparticle networks, functionalization of nanofiller surfaces, and
the inclusion of metal or metal oxide nanoparticles. The selection of appropriate preparation
technologies and the optimization of nanofiller concentration and dispersion are vital for
achieving desired thermal properties. Overall, further research and development in the field of
polymeric nanocomposites are needed to unlock their full potential in heat dissipation
applications.

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References
[1] Almuallim, B., Harun, W.S.W., Al Rikabi, I.J. and Mohammed, H.A., 2022. Thermally conductive
polymer nanocomposites for filament-based additive manufacturing. Journal of Materials Science,
[online] 57(6), pp.3993-4019. Available at: <https://link.springer.com/article/10.1007/s10853-021-
06820-2#citeas> [Accessed 26 January 2024].

[2] Huang, X. and Zhi, C., 2016. Polymer Nanocomposites. 1st ed. pringer Series on Polymer and
Composite Materials. Switzerland: Springer.

[3] Huang, C., Qian, X. and Yang, R., 2018. Thermal conductivity of polymers and polymer
nanocomposites. Materials Science and Engineering: R: Reports, [online] 132, pp.1-22. Available at:
<https://www.sciencedirect.com/science/article/abs/pii/S0927796X1830113X?via%3Dihub>
[Accessed 24 January 2024].

[4] Oliveira, M.J., & Machado, A.V. (2013). Preparation of polymer-based nanocomposites by
different routes.

[5] Xu, X., Chen, J., Zhou, J. and Li, B., 2018. Thermal Conductivity of Polymers and Their
Nanocomposites. Advanced Materials, [online] 30(17), pp.1-10. Available at:
<https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.201705544> [Accessed 24 January
2024].

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