Progress in Polymer Science 59 (2016) 41–85

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Thermal conductivity of polymer-based composites:

Fundamentals and applications
Hongyu Chen a,∗ , Valeriy V. Ginzburg b , Jian Yang c , Yunfeng Yang a , Wei Liu a ,
Yan Huang a , Libo Du a , Bin Chen a
a
Dow Chemical (China) Investment Co. Ltd., Shanghai 201203, People’s Republic of China
b
The Dow Chemical Company, Midland, MI 48674, USA
c
The Dow Chemical Company, Freeport, TX 77541, USA

a r t i c l e i n f o a b s t r a c t

Article history: Thermal management is critical to the performance, lifetime, and reliability of electronic
Available online 26 March 2016 devices. With the miniaturization, integration and functionalization of electronics and
the emergence of new applications such as light emitting diodes, thermal dissipation
Keywords: becomes a challenging problem. Addressing this challenge requires the development of
Thermally conductive polymer composites novel polymer-based composite materials with enhanced thermal conductivity. In this
Modeling review, the fundamental design principles of highly thermally conductive composites were
Chain orientation
discussed. The key factors influencing the thermal conductivity of polymers, such as chain
Liquid crystalline polymers
structure, crystallinity, crystal form, orientation of polymer chains, and orientation of
Thermally conductive fillers
Microstructure control ordered domains in both thermoplastics and thermosets were addressed. The properties of
thermally conductive fillers (carbon nanotubes, metal particles, and ceramic particles such
as boron nitride or aluminum oxide) are summarized at length. The dependence of ther-
mal conductivity of composites on the filler loading, filler aggregate morphology and overall
composite structure is also discussed. Special attention is paid to recent advances in control-
ling the microstructure of polymer composites to achieve high thermal conductivity (novel
approaches to control filler orientation, special design of filler agglomerates, formation
of continuous filler network by self-assembly process, double percolation approach, etc.).
The review also summarizes some emerging applications of thermally conductive poly-
mer composites. Finally, we outline the challenges and outlook for thermally conductive
polymer composites.
© 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2. Modeling of thermal conductivity in composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.1. Constitutive (micromechanical) modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.2. Finite element modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3. Interfacial thermal resistance modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

∗ Corresponding author. Tel.: +86 21 38513128; fax: +86 21 58954173.

E-mail address: HChen@dow.com (H. Chen).

http://dx.doi.org/10.1016/j.progpolymsci.2016.03.001
0079-6700/© 2016 Elsevier Ltd. All rights reserved.
42 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

3. Thermal conductivity measurement techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .51

3.1. Steady-state methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.1.1. Guarded hot plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1.2. Axial flow method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1.3. Heat flow meter method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.1.4. Pipe method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.2. Transient methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.2.1. Flash method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.2.2. Transient hot wire method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.2.3. Transient plane source method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4. Thermal conductivity of thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.1. Effect of chain structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2. Effect of crystallinity and crystal form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.3. Effect of orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3.1. Orientation of crystalline/semicrystalline polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.3.2. Orientation of amorphous polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.3.3. Orientation of liquid crystalline polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.4. Polymer blends by engineered interchain interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
5. Thermal conductivity of thermosets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5.1. Effect of liquid crystal domain size and content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.2. Effect of curing condition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.3. Effect of orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
6. Thermally conductive fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
6.1. Metallic fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
6.2. Carbon based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
6.3. Ceramic fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
7. Influence of the filler morphology and properties on thermal conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
7.1. Effect of filler loading level . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
7.2. Effect of filler shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
7.2.1. One-dimensional fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
7.2.2. Platelet-like fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
7.2.3. Spherical fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
7.3. Size effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
7.4. Hybrid fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
7.4.1. Mixture of fillers with different sizes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
7.4.2. Mixture of fillers with different shapes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
7.4.3. Mixture of different types of fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
7.5. Surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
8. Microstructure control of heat conductive polymer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
8.1. Filler orientation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
8.1.1. Orientation by shear or extensional flow during processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
8.1.2. Orientation by external fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
8.1.3. Orientation of carbon nanotube by chemical vapor deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
8.2. Filler agglomerates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
8.3. Formation of continuous filler network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
8.3.1. Molding of the mixture of filler and polymer powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
8.3.2. In situ polymerization in porous heat conductive filler network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
8.3.3. Self-assembly process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
8.3.4. Double percolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
9. Applications of thermally conductive polymer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
9.1. LED devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
9.2. Electronic packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
9.2.1. Single chip packages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
9.2.2. 3D chip stack assembly and packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
9.2.3. Automotive electronic control units (ECUs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
9.3. Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
9.4. Solar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
10. Conclusions and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85 43

Symbols
Cu copper
A cross sectional transfer area CuNWs copper nanowires
Cp specific heat capacity per unit volume DC direct-current
Dint interparticle distance DDE 4,4 -diaminodiphenylethane
k or TC thermal conductivity DDM diffuse mismatch model
kB bulk thermal conductivity DGEBA diglycidyl ether of bisphenol A
kc thermal conductivity of the composite DGEBP diglycidyl ether of 4,4 -biphenol
keff effective heat conductivity DGEDH diglycidyl ether of 1,4-diaminobenzene-bis
kf thermal conductivity of filler (4-hydroxy-benzaldehyde)
kp thermal conductivity of polymer matrix DGEHAP diglycidyl ether of 4-((4-
ij thermal conductivity tensor hydroxybenzylidene)amino)phenol
h interfacial thickness DGEHH diglycidyl ether of hydrazine-bis(4-
J heat flux hydroxybenzaldehyde)
L conduction path length DGETAM diglycidyl ether of terephthalylidene-bis-
l phonon mean free path (4-amino-3-methylphenol)
L11 , k33 geometrical factors DGETMBP diglycidyl ether of 3,3 ,5,5 -tetramethyl-
Mn number average molecular weight 4,4 -biphenol
q rate of heat transfer DSC differential scattering calorimetry
r filler aspect ratio ECU electronic control units
Rksm interfacial thermal resistance between EMA effective medium approximations
SWCNT and matrix EMC epoxy molding compound
T0 constant temperature EMT effective medium theory
T temperature difference EN European Standard
TC|| TC along the orientation direction EVA poly(ethylene vinyl acetate)
TC⊥ TC perpendicular to the draw direction EVs electric vehicles
˛ thermal diffusivity FD finite difference
ı kf /kp Fe3 O4 ferroferric oxide
 volume fraction of fillers FEA finite element analysis
 draw ratio FeCr Fe–Cr steel particles
 interfacial thermal conductivity GBN glycidyl methacrylate-butyl acrylate-
 phonon velocity maleic anhydride
 density GNSs graphene nanosheets
 electrical conductivity H3 BO3 boric acid
hBN hexagonal boron nitride
Abbreviations HDPE high density polyethylene
1-D one-dimensional HEVs hybrid electric vehicles
2-D two dimensional ISO International Organization for Standardiza-
3-D three-dimensional tion
a-PT amorphous polythiophene ITRS International Technology Roadmap for
ABS poly(acrylonitrile-butadiene-styrene) Semiconductors
copolymer LABNs linear assembles of BN nanosheets
AgNWs silver nanowires LADFs linearly aligned diamond fillers
AgNWs@SiO2 silica-coated silver nanowires LCP liquid crystalline polymers
Al aluminum LDPE low density polyethylene
Al2 O3 aluminum oxide LED light-emitting diode
AlN aluminum nitride MG model Maxwell–Garnett approximation
ASTM American Society for Testing and Materials MPP mesophase pitch
BACE bisphenol A cyanate ester MWCNTs multi-walled carbon nanotubes
BeO beryllium oxide Ni nickel
BN boron nitride PA 6 polyamide-6
BNNT boron nitride nanotubes PA66 polyamide-6,6
BNNTs boron nitride nanotubes PAA poly(acrylic acid)
BZE 4-(4-oxylanylbutoxy)benzoic acid-1,4 - PAN polyacrylonitrile
phenylene ester PAP poly(N-acryloyl piperidine)
c-PBO crystalline polybenzobisoxazole PBO poly(p-phenylene benzobisoxazole)
c-PE crystalline polyethylene PBT poly(butylene terephthalate)
CNF carbon nano fibers PC polycarbonate
CNT carbon nanotube PCM phase change materials
CTE coefficient of thermal expansion PDMS poly(dimethyl siloxane)
44 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

1. Introduction

PE polyethylene Thermal dissipation is critical to the performance,

PEEK polyetheretherketone lifetime, and reliability of electronic devices. With the
PEI polyetherimide miniaturization, integration and functionalization of elec-
PET poly(ethylene terephthalate) tronics and the emergence of new applications such
PI polyimide as three-dimensional chip stack architectures, flexible
PIB polyisobutylene electronics, and light emitting diodes, thermal dissipa-
PIPD polyhydroquinone diimidazopyridine tion becomes a challenging problem. Thus, new highly
PMDA pyromellitic dianhydride thermally-conductive materials are needed to help address
PMMA polymethylmethacrylate this challenge [1,2].
POM polyoxymethylene For one-dimensional, steady state heat flow, the heat
POSS polyhedral oligosilsesquioxane conduction rate is expressed by Fourier’s equations (1) and
PP polypropylene (2) [2]:
PPS polyphenylene sulfide
PPSU polyphenylsulfone T
q = kA (1)
PS polystyrene L
PSU polysulfone or
PT polythiophene q dT
J= = −k (2)
PTFE polytetrafluoroethylene A dx
PU polyurethane
where q is rate of heat transfer (W); J is heat flux (W/m2 ), k is
PV photovoltaic
thermal conductivity W/(m K); A is cross sectional transfer
PVC polyvinyl chloride
area (m2 ); T is temperature difference (◦ C); L is conduc-
PVDC polyvinylidene chloride
tion path length (m).
PVDF polyvinylidene difluoride
In solids, heat may be transported by charge carri-
PVF polyvinyl formal
ers (such as electrons and holes) or by phonons (energy
PVP polyvinylpyrrolidone
quanta of atomic lattice vibrations). For insulators and
PVPh poly(4-vinyl phenol)
semiconductors the thermal conductivity is dominated
PWD pine wood dust
by the contribution from phonons, while in metals the
RVE representative volume elements
electronic contribution greatly outweighs the phonon con-
SAN styrene–acrylonitrile copolymer
tribution. For most polymers, the primary mechanism of
SB styrene/polybutadiene copolymer
heat conduction is through phonons [3].
SEBS hydrogenated styrene/butadiene copoly-
The thermal conductivity (TC) of polymers (usually rep-
mer
resented by Greek letter  or Latin lowercase k), can be
Si3 N4 silicon nitride
obtained from the Debye equation, i.e.
SiC silicon carbide
SiO2 silica Cp  l
k= (3)
SiO2 @CNTs SiO2 coated carbon nanotubes 3
SiO2 @MWCNTs SiO2 coated multiple wall carbon where Cp is the specific heat capacity per unit volume,
nanotubes  is the phonon velocity, and l is the phonon mean free
sPS syndiotactic poly(styrene) path. For most polymers, l is extremely small due to scat-
SWCNT single-wall carbon nanotube tering with other phonons, defects, and grain boundaries.
TiB2 titanium boride Therefore, most polymers have a low TC in the range of
TIMs thermal interface materials 0.1–0.5 W/(m K), which is not sufficient for many appli-
TME4 4-(oxylanylmethoxy)benzoic acid-4,4 - cations that require high heat conduction [4]. However,
[1,4-butane-diylbis(oxy)]bisphenol ester polymers have the advantages of good processability, light
TME6 4-(oxylanylmethoxy)benzoic acid-4,4 - weight, low water absorption, high electrical resistivity,
[1,6-hexane-diylbis(oxy)]bisphenol high voltage breakdown strength, corrosion resistance,
ester and most importantly, low cost. Polymer-based thermally
TME8 4-(oxylanylmethoxy)benzoic acid-4,4 - conductive materials are therefore often desired in many
[1,8-octane-diylbis(oxy)]bisphenol ester applications.
TPEE thermoplastic polyester elastomer Typically, heat conductive fillers, such as aluminum
TPU urethane base TPE oxide, boron nitride, aluminum nitride, silicon nitride,
TSV through silicon via diamond, graphite, metal particles, carbon nanotube,
UHMWPE ultrahigh molecular weight polyethylene graphene, etc., are introduced into polymers to increase TC.
VA-MWCNT vertically aligned multiwalled carbon For applications that require both high TC and electrically
nanotube insulating properties, electrically insulating fillers, such as
VDOS vibrational density of states aluminum oxide, boron nitride, aluminum nitride, etc. can
VDP vertical double percolation be used, while graphite, metal particles, carbon nanotube,
WAXD wide angle X-ray diffraction and graphene are often utilized in applications where elec-
ZnO-NPs zinc oxide nano particles trical insulation is not required.
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
The thermal conductivity of polymer composites is a
function of the TC of both polymers and fillers. However,
the importance of the TC of polymers is often neglected
in the design of thermally conductive polymer compos-
ites because it is usually quite low compared to that of
the filler. The TC of polymers is particularly important at
low filler loadings, as the thermally conductive fillers are
separated by polymer matrix, which acts as a thermal bar-
rier and becomes rate-limiting in the thermal conduction
pathway.
The addition of thermally conductive inorganic fillers is
indispensable for achieving high TC. The filler type, loading
level, filler size, and filler shape have a strong influence
on the TC of polymer composites. Moreover, the spatial
arrangement of the fillers and the orientation of fillers are
also important to the TC. Many types of filler have non-
spherical shapes (plate-like or needle-like). They can be
oriented during processing, which leads to composites with
anisotropic thermal conductivity (e.g., if plate-like fillers
are strongly aligned, the “in-plane” TC would be larger than
the normal or “through-plane” TC). In some applications, an
anisotropic TC is not preferred or the orientation direction
of the fillers is not in the desired direction. Novel techniques
are being developed for obtaining desired filler orientation.
Often creating a continuous filler network is the key to
obtaining high TC in composite structures. Network for-
mation, however, usually takes place at high filler loading
levels. This can lead to poor processability, poor mechani-
cal properties, and high cost. Studies are ongoing to develop
composites with high TC at a lower filler loading level by
carefully controlling filler spatial arrangement.
The interaction of filler with polymer matrix is also
important to the TC. Poor interface between filler and
polymer could lead to high thermal interfacial resistance
and reduce the TC. Improving polymer-filler interfacial
interaction can increase the overall composite TC quite sub-
stantially [4].
The TC is determined by the structure and properties of
polymer and fillers, as well as the morphology of the com-
posites and the interaction of polymers and fillers, as shown
in Fig. 1. When we design thermally conductive polymer
composites, a holistic approach to satisfy all the applica-
tion requirements is needed. It is not sufficient just to select
appropriate polymers and fillers. The morphology and the
Interaction
(filler surface treatment)
Thermal
Conductivity
Polymer Type Morphology
Filler (orientation of fillers and
(size, shape, type, polymers, ordered structure,
hybrid filler) filler arrangement/packing)
Fig. 1. Thermal conductivity of composites depends on multiple factors
that need to be considered when designing new materials.
45
interaction of polymers and fillers also need to be care-
fully understood and controlled. Furthermore, not only the
TC, but also other properties and processability need to be
considered and balanced.
In this review, key factors that influence the TC of
composites are discussed. Special attention is given to ther-
mally conductive nanocomposites. Despite the fact that
there has been an excellent review on the TC of car-
bon nanotubes and their polymer composites [3], they
are still included in this review, but in less detail. Novel
techniques for microstructure control of heat conductive
composites are reviewed. Various applications of thermally
conductive polymer composites are summarized. Finally,
the challenges and outlook for thermally conductive poly-
mer composites are discussed.
2. Modeling of thermal conductivity in composites
Due to the almost infinite number of possible mate-
rial compositions (the choice of polymer matrix, the type
of thermally conductive fillers, the filler weight fraction,
etc.), it is imperative to find ways to limit the number
of possible experiments and to be able to estimate the
properties of the candidate materials. Thus, theory and
modeling play important role in the process of screening
potential compositions and selecting the more promising
ones. First, modeling (such as molecular dynamic simu-
lations) can predict “ideal” thermal conductivity of many
“pure” materials (carbon nanotube, graphite, ceramic par-
ticles, and various polymers). Over the course of this
review, we will often reference such studies. Second, using
models, one can determine – often in a qualitative fash-
ion, sometimes semi-quantitatively or quantitatively – the
dependence of composite thermal conductivity on the
matrix TC, filler TC, and filler volume fraction (“loading”).
Other factors that influence the overall composite TC – and
are often neglected in the models – include the filler mor-
phology (dispersed individual particles; aggregates; fractal
clusters; percolated network, etc.), anisotropy (especially
in the case of non-spherical filler particles), properties
of filler–matrix interfaces, and effects of processing his-
tory. Sometimes, these effects are difficult to predict from
first principles, and then modeling should be combined
with experimental inputs (such as electron microscopy) to
provide explanation of observed trends and design subse-
quent experiments.
Broadly, composite models can be divided into two
classes – analytical micromechanical models and finite
element simulations. Analytical micromechanical models
(also known as constitutive equations) provide closed-
form expressions for the composite TC as functions of the
TCs of the matrix and filler materials. Usually, these models
assume ideal filler-matrix interfaces (no thermal resistance
for phonons to go through) and idealized morphology (e.g.,
uniform dispersion of filler particles). As a result, those
models can provide very quick estimates of the depend-
ence of composite TC on both filler and matrix TCs and the
filler loading; however, the predictions are usually qualita-
tive. Finite element models usually offer more opportunity
to calculate composite TC fairly accurately by taking
into account realistic composite morphology and possible
46 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

interfacial resistance; however, they are often time-

consuming and – until recently – have been used mainly to
refine and test predictions of constitutive models. Below,
we review both approaches in more detail.

2.1. Constitutive (micromechanical) modeling

The simplest (and crudest) approach – that often works

as the first approximation – is to consider two limiting
cases: linear mixing rule (also known as the parallel model)
and inverse mixing rule (often referred to as the series
model). It can be rigorously shown that all linear proper-
ties (TC, electrical conductivity, tensile modulus, etc.) are
bracketed by these two values, with the parallel model
providing the upper bound, and series model providing
the lower bound. Formally, the parallel model is based
on the assumption that the temperature gradient is uni- Fig. 2. Effective thermal conductivity of composites as a function of filler
loading, calculated using MG model. Different curves correspond to dif-
form and the heat flux is the weighted sum of heat fluxes ferent filler thermal conductivities. [8], Copyright 2010. Reproduced with
through the matrix and filler domains. The series model permission from John Wiley & Sons.
is based on the assumption that the heat flux is uni-
form, and the temperature gradient is the weighted sum Maxwell–Garnett [6] derived the expression for the
of temperature gradients through the matrix and filler conductivity k for suspension of spherical non-interacting
domains. particles, as defined in Eq. (6):
In the parallel model, filler and matrix contribute  
independently to the overall thermal conductivity, in pro- 3(ı − 1)
kc = kp 1+ (6)
portion to their relative volume fractions (see Eq. (4)). 2 + ı − (ı − 1)

kc = (1 − )kp + kf (4) where ı = kf /kp . Dependence of the composite TC on the

filler loading, as computed on the basis of the MG model, is
shown in Fig. 2. The ratio of filler TC to matrix TC is varied
Here, kc , kp and kf are the TC of the composite, polymer
from 10 to 300. It can be seen that at low filler loadings,
matrix and filler respectively, and  is the volume fraction
the dependence of composite TC on filler content is nearly
of fillers. The parallel model maximizes the contribution
linear.
of the filler phase and assumes perfect contact between
Later, Fricke [9] generalized Maxwell–Garnett’s model
particles in a fully percolating network implicitly. This
for the case of the spheroidal inclusions. Again, the suspen-
model has some relevance to the case of continuous fiber
sion has to be diluted enough so that suspended particles
composites in the direction parallel to fibers, but gener-
are considered to be thermally isolated one from another.
ally results in very large overestimation for other types of
We can re-write Fricke’s equation to make it consistent
composites.
with Maxwell-Garnett’s formula (see Eq. (7)).
The series model is most applicable for composites
where the fillers are dispersed in a matrix and there is no
 
n(ı − 1)
percolation even at high filler volume fractions. Within this kc = kp 1+ (7)
n − 1 + ı − (ı − 1)
model, the composite thermal conductivity is given by
Here
 −1  
(1 − )  ˇ(ı − 1)
kc = + (5) n= (8)
kp kf (ı − 1) − ˇ

1
 2 1

Most of the experimental results were found to fall ˇ= (ı − 1) + (9)
somewhere between these two types of models. However, 3 1 + L11 (ı − 1) 1 + L33 (ı − 1)
the series model is usually closer to the experimental data Constants L11 and L33 are geometrical factors depend-
as compared to the parallel model [5], leading to the devel- ent on the filler aspect ratio r (which is defined as the size
opment of many different models derived from the basic divided by thickness, so it is always larger than unity).
series model. These models generally introduce some more
complex weighted averages on thermal conductivities and r2 r
L11 = − cosh−1 r
volume fractions of particles and matrix. The models often − 1)
2(r 2 2(r 2 − 1)
3/2 (10)
include semi-theoretical fitting parameters and rely on L33 = 1 − L11
so-called effective medium approximations. Two com-
monly used effective medium approximation methods are For a sphere, r = 1 and the geometrical factors are all
the Maxwell–Garnett (MG) model [6] and the Bruggeman equal to 1/3. In this case, the shape factor n becomes equal
model [7]. to 3, which recovers Maxwell–Garnett’s formula.
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 3. Bruggeman model prediction of composite TC as a function of par-
ticle loading (volume fraction) with fixed filler TC and various matrix TC
(kp ) ranging from 0.2 to 1.0 W/(m K).
Both original and modified Maxwell–Garnett models
assume that temperature experiences no discontinuity
at the filler surface. This assumption works well on a
macroscopic scale, but breaks down on much smaller char-
acteristic length scales where the thermal energy carriers
(electrons or phonons) scatter at the interface. Kapitza [10]
suggested that temperature at the interface undergoes a
change proportional to the normal component of the heat
flux through the interface. Nan [11] further generalized the
equation for TC of composite material to include the impact
of the interfacial resistance in the form of an effective-
medium theory.
Despite many successful cases where the above
approach is applied, the basic assumption of separated
particles in the effective medium approach is not valid in
principle for highly filled composites, where contacts are
likely to occur, possibly leading to thermally conductive
paths [12]. For those types of composites, the so-called
Bruggeman model [7] provides a much better descrip-
tion. In this model, mean field approach is used to capture
the interactions among the randomly distributed fillers.
There is no limitation on the concentration of inclusions for
Bruggeman model. As a result, it is widely used for particle
percolation in suspensions, i.e. particle clustering effect. For
a binary composite containing matrix and spherical fillers,
the Bruggeman model yields the following implicit Eq. (11)
for kc ,
   
kf − kc kp − kc
 + (1 − ) =0
kf − 2kc kp + 2kc
In the illustration (Fig. 3), we demonstrate how the com-
posite TC depends on the matrix TC and the filler loading
as predicted by the Bruggeman model. Assuming a high-
TC inorganic filler such as boron nitride (kf ∼ 300 W/(m K)),
we can clearly see that composite TC depends substantially
on the matrix TC, especially at low and intermediate filler
volume fractions. And at high loadings (above 50%), the
composite TC approaches the filler TC. This dependence will
be discussed more extensively in subsequent sections.
For composites with low filler loading, Bruggeman and
Maxwell–Garnett models give very similar predictions.
For composites with higher filler loading and in those
systems where thermally conductive fillers form perco-
lated pathways, the MG model significantly under-predicts
the composite thermal conductivity, while the Bruggeman
model can describe experimental data reasonably well.
Hence, Bruggeman model is used to predict the effective
47
Fig. 4. Schematic of well-dispersed aggregates in composite materials. A
thermally conductive path is identified with a solid line.
TC of particle clusters, and the MG model is used otherwise
to approximate the effective TC of composites [13]. The
schematic representation of this combination approach is
shown in Fig. 4.
Apart from the above models, other theoretical
approaches [14] include equations by Hashin and Shtrik-
man [15,16], Hamilton and Crosser [17,18], Hatta and Taya
[19], Agari [20], Cheng and Vachon [21] as well as by Lewis
and Nielsen [22–24]. These models also appear to reason-
ably fit most of the experimental data for composites based
on isotropic particles as well as short fibers and flakes with
limited aspect ratio, up to loadings of about 30% in volume.
Analytical models are often used as the first-pass esti-
mate for the dependence of TC on the filler volume fraction,
as well as filler and matrix TC. These models have two types
of uncertainties. First, morphology in real applications is
different from the special, idealized cases used in model
as assumptions (monodisperse spherical fillers; perfectly
aligned or perfectly isotropic monodisperse cylinders, etc.).
Even in these cases, the models are usually only semi-
quantitative and often are unable to capture effects such
as interfacial thermal resistance (discussed in more details
in Section 2.3). For these and other reasons, more accurate
analysis often requires the use of numerical approaches
discussed next.
(11) 2.2. Finite element modeling
In the previous section, we described various analytical
or closed-form expressions evaluating TC of composites as
a function of their composition and the characteristics of
the matrix and the fillers. While those approaches are very
useful for quick evaluation of the trends expected upon
changes in filler loading or filler type, they are limited to
some very specific situations (e.g., monodisperse spheri-
cal fillers in a homogeneous matrix or perfectly aligned
ellipsoidal fillers in a homogeneous matrix). In general,
however, composite morphology could be more compli-
cated, in which case numerical approaches, such as finite
element analysis (FEA) or finite difference (FD) modeling,
could be better suited. Here, we provide several examples
of the FEA modeling of TC in polymer-based composites.
Comprehensive description of the FEA approach to com-
posite TC is certainly beyond the scope of this paper –
we refer the reader to several recent books and reviews
48 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

that provide a general description of the method and its

application to TC [25–29]. In general, within FEA-based
approaches, one considers the morphology of a composite
material and attempts to numerically solve the stationary
equation (Eq. (12)) of heat transfer in solids,

∇ ((r)∇ T (r)) = 0 (12)

subject to the boundary condition,

∂T
 = −J (13)
∂n
where ∂T/∂n denotes the normal derivative at the bound-
ary. If we assume, for example, that heat flux J is applied at
the X = 0 boundary, while the boundary X = X0 is maintained
at constant temperature T0 , and the heat flow through the
XY and XZ boundaries can be neglected, then effective heat
conductivity of the sample can be computed as
JX0
eff = (14)
T (x = 0) − T0
where the  brackets indicate averaging over y and z in
the x = 0 plane. If the composite is anisotropic, similar cal-
culations could be done in other directions to compute the
principal components of the symmetric tensor kij (the sym-
metry of the tensor follows from the Onsager reciprocal
relations [30,31]). In most cases, polymer-based compos-
ites turned out to be either isotropic (so that only one
TC number is needed) or having a preferential filler plane
orientation (so that two TC numbers, in-plane and through-
plane, are required). While there certainly are many cases
with more complex anisotropy, these will not be discussed
here.
Fig. 5. Composite thermal conductivity in HDPE/Al binary mixtures as
One of the early numerical studies of TC in function of Al filler volume fraction. Experimental data are compared with
polymer–inorganic composites was performed by Kum- predictions using various micromechanical models, as well as FEA simu-
lutas and co-workers [32]. They investigated composites lations. [32], Copyright 2007. Reproduced with permission from Elsevier
of high-density polyethylene (HDPE) and spherical alu- Ltd.
minum metal particles. The particles were dispersed
uniformly and homogeneously in the matrix, and there Bruggeman model which is expected to work better at
was no anisotropy or directionality. The authors took high filler loadings.
electron microscopic images of composites correspond- Annapragada and co-workers [35] studied TC of partic-
ing to various filler loadings, and used finite difference ulate composites with polydisperse spherical fillers. They
modeling in two dimensions to compute TC, assuming developed packing algorithms to generate representative
that k(LDPE) = 0.543 W/(m K) and k(Al) = 204 W/(m K). volume elements (RVE), both in two and three dimen-
Numerical results were then compared to experimental sions. The predicted TC was shown to be fairly close to the
data, as well as to a number of theoretical models (Fig. 5). experimental value, and the approach certainly could be
It was observed that the numerical predictions (squares) generalized to other composites with spherical fillers. Liang
and the experimental data (triangles) were in a fairly good and Li [36,37] studied TC of polypropylene filled with hol-
agreement at high filler loadings (>15 vol.%); at lower filler low glass latex particles; in this case, TC of the composite
loadings, numerical predictions were substantially higher is lower than that of the pure matrix. As shown in Fig. 6,
than the measured values. There can be a number of expla- the predicted TC agrees with the measured data reasonably
nations for this discrepancy. For example, the model did well, both when two-dimensional and three-dimensional
not consider the role of interfacial resistance [33,34]; also, FEA models were used. Again, the role of thermal resistance
the digitization of the images could have led to incorrect at particle interface was not considered.
assignment to some pixels in the regions crowded with Nayak et al. [38] investigated TC of epoxy/pine wood
filler particles. On the other hand, it was shown that con- dust (PWD) composites; again, the filler TC (k(PWD) =
stitutive models, such as Cheng and Vachon [21], predict 0.068 W/(m K)) was less than that of the matrix
TC fairly well at filler loading of less than 10 vol.%. This (k(epoxy) = 0.363 W/(m K)), so the overall TC should
is consistent with the notion that the effective medium decrease as the filler loading is increased. The authors used
theories lose accuracy at higher filler volume fractions as three-dimensional (3D) sphere-in-cube lattice model,
the fillers tend to form large aggregates. Interestingly, the varying the effective sphere radius to change the volume
authors did not attempt to compare their results with the fraction. The problem was solved using ANSYS software.
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 6. Comparison between experimental data (line) and FEA simulations
(2D – filled squares; 3D – open circles) for the polypropylene/hollow glass
particle composites. [37], Copyright 2007. Reproduced with permission
from Elsevier Ltd.
Fig. 7. Thermal conductivity of epoxy/pine wood dust (PWD) compos-
ites as function of the filler volume fraction. Triangles are FEA simulation
results, and squares are experimental data. [38], Copyright 2010. Repro-
duced with permission from Elsevier Ltd.
Fig. 7 shows the dependence of TC on the PWD volume
fraction; simulations and experiment are in a reasonable
agreement, although the non-monotonic behavior of the
simulated TC is not fully explained and could be an artifact
of the lattice model.
The examples above considered composites with spher-
ical fillers, monodisperse or polydisperse. Anisotropic
fillers provide further complexity since both positional
and orientational distribution of fillers needs to be con-
sidered. In recent years, many studies have been devoted
to polymer–carbon nanotube (CNT) composites [3,39–42].
Indeed, with nominal TC of CNTs being in excess of
1000 W/(m K), one can expect to produce high-TC compos-
ites with relatively small CNT volume fractions. It has been
shown [39,43,44] that for polymer/CNT nanocomposites,
their electrical conductivity, , increases dramatically (by
5–6 orders of magnitude) as the CNT volume fraction is
changed from about 0.2 volume percent to about 1 vol.%.
Indeed, according to percolation theory, high-aspect ratio
fillers such as CNT form continuous network at very low
concentrations (for the dependence of percolation thresh-
old on aspect ratio, see, e.g., review by Bicerano et al. [45]).
This percolated network accounts for most of the charge
49
Fig. 8. FEA simulations of relative thermal conductivity of polymer/CNT
composites as function of CNT volume fraction. Different curves corre-
spond to different interfacial thermal conductivities. [34], Copyright 2007.
Reproduced with permission from Elsevier Ltd.
conduction, making polymer/CNT nanocomposites reason-
ably good conductors, even if not on the same scale as
metals. However, TC increases in polymer/CNT nanocom-
posites are not as significant as the electrical conductivity
increases, despite the similarity between the two trans-
port properties. Moniruzzaman and Winey [39] reviewed
a number of experimental studies on polymer–CNT ther-
mal conductivity, concluding that in general, the composite
TC can exhibit about two- to three-fold increase over
the matrix TC; this is a substantial increase but nowhere
near what is seen for electrical conductivity. Accord-
ingly, several computational and theoretical studies have
been performed to explain this discrepancy. For example,
Shenogina et al. [46] simulated the heat flow between two
nearby nanotubes in a polymer matrix using ABAQUS finite
element software. They concluded that the rate of heat
flow was fairly independent of the distance between the
nanotubes, thus suggesting either absence or weakness
of percolation effects. Singh et al. [34] used element-free
Galerkin method to numerically compute effective TC of
polymer/CNT composite as function of CNT volume frac-
tion and interfacial thermal resistance. The nanotubes were
assumed to be perfectly aligned, and the calculated TC
was along the direction of their alignment. As shown in
Fig. 8, if the interfacial TC is equal to the nominal CNT
thermal conductivity of about 3000 W/(m K), the com-
posite TC increases rapidly with CNT concentration and
could become an order of magnitude higher than that of
the matrix (and thus, be on the order of 1–5 W/(m K)) at
moderate CNT volume fractions (15–20%). However, if the
interfacial TC is relatively low (comparable to that of the
matrix), the increases in TC are more modest, in line with
experimental observations.
More recently, Li et al. [47] used 3D finite element mod-
eling of polymer/single-wall-carbon nanotube (SWCNT)
composite with disordered nanotubes, and compared
results with experimental data on two model systems,
epoxy/SWCNT and polyolefin/SWCNT (Fig. 9). The results
50 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

Fig. 9. (a) A finite element model of a randomly distributed SWCNT/polymer composite. The volume fraction of SWCNTs is 22%. (b) A temperature
distribution of a steady-state thermal analysis of a randomly distributed SWCNT/polymer composite. The volume fraction of SWCNTs is 22%. (c) Calculated
and experimental thermal conductivity (kc ) of SWCNT/epoxy composites as function of SWCNT volume fraction. (d) Same as (c) but for polyolefin/SWCNT
composites. Here, Rksm is the interfacial thermal resistance between SWCNT and matrix. [47], Copyright 2012. Reproduced with permission from Elsevier
Ltd.

demonstrated, once again, the importance of interfacial
thermal resistance for proper understanding of heat trans-
fer in these materials. Even so, the mechanism of heat
transfer in the polymer/CNT composites is not yet fully
understood, as more recent experimental studies [48,49]
indicated that the increase in heat conductivity as function
of the CNT volume fraction could be indeed consistent with
the nanotube percolation.
Other recent applications of FEA modeling include
those of polymer/platelet composites [50,51] and those
where mixed fillers are used [52]. Additionally, several
authors have been working to combine FEA approach with
molecular-level modeling (such as molecular dynamics)
to derive interfacial resistivity in a fundamental manner
[51]. One can expect that in the next several years, FEA
simulations of composite properties, including TC, will be
dramatically expanded and will include formulations with
multiple fillers, varying degree of anisotropy, and other
complexities. Furthermore, as computers become faster,
our ability to use simulations to screen formulations and
design candidate systems will increase dramatically.
As already mentioned, one critical challenge in ensuring
the validity and accuracy of the continuum-level models
(whether constitutive or FEA) is description of the heat
transfer through interfaces. Below, we briefly review recent
progress on this topic.
2.3. Interfacial thermal resistance modeling
Interfacial thermal resistance (often called Kapitza
resistance following the pioneering work by Kapitza [10])
can be understood as follows. The matrix (such as poly-
mer) and the filler (CNT or an inorganic particle) have
different spectra of quantum states for the heat carri-
ers (electrons, holes, and phonons). In most polymers,
heat is carried only by phonons, and their density of
states is substantially lower than in highly crystalline
CNTs or inorganic fillers. As a result, many phonons are
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
back-scattered at the interface between the matrix and the
filler. The problem can be exacerbated if the interfacial cou-
pling between the filler and the matrix is weak [53–55].
This results in a temperature discontinuity, T, at the
interface; this discontinuity is proportional to the heat flux,
J (Eq. (15))
J = (T ) (15)
The proportionality constant, , is the interfacial ther-
mal conductivity and has units of W/(m2 K); the inverse of
 is the interfacial thermal resistance (usually labeled Rk ).
It is often convenient to define interfacial thickness, h (Eq.
(16)), as follows:
kB
h= (16)
 est value, leading to the most effective reduction in
where kB is the bulk thermal conductivity in unit of
W/(m K). Typical values of h are on the order of nanometers
[54]; thus, it is often reasonable to disregard the interfa-
cial effects if the filler size is on the order of microns. In
many FEA simulations of conventional polymer–inorganic
composites discussed above, the assumption of “perfect”
interface (T = 0) was thus justified since the typical finite
element size was much greater than h. However, if one
tried to increase the composite thermal conductivity sub-
stantially higher, by increasing the filler loading and/or
reducing the filler size, the interparticle distance Dint would
eventually decrease to the point where it becomes compa-
rable to h. Further increases in the filler volume fraction
would then lead to no improvement in the overall TC. As
Shenogin et al. [54] emphasized, in these nanocomposites,
the fillers could be separated by 1 nm physically, yet from
thermal standpoint, their separation could be as large as
h ∼ 10–20 nm. This insight helps us better understand the
results from the FEA simulations in which the interfacial
resistance was varied parametrically (Figs. 8 and 9) – once
the filler volume fraction increased to the point where the
interparticle distance becomes comparable to the thermal
interfacial thickness, the overall thermal conductivity stops
increasing.
So far, we mainly discussed continuum approaches to
thermal conductivity, where heat transfer through matrix,
filler, and interface was described in a phenomenologi-
cal manner. In order to predict the interfacial thermal
resistance, one needs to turn to molecular models. We
already mentioned the study by Shenogin et al. [54]
who used molecular dynamics to study interfacial heat
transport between a carbon nanotube and octane liq-
uid. Alzina and co-workers [56] used multiscale modeling
to study heat transfer in epoxy/glass composites at very
low temperatures. They showed that theory and exper-
iment agreed fairly well if one assumed the so-called
diffuse mismatch model (DMM), in which all phonons
were assumed to diffusely scatter at the interface. Roy
et al. [57,58] demonstrated using molecular dynamics the
importance of coupling between the carbon nanotube and
the polymer matrix. Shin et al. [59] developed a multiscale
model combining nonequilibrium molecular dynamics and
finite element analysis to compute thermal conductivity in
SiC/epoxy composites. Similar approaches have been also
applied to various other systems [55,60–62].
51
One important conclusion from these and other stud-
ies was that the surface functionalization of the filler could
be crucial to improving thermal conductivity of compos-
ites. Within both theories of interfacial resistance (acoustic
mismatch model and diffuse mismatch model), the inter-
facial thermal conductivity is directly proportional to the
overlap between vibrational density of states (VDOS) spec-
tra of the matrix and the filler. Wang et al. [55] computed
VDOS of pristine or organically modified graphene sheet
and compared it with those of a model paraffin (Fig. 10).
The calculation shows that accurately matching the
VDOS of the matrix by using the right surface modi-
fier is very important. Even though the overlap integral
S increases substantially upon addition of virtually any
organic modifier, butyl surfactant results in the high-
the interfacial resistance for a given surface coverage
(Fig. 11). This analysis shows that even modest surface
functionalization could lead to substantial improvement
in the interfacial thermal transport. Recent experimental
studies suggest that surface functionalization can indeed
lead to some improvement in thermal conductivity in
alumina/NylonTM -6 composites [63].
Prediction of interfacial thermal properties is still rel-
atively new and rapidly developing field, and this short
review does not attempt to be comprehensive. As com-
puters become more powerful and atomistic force fields
more accurate, we can expect to see more advances in pre-
dicting interfacial thermal resistance for more and more
diverse filler/matrix pairs. Creating such a library will help
in developing more accurate macroscopic FEA models and
thus using modeling as part of new material design.
One critical remaining challenge for composite simula-
tions so far is our limited ability to predict the morphology
and the filler dispersion and aggregation. Thus, most FEA
simulations require the a priori knowledge of the mor-
phology (which could be either assumed theoretically or
taken from experimental measurements such as electron
microscopy). Overcoming this difficulty would require bet-
ter understanding of the material preparation process,
hydrodynamics and thermodynamics of fillers in polymer
melt (for thermoplastics) or balance of flow, reaction, and
filler motion (for thermosets).
3. Thermal conductivity measurement techniques
The measurement techniques of thermal conductivity
can be divided into two groups. They are steady-state
methods and transient methods. Steady-state methods are
applied when the system has achieved stability, while the
transient methods are used during the process of heating
up or cooling down a material. Table 1 gives an overview
of main thermal conductivity measurement methods.
3.1. Steady-state methods
Steady state condition means that temperature varies
across the sample but is generally time-independent (apart
from small random fluctuations). The determination of the
thermal conductivity is based on the measurement of a
heat flux and a temperature gradient. The main steady
52 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

Fig. 10. Comparison of VDOS between paraffin (blue) and graphene with various surface functionalities (red). The captions (S = 0.006, etc.) describe the
calculated VDOS overlap integrals. [55], Copyright 2015. Reproduced with permission from the American Chemical Society.

state methods include guarded hot plate method, axial flow
method, heat flow meter method, pipe method.
3.1.1. Guarded hot plate
Guarded hot plate method is used for testing materi-
als with low thermal conductivity. The guarded hot plate
device consists of one or two cold plates, a hot plate, a sys-
tem of guard heaters and thermal insulation. The technique
concept is to form a temperature gradient by applying a
known heat flux on one side of the plate-like sample, and
let the heat pass through the test sample to a cold plate
on the opposite side of sample. The temperatures at each
side of the samples are measured when the system reaches
steady state [64]. Thermal conductivity can be calculated
based on heat flux, sample thickness and surface areas, and
temperature difference [65–67].
3.1.2. Axial flow method
Axial flow method is the most widely used method for
thermal conductivity measurements at low temperatures.
In this method, a temperature gradient is created by locat-
ing the test specimen between two reference specimens of
known thermal conductivity to form a sample column with
a heater and a heat sink in the two ends [68–70].
3.1.3. Heat flow meter method
The design of the heat flow meter method is quite sim-
ilar to the single-specimen guarded hot plate apparatus,
with the difference that the main heater is replaced by
a heat flux sensor. Temperature difference was measured
across a thermal resistor which contains a series of ther-
mocouples [71–73].
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85 53

Table 1
Comparison of different thermal conductivity test methods.

Methods Temperature Conductivity range Accuracy Materials Test standards

range (W/m K)

Guarded hot plate 80–800 K <0.8 2% Glass, polymers and ASTM C177
Steady-state method [64–67] insulation materials ISO 8302
methods EN 12667
Axial flow method 90–1300 K 0.2–200 2% Polymer, ceramics, metals ASTM E1225
[68–70]
Heat flow meter 253–523 K <10 3% Glass, polymers and ASTM C 518
method [67,71–73] insulation materials, ASTM E1530
ceramics ISO 8301
EN 12667
Pipe method [64,74] 293–2770 K 0.02–200 2% Metals, high conductivity ISO 8497
inorganics, polymer
composites

Laser flash method 373–3273 K >0.01 3–5% Glasses, polymers, ASTM E1461
Transient methods [64,75–78] ceramics, metals ISO 22007-4
ISO 18755
Transient hot wire 293–2273 K <25 1–10% Glasses, polymers, ASTM-C 1113
method [64,79–83] ceramics, most of liquid, ISO 8894-1
gas, powders ISO 8894-2
Transient plane source 20–1273 K 0.005–1800 5% Insulation materials, ISO 22007-2
method [84–87] powders, polymers,
ceramics, metals, liquids

Note: Data are cited from the references noted in method name cell.

3.2. Transient methods

The transient methods are generally used to measure

thermal diffusivity by recording temperature as function
of time following a transient or periodic heat added at the
sample surface. Thermal diffusivity can be calculated from
the specimen thickness and the time required for the tem-
perature rise to reach a percentage of its maximum value.
Thermal conductivity can be calculated through Eq. (17)

k = ˛Cp  (17)

where k is the thermal conductivity, ˛ is the thermal diffu-

Fig. 11. Interfacial thermal resistance (relative to that of pristine
graphene) as function of surfactant coverage for various functional-
izations. [55], Copyright 2015. Reproduced with permission from the
American Chemical Society.
3.1.4. Pipe method
The pipe method is also referred to as the radial heat
flow method. In most cases the apparatus consists of a
core heater placed at the central axis of cylindrical sam-
ple and a heat sink around sample outside. Thermocouples
are mounted in the sample to record the temperature gra-
dient. In order to minimize the heat loss to the top and
bottom, the ratio of sample length to radius should be
large [64,74].
sivity,  is the density, Cp is the specific heat. The transient
methods are much faster than steady-state methods. Typ-
ical measurement duration of one hour for a steady-state
measurement is reduced to a few minutes or to a subsec-
ond interval for a transient method. However, transient
methods usually have lower accuracy and require more
complicated data analysis.
3.2.1. Flash method
The flash method is the most frequently used method for
measuring solid thermal transport properties because of
its very wide temperature and thermal conductivity range.
The principle of the laser flash method is to heat a small disk
sample which is located in a furnace by a short laser pulse
on the front side and to monitor the temperature increase
at its rear side by an infrared detector [64,75–78,88,89].
3.2.2. Transient hot wire method
Transient hot wire method is a modification of the
steady-state pipe method with radial heat flux. The tran-
sient hot wire technique is based on a linear heat source
(the hot wire) embedded in a test sample. The hot wire
acts as both a temperature sensor and a heater. A constant
54 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

electrical current is applied to the wire. Thermal conduc- Table 2

Thermal conductivity of general thermoplastic polymers [3,95].
tivity can be calculated based on the rate of temperature
increase of the wire and power input [64,82,83]. Thermoplastic polymers Thermal
conductivity at
3.2.3. Transient plane source method room temperature
(W/(m K))
The transient plane source method, also called hot
disk method, is a transient pulse heating technique used High density polyethylene (HDPE) 0.33–0.53
Ultrahigh molecular weight polyethylene 0.41–0.51
for thermal conductivity and thermal diffusivity mea-
(UHMWPE)
surements. This technique uses a thin, plane, electrically Commercial thermotropic liquid crystalline 0.30–0.40
insulated resistive element, usually in a spiral pattern, as polymers (LCP)
both the temperature sensor and the heat source. Heating Polyoxymethylene (Homo) (POM) 0.30–0.37
element is placed between two test samples of the same Low density polyethylene (LDPE) 0.30–0.34
Poly(ethylene vinyl acetate) (EVA) 0.35
material. By recording the increase in resistance as a func- Polyphenylene sulfide (PPS) 0.30
tion of time while heating with an electrical current pulse, Poly(butylene terephthalate) (PBT) 0.25–0.29
the thermal conductivity can be deduced from one single Polytetrafluoroethylene (PTFE) 0.27
transient recording [84,85]. Polyamide-6,6 (PA66) 0.24–0.33
Polyamide-6 (PA 6) 0.22–0.33
Polyetheretherketone (PEEK) 0.25
4. Thermal conductivity of thermoplastics Polysulfone (PSU) 0.22
Polymethylmethacrylate (PMMA) 0.16–0.25
As discussed previously, polymer matrix TC plays a cru- Polycarbonate (PC) 0.19–0.21
cial role in determining the overall TC of thermoplastic Urethane base TPE (TPU) 0.19
Poly(acrylonitrile-butadiene-styrene) 0.15–0.20
composites [44,90]. It is therefore necessary to review our copolymer (ABS)
current understanding of TC of thermoplastic polymers. Polyvinyl chloride (PVC) 0.13–0.29
Molecular dynamics simulations and experimental Polyvinylidene difluoride (PVDF) 0.19
studies have shown that an individual polymer chain which Styrene/polybutadiene copolymer (SB) 0.17–0.18
Styrene-acrylonitrile copolymer (SAN) 0.15–0.17
is a low dimensional material, can in principle, have a rather
Poly(ethylene terephthalate) (PET) 0.15
high TC [91–94]. Henry and Chen [91] found that the TC Polystyrene (PS) 0.10–0.15
of single polyethylene (PE) chains with an extended con- Polyvinylidene chloride (PVDC) 0.13
formation could be as high as 350 W/(m K) when a chain Polyisobutylene (PIB) 0.12–0.20
length is longer than 100 nm. Even for PDMS with strong Polypropylene (PP) 0.11–0.17
Polyimide, thermoplastic (PI) 0.11
phonon scattering due to conformational disorder, its sin-
gle chain still has a TC of ∼7 W/(m K) [92]. However, bulk
polymers on a macro scale are usually thermal insulators. micrometer-size was recently reported to have exception-
Table 2 lists thermal conductivities of various commercial ally high TC up to 416 W/(m K) [101], which is due to its
thermoplastic polymers [3,95,96], which is in the range well-organized, highly crystalline, ordered, and oriented
of 0.1–0.5 W/(m K) as mentioned above. It is obvious that morphology, formed by a near-perfect self-assembling pro-
bulk polymers have much lower TC than corresponding cess.
single chains. For most polymers, both heat capacity Cp The above data suggest some general trends:
(primarily determined by the character of monomer repeat
unit) and phonon group velocity  (strongly related to (1) Crystalline polymers (e.g. various PE) have higher TC
character/strength of backbone bonding) of bulk polymer than amorphous ones (e.g. PMMA, PS, SB, SAN, PI)
are almost the same as those of individual chains. There- and high crystalline polymers (e.g. HDPE, UHMWPE,
fore, it is the phonon mean free path (l) that causes the PBT) have higher TC than low crystalline ones (e.g.
large difference between the TC of single chains and that LDPE, EVA, PET, PEEK, PSU, PC). Exceptionally, PP is a
of bulk polymers. It has been known that phonon mean highly crystalline polymer, but has a very low TC either
free path along a chain is much larger than in a trans- because of relatively high free volume in its crystal-
verse direction since lattice vibrations associated with lites or due to the possible phonon scattering created
covalent bonds are much less anharmonic than those asso- by vibrational mode of side group methyl.
ciated with secondary bonds [97–99]. In a bulk polymer, (2) Addition of heavier atoms and presence of side chain
polymer chains are in the state of twisted random orien- or pendant group usually result in lower TC. The role
tation and intermolecular weak coupling, mainly via van of heavy atoms is illustrated by comparing, e.g. HDPE
der Waals forces. These make the average phonon mean vs. (POM, PBT, polyamide); for side group, e.g. HDPE vs.
free path for bulk polymer to be much smaller than that (EVA, PVC, PVDF, PVDC, PS, PP, PIB) (the presence of side
of a single polymer chain. Furthermore, there are inher- group can affect crystallization to some extent).
ent defects in bulk polymer, such as voids, impurities,
polymer chain ends, and entanglements [100], which fur- Below we elaborate on these general observations.
ther reduce the phonon mean free path and the TC of
bulk polymer. Clearly, to increase TC, attention should be 4.1. Effect of chain structure
paid to improving the orientation of polymer chains and
increasing the amount of ordered and oriented regions in Chain structure including molecular composition and
bulk polymers. For example, spider dragline silk with a conformation is the first level of structure that determines
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 12. Thermal conductivity and structure of polymers. ␲-Conjugated polymers are plotted by solid lines with circle markers, while others are plotted
by dashed lines with triangular symbols. [102], Copyright 2014. Reproduced with permission from the American Chemical Society.
TC of various polymers. Simulation is the most widely
used tool for studying the effect of chain structure on
TC [102–104]. A recent large-scale molecular dynamics
simulation [102] systematically investigated the effect of
various molecular structures (as shown in Fig. 12) on TC
and showed that higher TC can be achieved in polymers
with rigid backbones, exemplified by ␲-conjugated poly-
mers (such as polyacetylene, poly[diimidazo pyridinylene
(dihydroxy) phenylene], poly(p-phenylene benzobisthia-
1.00 g/cc of
zole), poly-(p-phenylene), polythiophene). It is because
the ␲-conjugated rigid backbone can suppress segmen-
tal rotation and enable high bond strength for larger
phonon group velocity . Strong interchain interaction
in polyketone, NylonTM , TeflonTM , and KevlarTM can sup-
press segmental rotation to some extent. However, the
presence of heavier atoms (e.g. oxygen), weaker back-
bone bonds and segments vulnerable to random rotations
lead to lower  and thus lower TC. Another simulation
[104] also indicated that TC of polymer chains with mass
disorder (other atoms or functional groups incorporated
into aliphatic/aromatic pristine chains) should be about
25 times lower than TC of PE chain. It is the disorder
that creates localized vibrational modes, which impede the
energy transport (driven by delocalized, long-wavelength
phonon modes). In addition, polymers with intrinsic ran-
dom segmental rotation (e.g. PTFE and PDMS [92]) have
low TC due to the conformational disorder-induced phonon
scattering.
4.2. Effect of crystallinity and crystal form
As seen from Table 2, crystalline polymers gener-
ally have higher TC than amorphous ones. In amorphous
55
polymers, thermal conductance path that follows the
chain conformation is essentially random, which reduces
l and causes phonon scattering [105]. Crystallization can
increase the intrinsic order, which is likely responsible for
higher TC in poly(ether ether ketone) [106], polytrifluo-
rochloroethylene [105] and PE [107,108]. Polypropylene is
an interesting exception – it is highly crystalline but has
a low TC. This can be attributed to its low crystal density
(i.e. low chain stacking density, ∼0.93 g/cc
PE crystal) and/or the possible phonon scattering created
by vibrational mode of side group methyl. Among thermo-
plastic polymers, PE and especially HDPE have the highest
TC. Early study [107] indicates that the TC of HDPE can be
readily increased by increasing crystallinity and lamellar
thickness through processing conditions.
In addition to the overall crystallinity, the crystal form
also affects TC of crystalline or semi-crystalline ther-
moplastic polymers. High-pressure and high-temperature
treatment on HDPE and UHMWPE was conducted recently
in the stable hexagonal phase [108]. The treatment
increased the crystallinity of both resins to almost the
same level, ∼68% (DSC). However, UHMWPE underwent
homogeneous and significant change from thin lamellae to
extended chain crystal structure, while many thin lamellae
remained in HDPE. The lamellar thickness of UHMWPE was
enlarged from ∼20 nm to the range of 100–150 nm. There-
fore, TC of UHMWPE increased from 0.42 to 0.58 W/(m K)
(37% increase), while that of HDPE only increased from
0.42 to 0.48 W/(m K) (11% increase). These results sug-
gest that it is the extended crystal structure and increased
lamellar thickness that are responsible for substantial TC
improvement relative to a PE with randomly oriented
lamellae.
56 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
4.3. Effect of orientation
Heat is transferred more easily along the chains than
in transverse direction. Therefore, TC can be signifi-
cantly higher in the direction in which polymer chains
are preferentially oriented. As investigated by all-atom
model molecular dynamics simulation [109], mechani-
cal stretching is able to orient polymer chains that have
very high TC and thus enhance the TC of bulk polymers.
There are also numerous experimental studies on poly-
mer chain orientation for TC enhancement, encompassing
crystalline/semicrystalline, amorphous and various liquid
crystalline polymers.
4.3.1. Orientation of crystalline/semicrystalline polymers
Most work regarding the effect of chain orientation on
TC of crystalline/semicrystalline polymers was on PE. Sev-
eral methods for influencing PE chain orientation have been
developed, which include deformation by simple shear
[107], mechanical drawing [110], gel spinning [111–113]
and superdrawing [114] including superdrawing of sin-
gle crystal mats [115,116]. The general trend is that TC
along the orientation direction (TC||) rapidly increased with
increasing strain or draw ratio (), while TC perpendicular
to the draw direction (TC⊥) slightly decreased. Choy and
co-workers [110] investigated both TC|| and TC⊥ of ori-
ented HDPE at relatively low . At  = 25, TC|| increased
to 14 W/(m K) at 300 K and a TC anisotropy defined as
the ratio of TC|| to TC⊥ increased to around 60. Much
higher TC|| was obtained later in high modulus PE fibers
by significant increasing  through gel spinning [111–113]
and superdrawing of single crystal mats [115,116]. For
example, the TC|| of UHMWPE with a  of 250 reached
37.5 W/(m K) [113]. Through more advanced superdraw-
ing of UHMWPE single crystal mats, Choy et al. [116]
produced PE ultradrawn fibers with  up to 350 and
achieved TC|| of 41.8 W/mK. With the increase in , crys-
talline lamellae are broken into small crystalline blocks.
The crystalline blocks are stacked and connected by taut
tie molecules (intra-microfibrillar tie molecules) originat-
ing from partial chain unfolding, thus forming microfibrils
along the draw direction. The microfibrils are connected
laterally by bridging molecules, i.e. inter-microfibrillar tie
molecules. After ultra-drawing, microfibrils are further
deformed (accompanied by a decrease of its volume frac-
tion) and the inter-microfibrillar tie molecules can be
significantly aligned to form long extended-chain crys-
tals, even protofibril substructure (i.e. needle crystals)
[112,117,118]. Such morphology evolution leads to the
focus of group velocity into parallel direction and the
increase of mean free path, both of which can increase TC||.
It is expected that TC|| can be increased continuously with
the development of structure order and perfection.
Apart from PE, TC of various thermoplastic polymers,
such as polyacetylene [119], polyphenylene sulfide [120],
poly(ether ether ketone) [106], other semicrystalline poly-
mers (POM, PP, polychlorotrifluoroethylene, PVDF and PET)
[121] and certain polymer blend [122] was reported to
significantly increase by mechanical drawing/orientation.
Recently, TC of nine commercially available high-modulus
polymer fibers (diameters 10–30 ␮m) was systematically
Fig. 13. Thermal conductivities of various polymer fibers as functions of
their tensile moduli taken from the data sheets from the manufacturers.
For each fiber type, the thermal conductivity is averaged over a minimum
of four fibers. [123], Copyright 2013. Reproduced with permission from
the American Chemical Society.
investigated [123]. These fibers include PE (DyneemaTM
SK75, UHMWPE with a crystallinity of ∼80%) and SpectraTM
900/2000 (HDPE) and liquid crystal polymers with rod-like
segments (VectraTM , KevlarTM , poly(p-phenylene benzo-
bisoxazole) (PBO), polyhydroquinone diimidazopyridine
(PIPD, MA5S) and poly(p-phenylene benzobisthiazole)
(PBT)). Fig. 13 shows the axial TC (i.e. TC||) vs. tensile mod-
ulus of single fibers. PE and PBO fibers have the highest
values of ∼20 W/(m K). VectraTM has the lowest TC, which
is probably attributable to the disorder in the chain seg-
ments and also the relatively low crystallinity of about 20%.
For LCP fibers, the increase in the number of side chains in
each molecular unit is likely to reduce the axial conduc-
tivity due to additional phonon scattering created by the
vibrational modes of the side chains.
Besides the polymer microfibers above prepared by
various mechanical drawing techniques, nanofibers are
of particular interest due to their more perfect structure.
Shen and co-workers [124] recently developed a two-
stage heating method to further scale down the fiber size
and fabricated ultradrawn nanoscale fibers. The obtained
ultradrawn PE nanofibers have a diameter of 50–500 nm
and an estimated overall  of 60–800. The obtained TC||
was as high as 104 W/(m K), which was about three times
higher than previously reported values of micrometer-
sized fibers. It was found that such PE nanofibers had
a strong single-crystal nature, which confirmed that the
stretching did contribute to the nanoscale restructuring
of the polymer chains. Furthermore, fiber quality was
improved with the elimination of inherently large defects
such as voids, impurities or large entanglement regions in
nanoscale size. Higher draw ratios and greater volume frac-
tion of chain extended crystalline region are thus more
achievable, which leads to more ‘ideal’ single-crystalline
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
fibers and extremely high TC. However, the TC|| of ultra-
drawn PE nanofibers cannot approach the predicted values
for a single PE chain [91] because nanofibers are composed
of multiple chains so that the inter-chain van der Waals
interactions induce phonon–phonon scattering. Even so,
based on MD simulations, it was conjectured that TC|| of
PE nanofibers can be increased to about 180 ± 65 W/(m K).
There are other simple production approaches for mak-
ing highly thermally conductive polymer nanowires or
nanofibers. For example, by an improved nanoporous tem-
plate wetting technique, HDPE nanowire arrays with a
diameter of 100 nm and 200 nm were fabricated [125]. The
estimated TC of a single HDPE nanowire is 26.5 W/(m K),
which indicates that the nanowires have a similar ori-
entation degree to ultradrawn fibers with  of 50–100
[116]. NylonTM -11 nanofibers [126] were fabricated most
recently by electrospinning, a simple and versatile method
to produce polymer nanofibers. When the NylonTM -11 fiber
diameter was decreased to ∼200 nm, the TC was found
to rapidly increase because crystallites exhibited a signifi-
cantly higher degree of preferred orientation along the fiber
axis and crystal size started to grow. However, it should be
noted that the TC of electrospun NylonTM -11 nanofibers
(up to ∼1.6 W/(m K)) are much lower than that of the PE
nanofibers [124], which can be attributed to the intrinsic
difference in the molecular structure and the lower crys-
tallinity of NylonTM .
4.3.2. Orientation of amorphous polymers
Drawing of crystalline/semicrystalline polymers usually
increases not only chain alignment but also crystallinity
[116]. Thus, studying purely amorphous polymers can sep-
arate these factors and clarify how chain alignment affects
TC during drawing. Early studies [127–130] showed that
TC of stretched polymethyl methacrylate and polystyrene
could be increased in the stretching direction. However,
the TC increase was relatively small, less than two-fold
in most cases. A recent study [131] showed that pure
polythiophene (PT) nanofibers made via template-assisted
electropolymerization can achieve a TC up to ∼4.4 W/(m K)
while remaining amorphous. The TC of PT nanofibers
increased with decreasing diameter, a trend that agrees
with the measured molecular chain orientation along
the fiber axis. The PT fibers exhibited a distinct trend
of temperature-dependent TC when compared with two
commercial high-modulus and highly crystalline fibers: c-
PE and c-PBO [123]. As shown in Fig. 14, both commercial
fibers exhibited TC ∝ 1/T near room temperature, while TC
increased modestly (TC ≈ T0.4 for d = 71 nm and TC ≈ T0.2 for
d = 245 nm) for the amorphous PT nanofiber. The dominant
phonon-scattering mechanism in the drawn crystalline
fibers at room temperature is anharmonic phonon–phonon
scattering (not structural disorder), but the nanofibers here
appear still to be dominated by interchain scattering due to
structural disorder, despite some degree of chain orienta-
tion. It is likely that the PT nanofibers have a strong increase
in short-range order, but long-range order remains absent.
Compared with ultradrawn PE fiber, the PT fiber may be
more suitable for some high-temperature applications (e.g.
thermal interface materials) considering its better stability
57
Fig. 14. Single-fiber thermal conductivity as a function of temperature.
amorphous polythiophene (a-PT); crystalline polyethylene (c-PE) and
crystalline polybenzobisoxazole (c-PBO). Black dashed line represents the
predicted minimum thermal conductivity for PT. [131], Copyright 2014.
Reproduced with permission from the Nature Publishing Group.
and high TC comparable to PE fibers [132] at high temper-
atures (see Fig. 14).
4.3.3. Orientation of liquid crystalline polymers
The effect of chain orientation on TC of rigid-rod or
semi-rigid polymers, such as commercial nematic liquid
crystalline polymer (LCP) is quite different from the case of
flexible-chain polymers. LCP usually has ordered structure
in which molecular chains are micro-periodically oriented
in the nematic liquid crystalline phase. Such orientational
order can be easily maintained in the LCP samples obtained
via a common process. TC of LCP is, therefore, twice as
high as that of many other resins in the state in which the
molecules are not macroscopically aligned [133]. However,
it is not the case after mechanical drawing. In Fig. 15, the
 dependence of TC|| for LCP VectraTM B950 is compared
with that of several flexible chain polymers [134]. TC|| of
LCP rises sharply at low , then reaches a plateau, which is
exactly consistent with the trend of orientation degree of
LCP as a function of . The semi-rigid chains in the local-
ized domains of the LCP nematic melt already have parallel
orientation. Only a small elongational stress is needed to
induce the chain alignment and lead to saturation of both
orientation degree and TC|| at a low draw ratio. For flexible
crystalline/semicrystalline polymers, the degree of chain
orientation in amorphous regions and the number of taut
tie molecules increase steadily up to the highest achievable
 and thus TC|| increases continuously [116]. Therefore, the
TC of the VectraTM at high  is significantly lower than that
of PE and POM. The simulation study [102,104] attributed
such phenomenon to the chain segment disorder and mass
disorder, which was induced by the fact that the VectraTM
backbone consists of randomly distributed phenyl groups
as well as carbon and nitrogen atoms along the chain.
In addition to mechanical stretching, other approaches,
such as injection molding [133] and high magnetic field
58 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 15. Draw ratio dependence of the axial thermal conductivity of
VectraTM B950, HDPE, polyoxymethylene (POM), and polypropylene (PP)
at 300 K. [134], Copyright 1995. Reproduced with permission from John
Wiley and Sons.
[133,135,136] can enable LCP chain orientation as well.
Sumimoto’s research [133] showed that after injection
molding TC of EkonolTM type of LCP in flow direction was
five times higher than that in the traverse direction. When
a 10 T magnetic field was applied, the orientational order
parameter of LCPs (including EkonolTM (Type I), VectraTM
(Type II) and X7GTM (type III)) exceeded 0.8, sometimes
even 0.9. Accordingly, the TC in magnetic field direction
was at least tripled, even increased by one order of magni-
tude to higher than 2.5 W/(m K) [133]. In certain LCP film, a
TC over 10 W/(m K) has been achieved using a strong mag-
netic field [136]. However, such magnetic-field alignment
is not easy to realize in practical manufacturing processes
(e.g. injection molding), especially for parts with complex
shapes.
For most LCPs, TC usually increases in the flow or draw-
ing direction. However, Yoshihara and his co-workers [137]
recently demonstrated that some main chain LCPs can
achieve a high TC (greater than 1.0 W/(m K)) in the direc-
tion perpendicular to the flow during injection molding
process. Fig. 16(a) shows the molecular structure of that
LCP, which is a main-chain PB-n polyester, where n is the
even number of methylene units in the spacer moiety.
This type of polymer is known to form a highly ordered
smectic liquid crystalline phase with a chain-folding lamel-
lar structure in both smectic and crystalline phase [138].
When the PB-n is in a smectic phase, shear flow can induce
the orientation of the chain-folding lamellae [139–141],
either in parallel (Fig. 16(b)) or perpendicular direction
(Fig. 16(c)). It was found that injection molding of PB-n in
the smectic phase selectively induced the parallel orienta-
tion. Therefore, polymer chains were aligned in the normal
direction with respect to the molding surface, thus lead-
ing to a high TC⊥. The TC of this main chain LCP also has
a strong dependence on molecular weight (Mn ). For exam-
ple, PB-10 with Mn = 8000 g/mol had a TC⊥ of 1.20 W/(m K)
(0.3 W/(m K) in the other two directions). However, only
0.53 W/(m K) was achieved when the Mn doubled. In that
case, the chain-folding lamellae were randomly oriented,
even after injection molding. It was thought that molec-
ular entanglement and interlayer connectivity of lamellae
become greater with increasing Mn , which inhibits lamel-
lae sliding that is necessary for the parallel orientation.
Therefore, a low Mn is necessary to achieve high TC⊥ for
this kind of material, likely leading to inferior mechani-
cal properties. Further studies [142,143] on the composites
of this smectic LCP indicated that polymer lamellae tend
to lie parallel to the filler surface and are stacked toward
neighboring fillers. In other words, polymer chains are per-
pendicularly oriented between fillers and thus serve as
effective heat paths. The TC of the composites in both direc-
tions, in particular TC⊥, was significantly enhanced.
4.4. Polymer blends by engineered interchain
interactions
As discussed in the previous sections, molecular struc-
ture, crystallinity and chain orientation are the important
factors influencing TC. Chain orientation has been the
most explored route to increase TC in polymers. However,
usually high TC can be obtained only in the orientation
direction. It is thus desirable to explore polymers whose
TC can be increased in all directions, and yet still can be
processed with conventional manufacturing processes.
Most recently, a breakthrough finding [144] was
reported that a high TC (over 1.5 W/(m K)) can be achieved
in amorphous polymer blends by engineering inter-
chain interaction. There are several requirements for the
amorphous polymer blends to have high TC: (1) strong
intermolecular bonds to replace weak interactions; (2) the
intermolecular bonds must connect as closely as possi-
ble to polymer backbone; (3) homogeneous distribution of
these bonds at a concentration above percolation threshold
to form a continuous thermal network; H-bond-accepting
and -donating polymers have strong intermolecular bonds
(hydrogen bonding). However, they are required to be mis-
cible at the molecular level to allow polymers to intertwine
within the radius of gyration, as shown in Fig. 17(a). Such
requirements are demonstrated by the purposely designed
polymer pairs, as shown in Fig. 17(b). Results showed that
only certain blends of PAP and PAA with strong H-bond
concentration exceeding percolation threshold yielded a
dense and homogeneously distributed thermal network
and reached a TC as high as 1.5 W/(m K), which is nearly an
order of magnitude higher than that of typical amorphous
polymers. The rigid and short PAP chains were thought to
penetrate into the PAA radius of gyration and hold the flex-
ible PAA backbone in an extended state by means of strong
H-bonds. Such extended backbone is expected to improve
intrachain heat transfer, analogously to the oriented poly-
mers discussed previously. However, for PAP:PVA and
PAP:PVPh pairs, little or no TC improvement was observed
possibly due to the weak H-bonds, the presence of heavy
and large benzene linkers, lack of continuous network of
strong hydrogen bonds and blend homogeneity.
This work paves a novel way to increase TC for amor-
phous polymers. However, it should be also noted that the
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85 59

Fig. 16. (a) Chemical structure of the smectic LCP main-chain PB-n; (b) parallel and (c) perpendicular orientations of lamella by shear flow. The TC⊥ in (b)
is illustrated. [137], Copyright 2012. Reproduced with permission from John Wiley and Sons.

large increase was in the cross-plane TC in spin-cast (from
polymer solution) films with a nano thickness up to 70 nm.
It is interesting to know whether this high TC is isotropic
and can be maintained for bulk thick films. It is also inter-
esting to know whether these polymer blends still have
high TC if they are prepared by melt mixing.
5. Thermal conductivity of thermosets
Thermosets have also been used as the matrix for ther-
mally conductive composites due to their easy molding
capability, high thermal resistance, and high electrical
insulating characteristics. Similar to most thermoplas-
tics, thermosets such as epoxy resin are amorphous and
have a low thermal conductivity in a range from 0.17 to
0.21 W/(m K) [4,145]. As discussed before, the TC of the
matrix has a huge effect on the TC of final composites. Even
a small increase on the TC of matrix can lead to significant
improvement on the TC of final composites given the same
filler loading [146]. Thus, to achieve high TC in typical ther-
mosets, one needs to typically use high filler levels, thus
increasing the viscosity of composite resin and leading to
poor processability.
As discussed before, ordered structure in polymers
can promote the movement of phonons, and thus can
lead to resins with higher TC. Liquid crystalline ther-
mosets, possessing long rigid rod-like “mesogen” groups,
can form ordered structure. When thermosets with meso-
gen structure are cooled from isotropic state at high
temperatures, mesogen groups can aggregate and form
liquid crystal domain in matrix at a certain temperature
range. This ordered liquid crystal domain can effectively
increase the TC of matrix. Table 3 displays the TC of vari-
ous thermosets including both amorphous thermosets and
liquid crystalline thermosets. Normal non-mesogen ther-
mosets such as DGEBA can only form isotropic amorphous

Fig. 17. (a) Illustrations of heterogeneous (left) and homogeneous (right) distributions of thermally conductive interchain connections; (b) polymer pairs
designed to exhibit interchain H-bonding. The OH group is closely connected to the main chain for PAA and PVA, whereas it is attached to the backbone
via a benzene ring linker for PVPh. [144], Copyright 2014. Reproduced with permission from the Nature Publishing Group.
60 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85

Table 3
Thermal conductivities of various thermosets.

Thermosets Monomer Hardener Thermal conductivity

W/(m K)

0.19 [148]
DGEBA

0.20 [95]

0.20 [147]

BACE – 0.29 [149]

0.26 [148]
DGETMBP

0.29 [148]

0.15–0.17 [150]
PMDA
0.44–0.45 [150]

0.44–0.46 [150]

0.30 [145,148,151]
DGEBP

0.43–0.44 [150]

DGEHAP 0.33 [152]

DGETAM 0.38 [147]

DGEHH 0.39 [153]

DGEDH 0.50 [154]

BZE 0.69 [148]

TME8 0.83–0.85 [145,148]

0.88 [148]
TME6

0.89 [145]

0.96 [145]
TME4

1.05 [148]
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 18. Relationship between thermal conductivity and domain size and
content [148].
morphology, so the relevant TC is in a very low range of
0.19–0.20 W/(m K) [95,147,148]. Due to the existence of
ordered structure, liquid crystalline thermosets exhibit a
much higher TC. The highest value is around 5.5 times that
of DGEBA.
5.1. Effect of liquid crystal domain size and content
In fact, TC has a strong dependence on the liquid crys-
tal domain size and content [155]. As shown in Fig. 18, TC
increases with the ratio of anisotropic structure. The ratio
of anisotropic structure is defined as the volume percent-
age of anisotropic structure in the whole matrix, which also
indicates the content of liquid crystal domain [148]. More-
over, the dependence is much stronger when the size of
liquid crystal domain is larger than 400 nm and its content
exceeds a threshold of 25 vol.%.
Mono-mesogen thermosets which have one single
mesogen are the most common liquid crystalline ther-
mosets. As shown in Fig. 19, the mesogen groups can form
Fig. 19. Schematic representation of the strategy to afford macroscopic isotropic resin having high thermal conductivity. [145], Copyright 2003. Reproduced
with permission from John Wiley and Sons.
61
Fig. 20. Possible schematic image of smectic microstructure from twin-
mesogen thermosets. Dotted lines represent the lattice plane of smectic-
like structure. [145], Copyright 2003. Reproduced with permission from
John Wiley and Sons.
microscopic anisotropic liquid crystalline domains due to
␲–␲ stacking. This ordered structure leads to higher matrix
TC. However, most mono-mesogen thermosets can only
form weakly-oriented nematic liquid crystals with either
small liquid crystal domains (size less than 400 nm) or
low content of liquid crystal domain (less than 25 vol.%).
Therefore, the TC improvement is limited (about 2–3 times
compared to that of typical thermosets).
Some mono-mesogen hardeners can also result in the
formation of liquid crystal in thermosetting matrix and
higher thermal conductivities can be obtained as well. As
shown in Table 3, when PMDA is cured with a normal hard-
ener, a low TC of only 0.15–0.17 W/(m K) was obtained.
However, when it was cured with mono-mesogen harde-
ners, the TC can be increased to 0.44–0.46 W/(m K) [150].
It is worth noting that, even with both mono-mesogen
resin and mono-mesogen hardener, the liquid crystalline
domain size and content are still limited. Therefore, overall
TC was still below 0.70 W/(m K) [148].
Another kind of liquid crystalline thermosets are twin-
mesogen thermosets, which have two mesogens linked by
a spacer. As shown in Fig. 20, this special structure can
lead to highly oriented smectic liquid crystalline morphol-
ogy after curing [145,156]. Their liquid crystal domain size
and content are much higher than 400 nm and 25 vol.%,
62 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
respectively, which results in much improved TC. TME4,
TME6 and TME8 that are typical twin-mesogen thermosets,
as shown in Table 3, have very high liquid crystal domain
size (>1600 nm) and content (>40 vol.%). Their TC can reach
a very high range of 0.83–1.05 W/(m K) [145,148]. Although
twin-mesogen thermosets showed very high TC, their com-
plicated synthetic procedure and very high raw material
cost make them difficult to be commercialized.
5.2. Effect of curing condition
Curing condition is also a key factor to the forma-
tion of liquid crystal structure which exists at a certain
temperature range. Generally, when liquid crystalline ther-
mosets undergo heating, they transform from crystalline
state to strongly oriented smectic liquid crystalline state,
then to weakly oriented nematic liquid crystalline state.
With further temperature increase, the nematic liquid
crystal will eventually disappear and finally isotropic amor-
phous state is reached. Some liquid crystalline thermosets
do not exhibit smectic state, but directly transition from
crystalline state to nematic state. Therefore, for liquid crys-
talline thermosets, lower curing temperature will promote
the formation of highly oriented structure and thus lead to
a higher TC.
Harada et al. [147] cured diglycidyl ether
of terephthalylidene-bis-(4-amino-3-methylphenol)
(DGETAM) at different temperatures and compared ther-
mal conductivities of resulting thermosets. When cured
at 200 ◦ C, the system formed an isotropic amorphous
phase and the TC was 0.35 W/(m K). When the curing
temperature decreased to 160 ◦ C, clear birefringence
patterns indicated the formation of liquid crystalline
phase. The TC increased to 0.38 W/(m K). Another example
is 4-(4-oxylanylbutoxy)benzoic acid-1,4 -phenylene ester
(BZE) epoxy [148]. When cured at isotropic amorphous
state at 230 ◦ C, the TC of BZE was only 0.44 W/(m K). When
cured at liquid crystalline state at 180 ◦ C, its TC increased
to 0.69 W/(m K).
Song et al. [157] also studied the effect of curing condi-
tion. The authors found that there were many spherulitic
crystals formed in cured epoxy DGEBP, as shown in Fig. 21.
With decreasing initial curing temperature, the size of
Fig. 21. POM photograph of well-developed spherulite crystals. [157],
Copyright 2012. Reproduced with permission from Elsevier Ltd.
spherulitic crystals increased from 10 to 80 ␮m. The rele-
vant TC increased with the size of spherulitic crystals from
0.33 to 1.16 W/(m K).
It is also worthwhile to point out that liquid crystalline
thermosets with high TC usually have a high melting point.
As they need to be heated to above its melting point for
mixing with fillers and hardeners and processing, this could
lead to short gel time and poor processability.
5.3. Effect of orientation
For liquid crystalline thermosets, the application of a
powerful external field, such as an electric field [158] or a
magnetic field [159,160] is very effective for obtaining high
orientation of mesogen groups. In general, mesogen groups
will be aligned through the direction along the applied field.
Therefore, TC will significantly increase in the orientation
direction, while the TC in the direction across the applied
field will decrease to a certain degree.
Harada et al. [161] studied the effect of magnetic field
on the TC of liquid crystalline DGETAM epoxy cured with
4,4 -diaminodiphenylethane (DDE). The authors cured
DGETAM/DDE system with and without magnetic field of
10 T (superconducting magnet) at 170 ◦ C. For the system
cured without a magnetic field, the TC was 0.43 W/(m K).
For the system cured under the magnetic field (10 T), the TC
in the direction along the applied magnetic field reached a
very high value of 0.89 W/(m K), while the TC in the direc-
tion across the applied field was only 0.32 W/(m K). Wide
angle X-ray diffraction (WAXD) results confirmed that the
matrix cured under the 10 T of magnetic field had a highly
ordered network structure along the direction of the mag-
netic field as shown in Fig. 22.
Some other methods were also developed to obtain
highly oriented liquid crystalline thermosets. Geibel et al.
[162] coated the UV-curable liquid-crystalline monomers
on the top of uniformly rubbed polyimide. Homogeneous
orientation of liquid crystals in the rubbing direction was
obtained. The UV-curable monomer layer held in the liq-
uid crystalline state was cured by irradiation. The TC
reached up to 5.2 W/(m K) in the orientation direction.
However, the TC normal to the oriented direction was only
0.33–0.34 W/(m K).
Fig. 22. Model of DGETAM/DDE cured under the magnetic field. [161],
Copyright 2003. Reproduced with permission from John Wiley and Sons.
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85 63

Table 4
Thermal conductivities of some thermally conductive fillers.

Fillers Category TC W/(m K) Electrically conductive? Refs.

Aluminum Metal 234 Yes [167]

Copper Metal 386 Yes [168]
Silver Metal 427 Yes [169,170]
Carbon nanotube (CNT) Carbon-based 1000–4000 Yes [3,171]
Carbon fiber Carbon-based 300–1000 Yes [172,173]
Graphene Carbon-based 2000–6000 Yes [174,175]
Graphite Carbon-based 100–400 Yes [176]
␤-Silicon nitride (␤-Si3 N4 ) Ceramics 103–200 No [177]
Hexagonal boron nitride (h-BN) Ceramics 185–300 No [147,178,179]
Aluminum nitride (AlN) Ceramics 100–300 No [180,181]
Diamond Ceramics 1000 No [182]
␤-Silicon carbide (␤-SiC) Ceramics 120 [183]
␣-Alumina (␣-Al2 O3 ) Ceramics 30 No [184,185]
Beryllium oxide (BeO) Ceramics 270 No [186,187]

6. Thermally conductive fillers
Given that polymers have low TC (generally less than
1.0 W/(m K)), making high-TC polymer-based materials
requires introducing high-TC filler particles into polymer
matrix [163–165]. The TC of fillers is largely determined
by the way how heat transfers in filler particles. In gen-
eral, fillers with purely phonon heat transfer mechanism
(as opposed to those having both phonon and electron
ones) have lower TC. Metal oxide such as ␣-Al2 O3 only has
a TC around 30 W/(m K) [166]. Even for highly thermally
conductive ceramic materials, such as BN and AlN, TC can
only reach to 100–300 W/(m K). In contrast, free electrons
are much more efficient in transporting heat compared to
phonons since electrons are more resistant to scattering
and move at higher speeds. Thus, metallic and carbon-
based fillers show a much higher TC mainly due to free
electrons. Table 4 lists both thermal and electric properties
of commonly used thermally conductive fillers.
6.1. Metallic fillers
Various metallic fillers, such as nickel, copper, alu-
minum, silver, have been widely used in polymer
composites for improving TC [188]. In general they could
be quite effective in increasing TC of composites compared
to the pure matrix polymer. However, adding metallic par-
ticles into polymers will also cause a substantial increase in
the electrical conductivity of the composites and/or reduc-
tion in the dielectric breakdown voltage. Thus, metallic
fillers can only be used in applications where electri-
cal insulation and dielectric breakdown strength are not
important.
6.2. Carbon based materials
low TC and is not a very good candidate for high thermally
conductive composites [193]. Carbon fibers [194] and CNTs
are one-dimensional (1-D) fillers, and have a high TC along
the longitudinal direction. The TC of carbon fibers varies
over a wide range depending on the organic precursor
and processing conditions used. The two most important
precursors for carbon fibers are polyacrylonitrile (PAN)
[172] and mesophase pitch (MPP) [173]. Mesophase
pitch-based carbon fibers have a much higher TC (up to
1000 W/(m K)) resulting from highly crystalline graphitic
structure and its high degree of orientation parallel to
the fiber axis [172]. Therefore, a large number of research
efforts have been focused on using mesophase pitch-based
carbon fibers as thermally conductive reinforcements
[195,196]. Carbon nanotubes (CNTs) are an allotrope of
carbon having a cylindrical structure and show extremely
high TC [171]. There is a recent review on more detailed
treatment of polymer–CNT composites [3], in which the
influence of atomic structure, tube size, morphology,
defects, purification, micro/nano-structure, and interfaces
between CNTs and polymer matrix on the TC have been
discussed extensively. Recently, it was discovered that
graphene has extremely high TC, which even exceeds
that of CNTs [197]. Graphene is a two-dimensional carbon
material with a single layer structure, for which it is easy to
form effective pathways for heat transfer. It is considered
to be a good thermally conductive additive for thermal
engineering application. However, the large surface area
of graphene makes it difficult to be incorporated (“exfoli-
ated”) in polymer at high levels and its high material cost
is another concern that may limit its further industrial
applications. Even so, compared to other nanosized carbon
materials, graphene is abundant, relatively cheap, and
highly thermally conductive, and has already found many
industrial applications.

Carbon-based materials, including graphite [90], 6.3. Ceramic fillers

graphene [189,190], carbon nanotube (CNTs) [3], carbon
fiber [191], etc., have been widely studied as heat conduc-
tive fillers because of their high intrinsic TC [192]. Even a
very small loading of carbon-based fillers can significantly
increase the TC of composites. Another advantage is
their light weight compared with metal or ceramic fillers.
Among carbon-based materials, carbon black has relatively
Ceramic fillers have been widely studied for thermally
conductive and electrically insulating composites due to
their inherent properties. They lack free electrons, and
the heat transfer is predominantly through phonons. Gen-
erally, except for BeO, most metal oxide fillers such as
alumina (Al2 O3 ) [184,185] and silica (SiO2 ) have a lower
64 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
TC. Non-oxide fillers, such as aluminum nitride (AlN)
[198,199], boron nitride (BN), silicon nitride (Si3 N4 ) [200]
or silicon carbide (SiC) [183] have high TC as their strong
interatomic bonds and crystal structure can significantly
reduce phonon scattering. In particular, BN and AlN fillers
are widely used for thermally conductive and electrically
insulating composites [201]. However, these fillers also
have some limitations, e.g., BN has an extremely low TC
in the through-plane direction, and AlN particles are easy
to hydrolyze [179,202] (although the moisture reactivity of
AlN could potentially be mitigated by surface modification
such as silica coating [203]).
TC is closely related to the crystal structure and crys-
tallinity of fillers. The alignment of atoms and their
interactions affect the efficiency of the heat transfer
dramatically. In fact, even two materials with identical
chemical formula could have different TC, if they possess
different crystal structure. For example, there exist ␣ and
␤ phases in Si3 N4 crystals, corresponding to low- and high-
temperature polymorphs, respectively. The TC of ␤-Si3 N4
in the direction parallel to the c-axis is much higher than
that of the isotropic ␣-Si3 N4 [204]. Another example is
boron nitride, which can change from hexagonal structure
to cubic structure under high temperature and pressure
[205]. Hexagonal BN is comprised of planar sheets of cova-
lently bonded boron and nitrogen atoms, which make up
the in-plane structure of the crystal. Different layers are
held together in the through-plane direction through Van
der Waals forces. Due to its special crystal structure, it
shows anisotropic TC with ∼300 W/(m K) in in-plane direc-
tion and ∼2 W/(m K) in through-plane direction. After the
transition into cubic phase, boron nitride becomes more
isotropic, and its in-plane and through-plane TC become
nearly equal and high. Similar situation exists between
graphite and diamond [206]. Better crystallization means
fewer defects in crystal structure and can help improve heat
transfer by reducing the phonon scattering. Also, presence
of impurities will increase defects in the materials. Defects
can cause additional scattering of the electrons or phonons,
resulting in the lower overall thermal conductivity. Grain
boundaries between crystals (grains) in an inorganic filler
can be a significant source of phonon scattering.
7. Influence of the filler morphology and properties
on thermal conductivity
Besides the intrinsic TC of fillers, the main factors affect-
ing the thermal properties of composites are filler volume
fraction (also referred to as loading level), particle shape,
particle size, and adhesion between the fillers and matrix
and the thermal property of interface.
7.1. Effect of filler loading level
The dependence of composite TC on filler loading level
was largely discussed in Section 2, so here we only recap
very briefly. In general, TC of composites increases with
increase in the volume fraction of thermally conductive
filler. The increase is often non-linear [207]. At lower filler
loading levels (<35 vol.%), the TC increase can be rela-
tively small. Only at high filler loading levels can a more
drastic improvement be observed. This implies that effi-
cient thermally conductive pathways start to form at high
filler loading levels due to filler-to-filler connections. This
phenomenon is described well by various models [207]. It
should be noted that increasing loading level is not always
preferred, as a high filler loading level can cause the com-
posite to be brittle, have poor processability and result in a
high cost.
7.2. Effect of filler shape
The filler shape also has a significant influence on
the performance of polymer composites. The effects of
filler shape on the TC of composite materials, especially
when the fillers are distributed randomly, were extensively
studied [208,209]. It is important to note that thermal con-
ductivity is not the only property that depends on the
filler shape. For processing polymer composites, lower vis-
cosity is desired. However, high filler loading above the
percolation threshold is usually needed to achieve high TC.
High filler loading will normally cause a significant increase
on the viscosity of composites and make it more difficult
for composites to be processed by conventional polymer
processing techniques. The rise of viscosity mainly stems
from the interfacial friction between fillers, and between
fillers and polymers. Many low-cost fillers have irregular
shapes with many edges and corners, and can cause signif-
icant friction during mixing or compounding. The irregular
shape can cause a significant increase in the viscosity of
composites when the filler loading is high. When deal-
ing with irregular shaped fillers with high hardness, for
example, irregular Al2 O3 powders, tool wearing could be an
issue. Other characteristics of fillers, such as rough surface,
low flowability, aggregation, breakability, will be unfavor-
able for the processing of the composites, and may damage
TC of the composite as well. Fillers with smooth surface and
spherical morphology are favorable for lowering down the
friction and improving processability, yet they could be less
efficient in increasing the composite TC. Below, we discuss
the interplay of these trends for various filler types.
7.2.1. One-dimensional fillers
Polymer composites with low-aspect-ratio fillers usu-
ally exhibit a lower TC even at high filler contents. High-
aspect-ratio fillers are thus beneficial to achieve low per-
colation threshold for composites [210]. One-dimensional
(1-D) fillers, such as fibers, rods, wires or tubes, are
expected to significantly improve the TC of composites
compared with fillers with other shapes, as it is easier for
high-aspect-ratio fillers to construct long heat conductive
pathways along the longitudinal direction of 1-D fillers in
the composites.
For 1-D fillers with high-aspect-ratio, the TC along the
longitudinal direction is usually much higher than that in
the perpendicular direction. Therefore, if fillers are ori-
ented in composites, the composites will show anisotropic
TC. In fact, not only TC, but also other physical properties
may be anisotropic depending on 1-D filler orientation.
Glass fiber [211] is the most commonly used filler for
strengthening polymer composites; however, its TC is not
high. Carbon fibers [194] (and more recently CNTs [3])
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
are also commonly used in composites, as they can offer
mechanical strength and extra TC. Takafumi Kusunose et al.
[212] reported the synthesis of ␤-Si3 N4 nanowires and
evaluated the TC of ␤-Si3 N4 nanowire/epoxy composites.
For comparison, commercially available irregular ␤-Si3 N4
powders were employed to mix in the epoxy matrix with
the same loading level. The composite with irregular ␤-
Si3 N4 powders showed more isotropic TC. The in-plane
and through-plane TC are 2.5 and 2.6 W/(m K), respectively.
Unlike the irregular powders, the sample with ␤-Si3 N4
nanowires showed much higher TC in both directions
with 9.2 W/(m K) in in-plane direction and 5.7 W/(m K)
in through-plane direction. It is obvious that TC became
more anisotropic. Boron nitride nanotubes (BNNTs) are
also a promising candidate for various applications due
to their superb thermal and antioxidation stability, high
TC and excellent mechanical properties [213]. Metal wires
or fibers are another type of 1-D fillers. The most used is
silver nanowires (AgNWs) with large-aspect-ratios, which
would lead to a lower percolation threshold, and can
be preferred fillers for thermal interface materials (TIMs)
[214]. However, silver nanowires are very expensive, which
makes copper nanowires (CuNWs) more competitive as
1-D metal fillers. Wang et al. reported that by using a single-
crystalline CuNWs with a high-aspect-ratio as thermally
conductive filler, only 0.9 vol.% loading of CuNWs in poly-
acrylate can achieve a TC of 2.46 W/(m K) [168].
7.2.2. Platelet-like fillers
Platelet-shaped fillers are also characterized by high-
aspect-ratio and low percolation thresholds. As the
thickness of many platelet-shaped fillers is quite small,
they can be considered two dimensional (2-D) fillers. Dur-
ing processing, such as injection molding, they tend to be
aligned parallel to one another, and offer a high degree
of contact in parallel direction. Also, the fillers often have
a high TC in the in-plane direction. These often lead to
anisotropic thermally conductive composites with much
higher TC in the flow direction than that perpendicular to
the flow direction.
It should be mentioned that plate-like fillers are not
limited to those materials which have platelet molecular or
crystal structure, such as BN or graphene or graphite. Other
ceramic or metallic particles, such as Al2 O3 , TiB2 and SiC,
may also possess plate-like morphology and were used as
thermally conductive fillers for polymer composites [215].
7.2.3. Spherical fillers
In general, filler loading needs to be high to obtain high
TC. However, high filler loading will cause a significant
increase in viscosity and reduce its processability. Find-
ing the optimal composition window where the viscosity
is still relatively low while thermal conductivity is suffi-
ciently high is, then, the critical challenge. Spherical fillers
offer some promise in this regard because their viscos-
ity percolation threshold is fairly high (∼50–60 vol.%) [45].
Various spherical fillers including Al2 O3 , AlN, Si3 N4 , SiC,
etc. have been developed and used in thermally conduc-
tive composites [216–218]. Even for those with platelet
crystal structure, such as BN, various methods have been
developed for synthesizing spherical fillers that may permit
65
higher filler loading and improved processability [216,219].
For example, spherical BN was synthesized by the reac-
tion of aerosol droplets containing water-soluble boric acid
(H3 BO3 ) with ammonia gas at elevated temperatures in
an ammonia/nitrogen mixed gas atmosphere. The obtained
spherical BN was reported to have an average diameter of
1–2 ␮m with smooth surface, and can be a good candidate
for highly thermally conductive composites [219]. Ohashi
et al. [217] successfully prepared spherical AlN, and the
spherical AlN/epoxy showed better fluidity compared with
composites with commercially available irregular AlN. The
polymer composite with a high filler loading (74 vol.%)
was successfully obtained by adjusting the filler size dis-
tribution to the bimodal one, and achieved a high TC of
8.2 W/(m K), which is 9 times the TC of composite with
spherical silica fillers (0.9 W/(m K)), and twice that of the
composite with spherical alumina fillers (4.0 W/(m K)).
Besides those conventional shapes mentioned above,
the effects of 11 artificially designed filler shapes, such as
double Y, Y, quad Y shaped, triangle, elliptical, square, rect-
angular, and T shapes on the TC, were investigated by Wang
et al. [220]. It was found that filler shapes have great impact
on the effective TC of the composite materials. The best
fillers should be tree-like, which have a long heat conduc-
tion distance and large contact areas even when they are
placed unfavorably. From this respect, the double Y shaped
fillers are the best, followed by Y shaped fillers.
7.3. Size effect
Filler size is also important to the TC of composites.
Composites with small filler particles have large interfa-
cial area, causing phonon scattering and hindering phonon
transport, and often have a lower TC [221]. Composites
with large fillers have less filler/polymer interface and thus
lower thermal interfacial resistance, leading to improved
heat conduction. Wu et al. [222] studied the TC of graphite
nanoplatelets/polyetherimide (PEI) system with different
filler sizes from 1 ␮m to 15 ␮m. It was found that the TC
of composites filled with smaller particles was lower, even
though a better filler network was observed for the smaller
particle system. This fact indicated that the interfacial resis-
tance may be more important than filler connection, at least
in this particular example. Zhou et al. [223] showed that the
TC of silicone rubber filled with larger Al2 O3 was superior
to that of the rubber filled with the smaller particles. Li et al.
[224] enhanced the TC of polyimide films with micro- and
nano-sized boron nitride. The micro-sized filler gave higher
TC than nano-sized fillers.
However, there are also controversial reports on the
effect of particle size, in particular when particle size is
in the nanoscale. Some reports claimed that the inclu-
sion of nanofillers in polymers can lead to the same or
higher TC compared to their micro-sized counterparts
[170,225–227]. TC not only depends on the particle size,
but also depends on the surface chemistry of particles, filler
morphology in the composites, etc. It is hard to control the
particle size to be the only independent variable, when the
particle size effect was studied. In fact, in many cases, the
nano particles were prepared in a different way from micro
particles. The nano particles may have different properties
66 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 23. SEM image of (a) the microcomposite and (b) the nanocomposite. While in the microcomposite the silver fillers are not connected, a network
structure is revealed in the nanocomposites. [170], Copyright 2012. Reproduced with permission from AIP Publishing LLC.
and different surface chemistry, which leads to a different
dispersion state in the composites. The contribution from
these parameters sometimes dominates the contribution
from the reduced thermal interfacial resistance in micro
composites. This might lead to higher TC observed in the
composites with smaller particle size. For example, Pashayi
et al. [170] reported that epoxy-silver nanocomposites
had up to 50-fold higher TC than composites with silver
micro particles at a similar volume fraction of fillers, even
though they have been processed under similar conditions.
SEM images showed that the silver nanoparticles formed
a conductive network in nanocomposites while the micro-
particles did not, as shown in Fig. 23. It is clear that the filler
network in nanocomposites is responsible for the higher
TC. The network was formed via low temperature sinter-
ing of nanoparticle fillers during the curing of the epoxy,
as the silver nano particles have a lower melting point.
The details will be discussed in Section 8.3.3. Kemaloglu
et al. [226] found that the boron nitride/SEBS/EVA ternary
blends with smaller BN particles showed higher TC than
that of the composites with larger particles at the same
filler content. These small particles are really the mixture
of spherical BN particles and plate-like BN particles. There-
fore, the higher TC cannot be totally ascribed to the size
effect. Fu et al. [227] revealed that epoxy adhesives filled
with nanosized Al2 O3 had higher TC than those filled with
microsized ones. The authors acknowledged the nanopar-
ticles are somewhat more polydisperse and better able to
form network, thus the differences in TC cannot be totally
attributed to the difference in particle size.
Although nanoparticles have high interfacial area, and
thus increased thermal interfacial resistance, they could
enhance TC significantly when combined with micro-
particles. This has been demonstrated in several systems
[224,227]. This is because the nano-sized fillers acted as
bridges between micro-sized fillers to enhance thermal
contact, while the micro-sized fillers could form the pri-
mary thermally conductive path in composites.
It should be noted that nano-fillers often provide some
other advantages over micro-fillers. The nanocomposites
often have superior mechanical properties. For example,
the silica nanocomposites had better mechanical proper-
ties (higher modulus and strength) than composites with
their micron-sized counterparts [228]. The study on the
effect of filler size on the elastic modulus of epoxy/alumina
trihydrate also showed that modulus decreased with
increasing particle size at high filler loading levels [229].
Smaller calcium carbonate particles provided polypropyl-
ene composites with higher strength at a given particle
loading. Another big advantage that nano-sized fillers could
offer is the optical transparency. The composites with
nanoparticles are often transparent, provided the particles
are well-dispersed in the matrix. For example, a trans-
parent and highly heat-conductive composite film was
made by incorporating nanosized boron nitride nanotubes
(BNNT) into polyvinyl formal (PVF) [230].
7.4. Hybrid fillers
Hybrid fillers are commonly used in the thermally
conductive composites, as a better thermally conductive
network can be formed by using mixed fillers with differ-
ent sizes or types. Hybrid filler system can help to form
large thermally conductive network by building bridges
between fillers and maximizing the filler packing den-
sity. Another advantage of a hybrid filler system is that
it may help to significantly reduce the overall filler load-
ing, thus reducing the system viscosity. A small amount
of CNT (1 vol.%) in AlN/epoxy system with 25 vol.% AlN
loading showed comparable TC to that of epoxy compos-
ite containing 50 vol.% AlN [231]. Hybrid filler system not
only can increase the packing density and lower the sys-
tem viscosity, but also can improve through-plane TC for
some platelet filler composite systems, e.g. adding spheri-
cal or irregular fillers to BN/polymer composites to disrupt
the alignment of platelet fillers. Table 5 lists various hybrid
filler systems reported in the literature.
7.4.1. Mixture of fillers with different sizes
Mixing fillers with the same shape but different sizes
was employed for the optimization of packing density of
fillers. The mixture of large BN (0.4 ␮m) and small BN
(0.2 ␮m) gave a higher TC than those with a single parti-
cle size at the same filler volume fraction [238]. A binary
mixture of AlN with small particles around 2 ␮m and
large AlN particles around 30 ␮m, was filled into epoxy
composite, and showed improved flowability and TC com-
pared to the composite with a single sized filler. When the
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85 67

Table 5 polygonal AlN and platelet-shaped BN were added into

Various hybrid filler systems reported in the literature.
epoxy matrix to get the optimal TC [201]. It was found
Filler 1 Filler 2 Refs. that the packing efficiency is closely related to the diame-
h-BN Different sized h-BN [224,232]
ter ratio of the two filler particles. The optimal shape and
Irregular shaped Si3 N4 Irregular shaped SiO2 [233] composition of the AlN/BN composite systems were dis-
h-BN Carbon fibers [232] cussed (Fig. 25) and the maximum TC up to 8.0 W/(m K)
h-BN CNTs [232,234] was achieved in the AlN/BN hybrid system with a similar
Hollow glass Smaller-sized nitride [235]
particle size and 1/1 volume ratio of the two particles.
microspheres particles
AlN CNTs [231] A novel idea about hybrid filler system was to take
Nano sized SiC CNTs [236] advantage of 1-D fillers to create a 3-D interconnected ther-
Graphite Carbon fiber [237] mally conductive pathway throughout the polymer matrix.
Graphene BN [164] There are positive synergistic effects when combining 1D
Platelet h-BN ZnO whiskers [209]
Graphite nanoplatelets SiC microparticles [165]
and platelet-shaped fillers, as platelet-shaped fillers tend to
orientate in one direction, and most of them can only con-
tact with each other basically in the parallel direction. 1-D
fillers are more flexible and can serve as bridges to connect
platelet-shaped fillers in different layers to construct a 3-
D filler network. It was found that a significant synergistic
improvement on TC of the BN/polyphenylene sulfide (PPS)
composite has been achieved by adding a small amount of
CNT to form a hybrid filler system, as shown in Fig. 26 [234].

7.5. Surface treatment

As inorganic fillers are dispersed in organic polymer

Fig. 24. The concept of using particles with different sizes resulted in
more efficient packing of fillers. [240], Copyright 2013. Reproduced with
permission from Elsevier Ltd.
fraction of small particles in the binary mixture of the AlN
was around 0.2–0.3, the maximum improvement on the TC
was observed [239] (Fig. 24).
7.4.2. Mixture of fillers with different shapes
Fillers with same type, but with different shape and size
have also been blended to improve TC. Larger platelet fillers
were combined with smaller spherical fillers to get positive
synergistic effect. Spherical BN agglomerates (BN-PTX60)
and platelet BN (BN-PT110) were added to PPS in a melt-
blending process [232]. The smaller PTX60 fit between
larger PT110 platelets to create interconnectivity through-
out the polymer matrix, and increased the effective TC of
the composites.
7.4.3. Mixture of different types of fillers
Different types of fillers have also been combined to
get desired TC, processability and other properties. The
hybrid particles usually have different shapes and sizes. A
combination of irregular shaped Al2 O3 and AlN with dif-
ferent sizes was added into polymer matrix. Two cases
of large-sized AlN combined with small-sized Al2 O3 , and
large-sized Al2 O3 combined with small-sized AlN were
studied. At total filler loading of 58.4 vol.% and the volume
ratio of large particles/small particles was 7/3, a maximum
TC of 3.402 W/(m K) and 2.842 W/(m K) has been achieved
for the two systems, respectively [240]. The mixture of
matrix, numerous filler/polymer interfaces are created.
The interfacial thermal resistance between polymer matrix
and fillers is one of the main reasons for limited ther-
mal conductivity improvement in heat conductive polymer
composites (see also Section 2 for discussion on funda-
mentals and computer simulations of interfacial thermal
resistance). The interfacial thermal resistance can be clas-
sified in two ways: (1) by thermal contact resistance and
(2) by thermal boundary resistance. Thermal contact resis-
tance originates from mismatches in the surface conditions
of two solid bodies. Thermal boundary resistance is due
to the mismatch in the vibrational harmonics of energy
carriers (i.e. phonon spectra) and/or the flow of electronic
energy carriers between the materials [241]. Thermal con-
tact resistance depends on the contact area and how well
the filler and polymer matrix are bonded together. Sur-
face treatment of fillers is widely used to reduce the
thermal interfacial resistance and improve the thermal
conductivity. However, it must be mentioned that surface
functionalization may not always lead to improved thermal
conductivity, if it also leads to the formation of defects. For
example, carbon nanotubes were treated with strong acid
to introduce carboxylic group onto the surface of carbon
nanotubes. The functionalization increased the interface
coupling, but also led to the formation of defects, which
impede the acoustic phonon transport in the carbon nano-
tubes [242].
Various surface modifiers have been used to mod-
ifying filler surface to decrease thermal interfacial
resistance, including surfactants [243], coupling agents,
e.g. organo-silanes and titanates [63,236,238,244–259],
functional polymers [260–263], inorganic coatings
[264–277]. Organo-silanes with a general formula of
(RO)3 –Si–(CH2 )n –Y (where Y is a polymer reactive group)
are the most popular and effective surface modifiers.
The trialkoxysilane group can hydrolyze resulting in
68 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 25. Schematic of the prepared composite systems with the morphologies of the different filler sizes, and the bimodal distribution characteristics with
relative compositions of 2:1, 1:1, and 1:2. [201], Copyright 2012. Reproduced with permission from Elsevier Ltd.
Fig. 26. Schematic diagram of the BN/CNTs filler network in the polymer
matrix. [234], Copyright 2012. Reproduced with permission from Elsevier
Ltd.
the formation of silanol groups (Si–OH) and then con-
dense with filler surface hydroxyls to form permanent
attachments, while polymer reactive group can form a
chemical link to the polymer matrix. Thus, the adhesion
between polymers and fillers is improved and interfacial
scattering of phonons is reduced. The thermal conductivity
improvement depends on the filler surface chemistry,
polymer type, silane chemistry, and amount of silane.
Research results suggested that there was an optimum
amount of silane to be used; too little or too much of
silane would not lower the interfacial resistance [253].
The thermal conductivity enhancement of the composites
due to the improved interface also depends on the filler
loading. Below the critical concentration the covalent
bonding tends to result in higher enhancement of thermal
conductivity. Above the critical concentration, however,
covalent bonding results in less effective improvement of
thermal conductivity in the composites. The critical filler
concentration is interpreted as the percolation threshold
of fillers in polymer matrix. The covalent bonding between
the particles and the matrix is important to increase the
thermal conductivity of the composites with filler loading
lower than the critical concentration. Direct contacts
among neighboring particles, however, give higher ther-
mal conductivity enhancement in the composites where
particle loading exceeds the critical concentration [244].
It should be mentioned that silane treatment also
helped to improve the dispersion of filler in polymer and
reduce viscosity during processing. To improve the disper-
sion of AlN in epoxy, Lee et al. used a two-layer surfactant
approach with silane as the first layer and phosphate ester
as the second layer dispersant [278]. Hong et al. [279]
compared the TC of poly(dimethyl siloxane) (PDMS)/CNTs
composites prepared with raw CNT and surface modified
CNT. Better dispersion and 10% increase on TC of compos-
ites were observed after modifications. It was elucidated
that the thermal conductivity enhancement originating
from the interface improvement could be significantly off-
set by the defects (e.g., voids and pores). Voids and pores
can be reduced by a certain surface treatment technique,
i.e., functionalization of AlN by mercapto-terminated silane
for epoxy/AlN composites [244].
Silane treatment not only can improve TC, but also
can protect some moisture sensitive fillers, such as AlN.
Metal oxide has numerous –OH group on the surface and
can be easily modified. It is much easier to be incor-
porated in polymer matrix even without modification,
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 27. Schematic diagram illustrating process of as-grown BNNTs transformation to POSS fuctionalized BNNTs. [280], Copyright 2013. Reproduced with
permission from John Wiley and Sons.
comparing with nitride or carbide ceramic fillers. Among
those ceramic fillers, hexagonal BN is most difficult to
be surface-functionalized because of its layered hexago-
nal crystal structure. The platelet 001 plane is molecularly
smooth and there are no surface functional groups avail-
able for chemical modifications. The only spot that can be
used for grafting function groups is at the edge planes of the
platelets. The functional groups can be covalently bonded
to the boron atoms, and help h-BN to be well dispersed in
polymer matrix and improve the interface adhesion.
Polymers have also been used to modify fillers, as dis-
cussed by many researchers. These modified fillers have
a core–shell structure that exhibit enhanced physical and
chemical properties that are associated with shell surface
and encapsulated core materials. The core is usually sur-
rounded by a homogeneous spherical shell containing a
thermally different material. These core–shell structured
fillers are advantageous due to the improvements on ther-
mal and/or mechanical properties, modifications to the
surface properties of the fillers, and improvements in
the dispersion of the fillers in the binder matrix. Admi-
cellar polymerization was used to coat polystyrene and
polymethyl methacrylate on the BN surface to improve
the interfacial adhesion in the BN-filled epoxy compos-
ite. This admicellar surface treatment was found to be
69
more effective in improving the interfacial adhesion than
the more conventional silane treatment [260]. Glycidyl
methacrylate-butyl acrylate-maleic anhydride (GBM) ter-
polymers with different molecular weights were used
to treat aluminum nitride (AlN). It was shown that the
AlN treated with GBM gave higher thermal conductiv-
ity in cyanate ester composites than those modified with
silane [261]. Polyimide (PI)-modified AlN fillers referred
as AlN@PI were reported and used for electronic encap-
sulation in high performance polymer composites [181].
These AlN@PI/epoxy composites exhibited better thermal
and dielectric properties than the untreated AlN composite.
At 40 wt.% of filler loading, the TC of AlN@PI/epoxy compos-
ite reached 2.03 W/(m K). As shown in Fig. 27, polyhedral
oligosilsesquioxane (POSS) encapsulated BN nanotubes
were successfully achieved and were demonstrated to be
very effective nanofillers for making composites with high
TC [280].
Not only polymers can be coated on the surface of
inorganic filler, but also inorganic material can be coated
to form a core–shell structure. Core/shell structure of
metal/metal oxide, metal/carbon, metal/ceramic have been
reported. For many applications, thermally conductive
composites need to be electrically insulating. Metal parti-
cle have high TC. However, they are electrically conductive,
70 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 28. Schematic illustration depicting the formation process of
the Al@Al2 O3 @SiO2 nanoparticles and multilayer core–shell (AlF-
Al)@Al2 O3 @SiO2 fibers. [266], Copyright 2012. Reproduced with permis-
sion from AIP Publishing LLC.
and cannot be used in such applications. Metallic fillers
can be made electrically insulating after being coated
with an insulating layer. With this strategy, heat conduc-
tive and electrically insulating polymer composites can
be prepared. Silica-coated silver nanowires (AgNWs@SiO2 )
were intentionally designed and synthesized by a sol–gel
method and then incorporated into epoxy matrix [264].
The silica outer layer not only helps to disperse AgNWs
in epoxy with enhanced interfacial interaction, but also
improves the TC of the composites. Experimental data
showed that TC of an epoxy/AgNWs@SiO2 composite with
4 vol.% filler loading was increased to 1.03 W/(m K) com-
pared to 0.57 W/(m K) of an epoxy/AgNWs composite with
identical nanowire loading. In the meanwhile, the insulat-
ing silica nanolayer effectively avoided the formation of an
electrically conductive network of AgNWs in epoxy, lead-
ing to a highly electrical insulating composite. Al2 O3 coated
spherical Al particles [265] and SiO2 coated Al particles or
fibers [266] have also been proposed as thermally conduc-
tive fillers, as shown in Fig. 28. With similar concept, SiC
particles are thermally coated with a nano layer of SiO2
by oxidation at high temperatures [267]. Silane was used
to further treat the surface of silica coated SiC particles to
improve the interaction between filler and polymer matrix.
Choi et al. reported a synthesis of SiO2 coated graphite by a
polyvinylpyrrolidone (PVP)-assisted sol–gel reaction [268].
They found that both in-plane and through-plane TC values
of silica-coated graphite/TPEE composites were improved
comparing with those of raw graphite/TPEE composite.
Zhao et al. [269] reported a synthesis of SiO2 coated carbon
nanotubes (SiO2@CNTs) with different coating thickness
by a sol–gel method. SiO2 @CNTs was compounded with
polyurethane (PU) to prepare PU/SiO2 @CNT composites.
The effect of SiO2 @MWCNTs on the TC and electrical insu-
lation properties of PU was investigated and the results
showed that silica layer improved the interfacial interac-
tion between MWCNTs and PU, enhanced the dispersion of
MWCNTs in the PU matrix, and improved the TC of com-
posite. Due to the electrical insulation of the SiO2 outer
layer, PU/SiO2 @CNT composites had almost similar electri-
cal resistivity to pure PU.
The shell materials do not necessarily have to be elec-
trically insulating. Yu et al. [270] demonstrated a facile
synthesis of carbon fiber–copper core–shell structured
filler. Copper shells were coated on carbon fibers through
electroplating method and post-treated via rapid thermal
annealing technique, as shown in Fig. 29. The epoxy/Cu-
plated carbon fiber composites with Cu shell of 12.0 vol.%>
prepared via compression molding, had 18 times larger in-
plane TC (47.2 W/(m K)) and 6 times larger through-plane
TC (3.9 W/(m K)) than epoxy/carbon fiber composite. This
can be attributed to the Cu shell with a high degree of
crystal perfection providing continuous heat conduction
pathway.
Mesoporous materials can also be employed as shell
to construct a highly thermally conductive pathway.
Core/shell fillers consisting of FeCr metal core and meso-
porous Al2 O3 shell particles were fabricated [271]. The
composite with the core–shell structured fillers showed
a highly enhanced TC compared with that with typical
untreated FeCr particles. Because Al2 O3 had a lower TC than
metal core, the improved TC was considered to be the result
of better thermal conductance through the shell layer from
the core particle to the continuous polymer medium, as
shown in Fig. 30.
Beside metal oxides, nitride materials can also be used
as a shell. Various methods have been developed to coat BN
on the surface of carbon fibers, CNTs, SiO2 , GaN nanorods
[272]. For example, H3 BO3 –urea mixture was used as pre-
cursors. Upon heating process under N2 protection, H3 BO3
decomposed to B2 O3 , which reacts with NH3 produced by
the decomposition of urea to form highly thermally con-
ductive BN out layer [273,274].
8. Microstructure control of heat conductive
polymer composites
8.1. Filler orientation
Many heat conductive fillers have anisotropic TC. These
fillers have non-spherical shape, such as plate-like boron
nitride, fibers, carbon nanotubes, graphene sheets, graphite
flakes, wires. These non-spherical fillers can be oriented
during processing, which usually leads to high TC in the
orientation direction, but low TC in the direction perpen-
dicular to the orientation direction. Anisotropic TC due to
the orientation of fillers has been observed in the com-
posites with boron nitride [163,281–284], carbon nanotube
[285–288], carbon fibers [237,289–293], Al2 O3 fiber [294],
stainless-steel fiber [295], Hemp fiber [296], glass fibers
[293], silicon nitride nanowire [212], graphite [297,298],
graphene [299], Ni platelets [300], and diamond [301].
Some applications require composites with isotropic TC,
while in other applications high TC in a specific direction is
more desired. However, in many cases, the preferred direc-
tion to have high TC differs from the direction in which the
composites have a high TC. For example, in many cases,
the heat conductive fillers have been oriented in the flow
direction, which led to a high TC in in-plane direction,
while a high TC in through-plane direction is more desired.
Therefore, randomizing filler orientation or using specific
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85 71

Fig. 29. (a) Schematic of fabrication process of epoxy/Cu-plated CF composite and cross-view SEM micrographs of (b) pristine CF, (c) Cu-plated CF, (d)
epoxy/Cu-plated CF composite and side-view SEM micrograph (e) epoxy/Cu-plated CF composite. Arrows in part d indicate the epoxy matrix, Cu shell, and
carbon fiber core. [270], Copyright 2014. Reproduced with permission from the American Chemical Society.

orientation approaches to orient fillers into the desired

direction is needed.

8.1.1. Orientation by shear or extensional flow during

processing
Orientation of fillers can result from the shear or stretch-
ing force during various methods of processing, such as
injection molding [237,294,295], extrusion [288], com-
pression molding [212], tape casting [163,298], foaming
[283], solid state shear milling [297], multistage stretching
[282], electrospinning [281,285].

8.1.2. Orientation by external fields

Fig. 30. The improvement of thermal conductivity of the composite con-
sisting of core–shell particles and untreated uni-modal structure. [271],
Copyright 2015. Reproduced with permission from Elsevier Ltd.
Orientation of fillers can be also obtained by an external
field, such as magnetic and electrical field. Solis and Martin
[300] used magnetic fields to both orient and agglomerate
Ni spheres and platelets into structures that can efficiently
conduct heat. Field structuring increased the TC substan-
tially along the applied field without a significant reduction
in the transverse direction to the field. The most important
72 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
advantage of field structuring is that without increasing the
viscosity of filled resin, one could increase the composite
TC almost by a factor of three.
Yan et al. [299] used magnetic field to align graphene
nanosheets (GNSs) in epoxy composites. To serve
this purpose, the nanosheet surface was modified by
Fe3 O4 through a co-precipitation method. The resulting
epoxy/GNS–Fe3 O4 composites possessed high TC in a
parallel magnetic-alignment direction at low GNS–Fe3 O4
loadings, which greatly outperformed the composites with
randomly dispersed bare GNSs.
Electric field has also been used to orient thermally con-
ductive fillers. Linear assemblies of BN nanosheets (LABNs)
were fabricated in polysiloxane/BN nanosheet composite
film under a high DC electric field. The stretched structure
induced effective heat conduction through the out-of-
plane direction of the composite film [302]. This strategy
was further advanced to assemble BN nanosheets into a
LABN structure with extended length and denser popula-
tion in polymer based composites using microscopic molds
[284]. The relocation of diamond fillers was performed
in a prepolymer mixture of polysiloxane under different
electric fields AC, DC, and switched DC, before the mix-
ture became cross-linked. In the cured composite film, the
self-assemblies of linearly aligned diamond fillers (LADFs)
connect the film planes as bridges. Composites exhibited
enhanced TC and electrical insulation [301].
8.1.3. Orientation of carbon nanotube by chemical vapor
deposition
Vertically aligned multiwalled carbon nanotube (VA-
MWCNT) arrays have generated significant interest in
recent years. Aligned multi-walled carbon nanotubes
(MWCNTs) were made by chemical vapor deposition. By
placing CNTs vertically and spanning the system com-
ponents, one can reduce the number of CNT/polymer
interfaces in the through-thickness direction, thus mini-
mizing the effective thermal interfacial resistance in the
direction of heat flow.
A TC of 3.8 W/(m K) in a VA MWCNT–polymer composite
along the alignment direction with 2% volume fraction of
MWCNTs was reported by Borca-Tasciuc et al. [303]. Ivanov
et al. [304] reported a TC of 5.5 ± 0.7 W/(m K) for an epoxy-
infiltrated VA-MWCNT array (8 ± 1 vol.%, 2 mm long). Kaul
et al. [286] estimated the TC of their CNT epoxy com-
posites to be about 5.8 W/(m K); TC also exhibited slight
increase with temperature in the range of 240–300 K. It
was suggested that through-thickness thermal conductiv-
ities as high as 25 W/(m K) can be potentially fabricated,
as the TC of a VA-MWCNT array can be increased by an
order of magnitude by using a standard high-temperature
post-annealing step. Sihn et al. [287] incorporated aligned
multi-walled carbon nanotubes (MWCNTs) in the adhe-
sive layer to enhance the through-thickness TC in the
adhesively bonded joints. The measured value of the
through-thickness TC of the modified adhesive joint with
the MWNCT was over 250 W/(m K), which was greater than
the TC of neat adhesive joint by several orders of magni-
tudes. These studies suggest that the thermal conductance
at CNT-capping layer interfaces and the morphological
Fig. 31. Sketch of boron nitride agglomerates.
structure of the individual MWCNTs are the dominating
factors that control the overall TC of the composites.
8.2. Filler agglomerates
Plate-like fillers, such as boron nitride and graphite,
have anisotropic TC. The TC in the crystal plane is different
from the through-plane TC. For example, the in-plane TC
of hexagonal born nitride has been estimated to be higher
than 300 W/(m K), while the through-plane TC is only about
3 W/(m K). When BN powders are used as fillers, the com-
posite materials often have anisotropic properties, largely
determined by the orientation of the BN platelet in the final
part. To overcome this problem, boron nitride agglomer-
ates have been developed with/without binders (as shown
in Fig. 31). In such agglomerates, plate-like BN crystals are
held together to form a larger particle to randomize their
orientation. Using BN agglomerates, more isotropic TC has
been obtained. This has been demonstrated in HDPE [305],
silicone [216], polyimide [306], polycarbonate, NylonTM 6
and NylonTM 66 [307].
These agglomerates were produced via secondary
processing of BN platelets. A process of spray drying an
aqueous slurry comprising non-spherical shaped boron
nitride particles, water, an organic binder and a base for
maintaining the pH of the slurry basic was developed
to make the agglomerates [308]. The agglomeration of
the boron nitride primary particles can be also made by
compacting the plate shaped, hexagonal boron nitride
between two rotating opposite rollers. The rollers were
pressed against each other with a defined pressure. The
compaction step was carried out many times. A thermal
treatment was carried out as an additional step preferably
at 1600–1950 ◦ C, after the compaction step [309]. High-
density agglomerated particles of hexagonal boron nitride
can be also formed by a cold forming process carried out
at ambient temperature comprising the following steps:
crushing agglomerated chunks of relatively large size high
purity hexagonal boron nitride into boron nitride particles,
cold pressing the crushed particles into a compacted form,
granulating the compacted form into a granulated powder.
The steps of cold pressing and crushing can be repeated
several times until desired density has been achieved [310].
One of the biggest challenges of using BN agglomer-
ates is to preserve the structure through all the processing
steps. BN agglomerates are relatively weak and are likely
to break down into their component platelet crystals if
sheared aggressively during processing. In particular for
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 32. The PS composites with Cu shell networks revealed 60 times larger thermal conductivity than conventional simple melt-mixed Cu beads/PS
composite. [313], Copyright 2013. Reproduced with permission from the American Chemical Society.
thermoplastic composites, the BN agglomerates can break
down during the extrusion step and/or the molding step.
Both the screw configuration during extrusion and the
flow field during molding determine the extent of shear
exerted on BN agglomerates. These processing steps should
be monitored and controlled to preserve the agglomerates’
beneficial structure.
8.3. Formation of continuous filler network
As discussed earlier, the formation of the continuous
percolation structure of the fillers with large TC is the key to
achieve high TC for the composites. The high filler content
of above 60–70 vol.% could lead to a continuous heat con-
duction path of fillers in the polymer composite. However,
high filler loading makes processing difficult and increases
the cost. Various approaches have been used to form heat
conductive path at a lower filler loading level.
8.3.1. Molding of the mixture of filler and polymer
powders
One way to achieve heat conductive path is mixing filler
particles and polymer particles together and then compres-
sion molding the mixture to get a special filler dispersion
state in which the polymer particles are surrounded by
heat conductive filler particles. The segregated fillers in
the boundary between polymer particles can form heat
conductive paths at low filler content. This strategy [311]
has been demonstrated in the Si3 N4 particle filled epoxy
composite. Using particulate epoxy resin and molding pro-
cess, a continuous network was formed by the filler in the
composites. Heat conduction is mainly performed by the
filler, resulting in a high overall TC. This strategy has also
been used to prepare AlN filled PS [198]. PS and AlN were
mixed at room temperature, then compression molded.
It was found that the TC of composites was higher for a
PS particle size of 2 mm than that for a particle size of
0.15 mm. Four mixing methods, powder mixing, solution
mixing, roll-milled mixing and melt mixing, were used to
make PE and graphite composites [312]. It was found that
the powder mixing from which the specimens were cast
73
have the highest TC, while the melt mixing gave the lowest
TC. It is obvious that the TC of a composite was significantly
affected by the dispersion state in the composite. Powder
mixing can lead to a more connected filler network, while
in melt mixing, fillers were dispersed in isolated or passi-
vated phase with thermally insulating polymer matrix. A
similar approach was used to make polymer composites
with Cu thin film network [313]. The polymer compos-
ites were created by the Cu metallization of PS beads and
then hot press molding of Cu-plated PS beads. The unique
three-dimensional Cu shell-networks in the PS matrix were
responsible for isotropic and ideal conductive performance
at even extremely low Cu contents, as shown in Fig. 32.
8.3.2. In situ polymerization in porous heat conductive
filler network
The heat conductive network can also be formed by infil-
tration of monomer into a porous heat conductive filler
body with a percolated pore structure. In situ polymeriza-
tion occurs in the porous ceramic upon heating up, and
the final morphology of the composite consists of an inter-
penetrating polymer network which fills in an AlN ceramic
skeleton. This special interpenetrating network gave rela-
tively high TC [199].
8.3.3. Self-assembly process
Self-assembly process can also be used to construct
heat conductive metallic network. The self-constructed
networks in the polymer matrix are formed via low tem-
perature sintering of nanoparticle fillers during the curing
of the polymer. Nanoparticle fillers are desirable since they
can be sintered together at lower temperatures than those
for microparticles. High heat conductive epoxy–silver com-
posites have been obtained through this process, whose
heat conductivity is up to ∼50 times higher than that
of silver microcomposites at a similar volume fraction of
fillers [170,314]. The networks form through a three-step
process comprising of self-assembly by diffusion limited
aggregation of polyvinylpyrrolidone (PVP) coated silver
nanoparticles, removal of PVP coating from the surface,
74 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
Fig. 33. The mechanism for the formation of the self-constructed metallic
network in the nanocomposite and its synergy with its flow and thermal
properties: (a) high k nanoparticles functionalized with PVP and dispersed
in uncured epoxy form a high solids volume fraction slurry able to flow
and fill the roughness of two mating surfaces; (b) the molecular coating is
removed by low temperature processing and the metallic nanoparticles
start to agglomerate and sinter into high k networks of nanorods; (c) the
high network at the end of the process with the cured polymer matrix pro-
viding compliant mechanical support. [170], Copyright 2012. Reproduced
with permission from AIP Publishing LLC.
and sintering of silver nanoparticles in high aspect ratio
networked structures, as shown in Fig. 33.
8.3.4. Double percolation
Double percolation approach has been used to lower the
percolation threshold of electrical conductivity in electrical
conductive polymer composites [315–317]. However, only
recently this approach has been used to enhance TC. For
this technique, two-phase immiscible polymer blends, in
which at least one phase is continuous, can be used as a
polymer matrix, and conducting fillers are selectively and
preferentially localized and percolated in the continuous
phase. In this way, the TC can be increased more at the
same filler loading level or less filler is needed to achieve
the same TC.
A double percolation structure has been successfully
constructed to effectively reduce the volume fraction of
fillers in poly(vinylidene fluoride) (PVDF)/polystyrene(PS)
Fig. 34. (a) Thermal conductivity of hybrid films: (䊉) PI blends and ()
Homo-PIs. The lines are the  values calculated for an ideal PI blend model
(rigid line) and a Homo-PI model (broken line) based on the Bruggeman
theory. (b) Schematic representations for ideal model structures for PI
blends with VDP structures (left) and for homo-PIs with homogeneously
dispersed ZnO-NPs (right). [321], Copyright 2011. Reproduced with per-
mission from the Society of Chemistry.
blends. The TC of the blends were significantly improved
by selectively localizing SiC nanoparticles [318] or hybrid
fillers of multi-walled carbon nanotube (MWCNTs) and sil-
icon carbide (SiC) nano particles in the PVDF phase [319].
Double percolation approach has been used to make
composites with high heat dissipation, sharp and large
amplitude PTC effect and independent adjustability of elec-
trical conductivity and TC. It is a co-continuous structure
associating a thermally conductive polymer phase (syn-
diotactic poly(styrene) (sPS) filled with aluminum oxide
(Al2 O3 ) or boron nitride (BN)) with an electrically con-
ductive polymer phase (high-density polyethylene)(HDPE)
filled with carbon nanoparticles (CNP) in appropriate pro-
portions [320].
The “vertical double percolation (VDP)” morphology
were spontaneously formed in the PI blend films composed
of a sulfur- and a fluorine-containing PI and ZnO nano par-
ticles [321], as shown in Fig. 34. The two phases were
separately aligned along the out-of-plane direction, and
ZnO-NPs were preferentially precipitated in the fluorine-
containing PI phase. At 27 vol.% of ZnO nano particles, the
blend film exhibited 410% enhancement of TC, whereas
only 90% enhancement was observed in the monophase PI
film containing homogeneously dispersed ZnO-NPs.
The double percolation concept has also been used to
increase the TC of epoxy molding compound (EMC). An
island-sea structure has been designed by filling epoxy
resin with heat conductive Si3 N4 particles and precured
epoxy-SiO2 composite particles obtained by crushing the
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
cured epoxy-SiO2 composites [233]. As Si3 N4 particles can-
not enter the precured epoxy composite particles, they will
be confined in the epoxy-sea phase. The composite gave
higher TC than the composites with homogeneously dis-
tributed Si3 N4 .
9. Applications of thermally conductive polymer
composites
Nowadays, with the increasing cooling demand in
emerging industries, new thermally conductive materi-
als are in high demand. Compared with other thermally
conductive materials, such as metals, ceramics, carbon
materials, polymer composites have following features:
(a) Electrical insulation and electrical conduction can be
controlled via selecting appropriate fillers.
(b) Easy processing for integrated parts or complex geom-
etry.
(c) Light weight.
(d) Corrosion resistant.
(e) Compliance to the geometry of the adjacent rough sur-
faces, if flexible polymer is used.
(f) Vibration damping due to resilience of polymer com-
posites.
This section lists some emerging application areas of
thermally conductive polymer composites: LED devices,
electronic assembly and packaging, battery and solar.
9.1. LED devices
Compared with conventional lighting, light-emitting
diode (LED) lighting has the advantages of a longer lifetime
and higher energy efficiency (30%). However, 70% energy in
LED devices is transformed into heat. Such large quantity of
heat can significantly influence the LED’s performance, in
terms of luminous efficiency and lifetime. At constant oper-
ation current, the luminous efficiency decreases by about
5% and the lifetime of LED decreased by half for every 10 ◦ C
rise in temperature. Therefore, a good thermal manage-
ment system for dissipating the heat from inside of the LED
package to the surroundings is very important.
A conventional LED thermal management system is
composed of a heat spreader, thermal interface material
(TIM) and heat sink. Copper and aluminum alloys are typ-
ically used for heat spreader. Silicon based grease, gels,
phase change materials (PCM) have been used as TIM.
There are continuous needs on increasing the TC of TIM or
decreasing the thermal interfacial resistance of TIM. Some
recent progress has been made on using a soft matrix mixed
with CNTs and/or nanofibers for TIM application [322]. In
order for TIM to achieve higher TC, the promising approach
is to align CNT perpendicularly with the contact surface
[323–326].
Aluminum alloys with high TC between 150 and
300 W/(m K) are typically used as heat sink material.
Although metal based heat sink has excellent TC and rel-
atively low raw material cost, the processing cost is high
and electrical conductivity is certain. Cost analysis indi-
cated that the majority of the heat sink cost (>80%) is from
75
processing. Moreover, aluminum based heat sink can add
substantially to the weight of a fixture or device. This might
have negative effects on both new designs and retrofit
installations. The trend in heat sink design is to develop
materials with less weight, lower cost and adequate ther-
mal dissipation performance. Heat conductive polymer
composites could be an alternative solution to this. Poly-
mer composites are steadily gaining more market share
for heat sink application due to their good processability,
lightweight, design flexibility, corrosion resistance, lower
processing cost, etc.
Placing chip directly on the heat sink is a new direction
for LED thermal management system development. In this
case, electrical insulation is required for heat sink materials.
Ceramic filled polymer composites are the main selection.
In general, a TC higher than 10 W/(m K) is needed for this
application. To achieve high TC, a sufficiently high filler
loading (>40 vol.%) is needed. At this high filler loading,
the polymer composites tend to have poor processability
and higher overall cost. How to reduce filler loading and
keep the same TC is one significant challenge for electri-
cally insulating polymer composites. Besides, the geometry
of heat sink could also influence the heat dissipation effi-
ciency at natural convection condition [327–329]. A final
heat management solution for LED heat sink could be
an appropriate thermally conductive polymer composites
combined with suitable design.
9.2. Electronic packaging
Higher power density and miniaturization have made
thermal management of consumer electronic devices one
of the major challenges for the semiconductor industry
[330]. The objective of thermal management in electron-
ics is to ensure that temperatures of all components in the
system are maintained within their functional temperature
range. Thus, there should be effective thermally conduc-
tive path for heat dissipation and eliminating hot spots
in electronic parts [1]. The discussion on the applications
of thermally conductive polymer composites in electronic
assembly and packaging will be focused on three areas with
pressing thermal management needs: single chip packages,
3D chip stack packages and automotive electronic control
units (ECU).
9.2.1. Single chip packages
The International Technology Roadmap for Semi-
conductors (ITRS) projected power density and junction-to
ambient thermal resistance for high-performance chips
at the 14 nm technology generation to be >100 W/cm2
and <0.2 ◦ C/W, respectively [330]. The main bottlenecks in
reducing the junction-to-ambient thermal resistance are
the thermal resistances of the thermal interface material
(TIM) and the heat sink. There is a need for TIM that pro-
vides the highest possible TC during chip operation, good
adhesion, and conformability to fill the gaps between two
rough surfaces.
The TC of TIM is relatively low, about 3–5 W/(m K).
Increasing TC of electrically insulating polymer composites
for TIM application is one challenge of single chip packag-
ing. As discussed in the earlier section, carbon-nanotubes
76 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
(CNT) or carbon nano fibers (CNF) [331–336] are potential
emerging materials used in TIMs that showed significant
improvement in heat conductivity. An insulating layer like
mica could be used to provide electrical insulation when
CNT is employed as TIM [337].
9.2.2. 3D chip stack assembly and packaging
3D chip stack technology with through silicon via
(TSV) interconnect can be used to enhance communica-
tion between ICs. However, the cooling of a stack of logic
chips becomes more complex as compared to the single
chip case. In a single chip, heat can be readily accessed and
removed from the back side (bulk silicon side) of the die.
In a 3D chip stack, there is no direct access to the back
side of the chips in the stack or a method of spreading
the heat laterally from the stack. Because of the increased
power density and various low-TC materials in the stack,
challenge of cooling becomes magnified. Increasing the TC
of the chip-to-chip interfaces within the stack would be
beneficial in 3D thermal management. High thermally con-
ductive underfill material is critical to the heat dissipation
of 3D chip stack packaging [185,338]. For this application,
underfill not only needs high TC, but also needs to have low
viscosity, good wetting to multiple surfaces, low shrink-
age during cure, and low CTE (10–14 ppm/◦ C) [339]. TC can
always be increased by increasing filler loading. However,
this causes underfill materials to have poor flowability,
which is critical to the capillary underfill application. How
to increase TC, but maintain good processability is still a
major challenge.
9.2.3. Automotive electronic control units (ECUs)
The ECU plays the crucial role of controlling and
integrating different complex actions such as mixture for-
mation, combustion and exhaust gas treatment. In order to
reduce the pollutant emissions and achieve the require-
ments of Euro 6 standards, it is expected that ECU will
have a greater functionality, a reduced size and weight,
and an increased power density. Thus, the challenge of
thermal management within the chip and surrounding
packaging is greater than ever. The die-level power dis-
sipation density is projected to exceed 100 W/cm2 in the
next 6 years [340]. Another concern is the impact of harsh
under-hood automotive ambient temperatures on elec-
tronics used in ECU assembly. The performance of thermal
grease, thermal pads and phase change materials (PCMs)
may degrade when exposed to elevated temperature over
a period of time [341,342]. Silicone polymer composites
are good option for TIM in ECU because of low modulus of
elasticity, good wetting characteristics, good thermal sta-
bility and excellent vibration damping capability [335,337].
However, the thermal resistance of gels is in the range of
0.4–0.8 (K cm2 )/W which is still considered high for this
application. Increasing TC and maintaining other proper-
ties in harsh environment is the main challenge for polymer
composites in ECU application.
9.3. Batteries
As batteries become more powerful and utilized in more
diverse applications, thermal management becomes one of
the central problems in their growing use. The heat gen-
eration rate can exceed heat dissipation rate when cells
are used at high discharge/charge rate or at high ambient
temperature. The cell may experience thermal runaway
accompanied by internal pressure buildup, which could
lead to bursting of the cell. Because of this safety issue,
highly thermally conductive materials are needed. Car-
bon nanotube/fiber filled PVDF [343] with higher TC is
a good option to replace conventional electrode material
which contain PVDF and carbon-black in Li-ion cells [344].
TC of polyacrylonitrile (PAN) nanofiber separators could
increase from 3.5 W/(m K) to 8.5 W/(m K) by only adding
8 wt.% graphene nanoflakes [345].
Electric vehicles (EVs) and hybrid electric vehicles
(HEVs) have many batteries which are combined together
in a pack. Uneven temperature distribution in a pack could
break electrical balance and reduce power output. For this
reason, it is important to reduce the temperature variations
among cells. A thermal management system is needed to
maintain a battery pack at an optimum average temper-
ature. In this case, phase changing material and coolants
can be used for heat dissipation of battery pack [346,347].
However, they are not very realistic to be applied to real
systems due to the lack of cost effectiveness and complexity
of structures. Thermally conductive polymer composites
may open a new window for thermal system design of
battery pack.
9.4. Solar
Solar as a renewable and sustainable energy is growing
rapidly in recent years. Because of the low conversion effi-
ciency of photovoltaic (PV) cells, most of the absorbed solar
energy converts into thermal energy within the cell [348].
It is well known that the solar conversion efficiency of the
PV cells decreased with the rise of its operating tempera-
ture. Increasing the temperature of PV cells by 1 ◦ C leads
to about 0.4–0.5% reduction of the relative conversion effi-
ciency for the crystalline silicon based cells [349,350] and
around 0.25% for the amorphous silicon cells [351]. In order
to increase conversion efficiency of PVs, it is desired to
remove the accumulated heat from the PV surface, espe-
cially for concentrated PV system [352]. How to conduct
heat efficiently from cell to outside is a key challenge.
EVA as the typical cell encapsulating materials has very
low TC (0.23 W/(m K)). Besides, a typical backsheet compo-
nent material DuPont TedlarTM (poly(vinylfluoride) film)
also has a low TC (0.36 W/(m K)). These two low thermally
conductive layers are the bottlenecks for heat dissipation
from cell. Using electrical insulating fillers to enhance the
TC of EVA [353] and backsheet could be an effective way to
improve the heat dissipation from cells. However, the cost
and impact of fillers on other properties, such as adhesive,
barrier properties, should also be considered.
10. Conclusions and future prospects
In this review, we discussed the research progress
on thermally conductive polymer composites and their
 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
potential applications. Based on these studies, we can for-
mulate several key messages.
(1) Thermal conductivity of polymer composites is a func-
tion of the thermal conductivities of polymer matrix
and fillers, the morphology of polymer composites and
the interaction of polymers and fillers. We need to take
a holistic approach when designing highly thermally
conductive polymer composites.
(2) Theory and modeling play an important role in the
screening potential compositions and selecting the
more promising ones. Modeling can help determine
(qualitatively or quantitatively) the dependence of
composite thermal conductivity (TC) on TC of the
matrix, TC of the filler(s), filler volume fraction and
filler shape and morphology. Combining modeling and
experimental inputs can provide not only explanation
of trends, but also quantitative designs for subsequent
experiments.
(3) Thermal conductivity of polymers is particularly
important at low filler loadings. At low filler contents,
polymer matrix acts as the thermal barrier and
becomes rate-limiting in the thermal conduction chan-
nel. Increasing the TC of polymer matrix can help
increase the TC of composites. Polymer ordering (crys-
talline and liquid crystalline) and orientation could be
possible ways to achieve higher TC of the matrix.
(4) The addition of thermally conductive inorganic fillers is
indispensable to achieve high TC. The filler type, loading
level, filler size, and filler shape have strong influence
on the TC of polymer composites. Unlike the electri-
cal conductive behavior, there does not seem to be a
clear percolation threshold for thermally conductive
composites. High TC can only be achieved at high filler
loadings, when fillers contact with each other and form
thermally conductive pathways.
(5) Filler size is also important to the TC of composites.
Composites with large fillers have less filler/polymer
interface, lower thermal interfacial resistance, and thus
higher TC. However, when the filler size is in the
nanoscale, filler properties could also change; for exam-
ple, the melting point of nano-metallic particles could
be significantly lower, thus leading to the sintering of
nanoparticles and formation of a heat conductive net-
work during polymer curing process.
(6) Hybrid fillers, such as mixture of fillers of different type,
size, and shape, can help achieve higher TC at a lower
filler loading level. They can also help to lower viscosity,
thus improving processability. Hybrid fillers can be also
used to control TC anisotropy. More isotropic TC can be
obtained with using appropriate hybrid fillers.
(7) Filler surface treatment can help improve filler disper-
sion, while also reducing the overall viscosity. More
importantly, it decreases thermal interfacial resistance;
therefore, higher TC can be obtained.
(8) Phase separated polymer blends with island-sea or
co-continuous structure can be used to design double-
percolated structures. Higher TC can be achieved at a
lower filler loading level, if the fillers are concentrated
in the continuous phase in the island-sea structure or
located in the interface in the co-continuous structure.
77
Many other techniques, such as self-assembly process,
are being developed to form heat conductive pathways
at a lower filler loading level.
(9) The orientation of fillers with anisotropic TC can lead
to the composites with anisotropic TC. Filler orien-
tation should be avoided or enhanced according to
specific application requirements. Orientation of fillers
can result from processing flow, or can be obtained by
external fields, such as magnetic and electrical field.
Despite all the successes, there are still many challenges
for heat conductive polymer composites. More research is
expected in the following areas:
(1) To achieve high TC, significant amount of fillers is
needed in polymer matrix. High filler loading not only
can cause the final composites to be brittle, but also
creates more challenges to the processing of polymer
composites. Moreover, as the fillers are more expen-
sive than polymer matrix, the cost of final composites
is high. Thus, further research is needed to obtain high
TC at low filler loadings.
(2) Thermal conductivity of polymers is important to the
TC of composites. Some liquid crystalline thermosets
can give high TC. However, they are usually expensive
due to the complicated synthesis procedure or com-
mercial non-availability of starting materials, which
prevent it from being used commercially. More impor-
tantly, most of them have very high melting point.
As they need to be heated to above melting tem-
perature for curing, the gel time will be extremely
short at high temperatures, which makes it impossible
to process them with conventional processing tech-
niques. Thermosets with high TC, good processability
and reasonable cost are still needed for practical appli-
cations. Liquid crystalline thermoplastics with smectic
structure can have a high TC. However, they usu-
ally have low molecular weight and give very poor
mechanical properties. Further improvement of their
mechanical properties is needed. Polymer blends with
highly packed structure and high density of hydrogen
bonds can give high TC. How to introduce this concept
into conventional polymers needs further exploration.
Highly oriented polymeric fibers can give high TC. It is
believed that they will find more applications on ther-
mally conductive composites in the future.
(3) Future research is needed to develop novel heat con-
ductive fillers. Fillers with high aspect ratio can giver
higher TC at low filler content. Heat conductive, but
electrical insulating inorganic fibers are particularly
useful for electrical insulating heat conductive com-
posites. However, those fibers are rarely commercially
available. The spherical fillers, such as spherical Al2 O3 ,
can give lower viscosity than fillers with irregular shape
or fillers with high aspect ratio. However, Al2 O3 has rel-
atively low TC. Spherical fillers with high TC, such as
spherical boron nitride particles could be very useful
for many applications.
(4) Controlling the orientation and location of fillers can
help to achieve high TC at lower filler content. Novel
processing techniques that can assist fillers to form
78 H. Chen et al. / Progress in Polymer Science 59 (2016) 41–85
heat conductive pathways will continue to emerge in
the future, for example, the recent development of 3D
printing could help to locate filler into a specific loca-
tion in the composites.
Acknowledgements
The authors are grateful to Kevin Howard, Michael Mills,
and Jeff Zawisza at The Dow Chemical Company for many
fruitful discussions during the preparation of this work.
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