We report a 40% improvement of the thermal conductivity of graphite nanoplatelets–epoxy composites by chemical functionalization of graphite nanoplatelets utilizing nitric acid treatment, which also serves to enhance the spreadability of the material. FTIR and Raman spectroscopy confirmed the presence of a variety of oxygen functional groups at the edges and basal plane of the functionalized graphite nanoplatelets, which contributed to improved interaction with the polymer matrix. A comparative statistical analysis of the particle size distributions in pristine and functionalized graphite nanoplatelets based on scanning electron microscopy showed an increasing degree of exfoliation of the functionalized material. We compare the performance of the functionalized graphite nanoplatelets and carbon nanotubes as fillers in the polymer matrix and discuss the prospects for utilization of graphite nanoplatelets-based thermal interface materials in electronic packaging.
Issue Section:
Carbon Nanotubes
Keywords:
graphite nanoplatelet (GNP),
thermal interface materials,
particle size,
polymer composites,
thermal properties,
carbon nanotubes,
Fourier transform spectra,
graphite,
nanostructured materials,
oxidation,
particle size,
polymers,
Raman spectroscopy,
scanning electron microscopy,
statistical analysis,
thermal conductivity,
thermal management (packaging)
References
1.
Schelling
, P. K.
, Shi
, L.
, and Goodson
, K. E.
, 2005, “Managing Heat for Electronics
,” Mater. Today
, 8
, pp. 30
–35
.2.
Samson
, E. C.
, Machiroutu
, S. V.
, Chang
, J.Y.
, Santos
, I.
, Hermerding
, J.
, Dani
, A.
, Prasher
, R.
, and Song
, D. W.
, 2005, “Interface Material Selection and a Thermal Management Technique in Second-Generation Platforms Built on Intel® Centrino™ Mobile Technology
,” Intel Technol. J.
, 9
, pp. 75
–86
.3.
Prasher
, R.
, 2006, “Thermal Interface Materials: Historical Perspective, Status, and Future Directions
,” Proc. IEEE
, 94
, pp. 1571
–1586
.4.
Chung
, D. D. L.
, 2001, “Materials for Thermal Conduction
,” Appl. Therm. Eng.
, 21
, pp. 1593
–1605
.5.
Biercuk
, M. J.
, Llaguno
, M. C.
, Radosavljevic
, M.
, Hyun
, J. K.
, Johnson
, A. T.
, and Fischer
, J. E.
, 2002, “Carbon Nanotube Composites for Thermal Management
,” Appl. Phys. Lett.
, 80
, pp. 2767
–2769
.6.
Leong
, C. K.
, and Chung
, D. D. L.
, 2004, “Carbon Black Dispersions and Carbon-Silver Combinations as Thermal Pastes That Surpass Commercial Silver and Ceramic Pastes in Providing High Thermal Contact Conductance
,” Carbon
, 42
, pp. 2323
–2327
.7.
Yasmin
, A.
, and Daniel
, I. M.
, 2004, “Mechanical and Thermal Properties of Graphite Platelet/Epoxy Composites
,” Polymer
, 45
, pp. 8211
–8219
.8.
Bryning
, M. B.
, Milkie
, D. E.
, Islam
, M. F.
, Kikkawa
, J. M.
, and Yodh
, A. G.
, 2005, “Thermal Conductivity and Interfacial Resistance in Single-Wall Carbon Nanotube Epoxy Composites
,” Appl. Phys. Lett.
, 87
, 161909
.9.
Yu
, A.
, Itkis
, M. E.
, Bekyarova
, E.
, and Haddon
, R. C.
, 2006, “Effect of Single-Walled Carbon Nanotube Purity on the Thermal Conductivity of Carbon Nanotube-Based Composites
,” Appl. Phys. Lett.
, 89
, p. 133102
.10.
Fukushima
, H.
, Drzal
, L. T.
, Rook
, B. P.
, and Rich
, M. J.
, 2006, “Thermal Conductivity of Exfoliated Graphite Nanocomposites
,” J. Therm. Anal. Calorim.
, 85
, pp. 235
–238
.11.
Yu
, A.
, Ramesh
, P.
, Itkis
, M. E.
, Bekyarova
, E.
, and Haddon
, R. C.
, 2007, “Graphite Nanoplatelet-Epoxy Composite Thermal Interface Materials
,” J. Phys. Chem. C
, 111
, pp. 7565
–7569
.12.
Yu
, A.
, Ramesh
, P.
, Sun
, X. B.
, Bekyarova
, E.
, Itkis
, M. E.
, and Haddon
, R. C.
, 2008, “Enhanced Thermal Conductivity in a Hybrid Graphite Nanoplatelet—Carbon Nanotube Filler for Epoxy Composites
,” Adv. Mater.
, 20
, pp. 4740
–4744
.13.
Lin
, C.
, and Chung
, D. D. L.
, 2009, “Graphite Nanoplatelet Pastes vs. Carbon Black Pastes as Thermal Interface Materials
,” Carbon
, 47
, pp. 295
–305
.14.
Veca
, L. M.
, Meziani
, M. J.
, Wang
, W.
, Wang
, X.
, Lu
, F. S.
, Zhang
, P. Y.
, Lin
, Y.
, Fee
, R.
, Connell
, J. W.
, and Sun
, Y. P.
, 2009, “Carbon Nanosheets for Polymeric Nanocomposites With High Thermal Conductivity
,” Adv. Mater.
, 21
, pp. 2088
–2092
.15.
Debelak
, B.
, and Lafdi
, K.
, 2007, “Use of Exfoliated Graphite Filler to Enhance Polymer Physical Properties
,” Carbon
, 45
, pp. 1727
–1734
.16.
Ganguli
, S.
, Roy
, A. K.
, and Anderson
, D. P.
, 2008, “Improved Thermal Conductivity for Chemically Functionalized Exfoliated Graphite/Epoxy Composites
,” Carbon
, 46
, pp. 806
–817
.17.
Keblinski
, P.
, and Cleri
, F.
, 2004, “Contact Resistance in Percolating Networks
,” Phys. Rev. B
, 69
, 184201
.18.
Shenogin
, S.
, Xue
, L. P.
, Ozisik
, R.
, Keblinski
, P.
, and Cahill
, D. G.
, 2004, “Role of Thermal Boundary Resistance on the Heat Flow in Carbon-Nanotube Composites
,” J. Appl. Phys.
, 95
, pp. 8136
–8144
.19.
Shenogina
, N.
, Shenogin
, S.
, Xue
, L.
, and Keblinski
, P.
, 2005, “On the Lack of Thermal Percolation in Carbon Nanotube Composites
,” Appl. Phys. Lett.
, 87
, 133106
.20.
Gao
, J.
, Zhao
, B.
, Itkis
, M. E.
, Bekyarova
, E.
, Hu
, H.
, Kranak
, V.
, Yu
, A.
, and Haddon
, R. C.
, 2006, “Chemical Engineering of the Single-Walled Carbon Nanotube-Nylon 6 Interface
,” J. Am. Chem. Soc.
, 128
, pp. 7492
–7496
.21.
Bekyarova
, E.
, Thostenson
, E. T.
, Yu
, A.
, Itkis
, M. E.
, Fakhrutdinov
, D.
, Chou
, T. W.
, and Haddon
, R. C.
, 2007, “Functionalized Single-Walled Carbon Nanotubes for Carbon Fiber-Epoxy Composites
,” J. Phys. Chem. C
, 111
, pp. 17865
–17871
.22.
Shenogin
, S.
, Bodapati
, A.
, Xue
, L.
, Ozisik
, R.
, and Keblinski
, P.
, 2004, “Effect of Chemical Functionalization on Thermal Transport of Carbon Nanotube Composites
,” Appl. Phys. Lett.
, 85
, pp. 2229
–2231
.23.
Prasher
, R.
, 2007, “Thermal Conductance of Single-Walled Carbon Nanotubes Embedded in an Elastic Half-Space
,” Appl. Phys. Lett.
, 90
, 143110
.24.
Martin
, W. H.
, and Brocklehurst
, J. E.
, 1964, “The Thermal Expansion Behaviour of Pyrolytic Graphite Bromine Residue Compounds
,” Carbon
, 1
, pp. 133
–141
.25.
Anderson
, S. H.
, and Chung
, D. D. L.
, 1984, “Exfoliation of Intercalated Graphite
,” Carbon
, 22
, pp. 253
–263
.26.
Chung
, D. D. L.
, 1987, “Exfoliation of Graphite
,” J. Mater. Sci.
, 22
, pp. 4190
–4198
.27.
Weng
, W. G.
, Chen
, G. H.
, Wu
, D. J.
, Lin
, Z. Y.
, and Yan
, W. L.
, 2003, “Preparation and Characterizations of Nanoparticles from Graphite Via an Electrochemically Oxidizing Method
,” Synth. Met.
, 139
, pp. 221
–225
.28.
Ramesh
, P.
, Bhagyalakshmi
, S.
, and Sampath
, S.
, 2004, “Preparation and Physicochemical and Electrochemical Characterization of Exfoliated Graphite Oxide
,” J. Colloid Interface Sci.
, 274
, pp. 95
–102
.29.
Hontoria-Lucas
, C.
, López-Peinado
, A. J.
, López-González
, J. de D.
, Rojas-Cervantes
, M. L.
, and Martín-Aranda
, R. M.
, 1995, “Study of Oxygen-Containing Groups in a Series of Graphite Oxides—Physical and Chemical Characterization
,” Carbon
, 33
, pp. 1585
–1592
.30.
Szabo
, T.
, Berkesi
, O.
, Forgo
, P.
, Josepovits
, K.
, Sanakis
, Y.
, Petridis
, D.
, and Dekany
, I.
, 2006, “Evolution of Surface Functional Groups in a Series of Progressively Oxidized Graphite Oxides
,” Chem. Mater.
, 18
, pp. 2740
–2749
.31.
Chen
, G. H.
, Weng
, W. G.
, Wu
, D. J.
, Wu
, C. L.
, Lu
, J. R.
, Wang
, P. P.
, and Chen
, X. F.
, 2004, “Preparation and Characterization of Graphite Nanosheets From Ultrasonic Powdering Technique
,” Carbon
, 42
, pp. 753
–759
.32.
Kinoshita
, K.
, 1988, Carbon Electrochemical and Physicochemical Properties
, Wiley
, New York
.33.
Mawhinney
, D. B.
, Naumenko
, V.
, Kuznetsova
, A.
, Yates
, J. T. J.
, Liu
, J.
, and Smalley
, R. E.
, 2000, “Infrared Spectral Evidence for the Etching of Carbon Nanotubes: Ozone Oxidation at 298 K
,” J. Am. Chem. Soc.
, 122
, pp. 2383
–2384
.34.
Ramesh
, P.
, and Sampath
, S.
, 2001, “Electrochemical and Spectroscopic Characterization of Quinone Functionalized Exfoliated Graphite
,” Analyst
, 126
, pp. 1872
–1877
.35.
Kim
, U. J.
, Furtado
, C. A.
, Liu
, X. M.
, Chen
, G. G.
, and Eklund
, P. C.
, 2005, “Raman and IR Spectroscopy of Chemically Processed Single-Walled Carbon Nanotubes
,” J. Am. Chem. Soc.
, 127
, pp. 15437
–15445
.36.
Niyogi
, S.
, Bekyarova
, E.
, Itkis
, M. E.
, McWilliams
, J. L.
, Hamon
, M. A.
, and Haddon
, R. C.
, 2006, “Solution Properties of Graphite and Graphene
,” J. Am. Chem. Soc.
, 128
, pp. 7720
–7721
.37.
Tuinstra
, F.
, and Koenig
, J. L.
, 1970, “Raman Spectrum of Graphite
,” J. Chem. Phys.
, 53
, pp. 1126
–1130
.38.
Dresselhaus
, M. S.
, Dresselhaus
, G.
, Eklund
, P. C.
, and Chung
, D. D. L.
, 1977, “Lattice-Vibrations in Graphite and Intercalation Compounds of Graphite
,” Mater. Sci. Eng.
, 31
, pp. 141
–152
.39.
Ferrari
, A. C.
, and Robertson
, J.
, 2000, “Interpretation of Raman Spectra of Disordered and Amorphous Carbon
,” Phys. Rev. B
, 61
, pp. 14095
–14107
.40.
Hung
, M. T.
, Choi
, O.
, Ju
, Y. S.
, and Hahn
, H. T.
, 2006, “Heat Conduction in Graphite-Nanoplatelet-Reinforced Polymer Nanocomposites
,” Appl. Phys. Lett.
, 89
, 023117
.41.
Sun
, X.
, Ramesh
, P.
, Itkis
, M. E.
, Bekyarova
, E.
, and Haddon
, R. C.
, 2010, “Dependence of the Thermal Conductivity of Two-Dimensional Graphite Nanoplatelet-Based Composites on the Nanoparticle Size Distribution
,” J. Phys.: Condens. Matter
22
, p. 334216
.42.
Prasher
, R. S.
, Shipley
, J.
, Prstic
, S.
, Koning
, P.
, and Wang
, J. L.
, 2003, “Thermal Resistance of Particle Laden Polymeric Thermal Interface Materials
,” ASME J. Heat Transfer
, 125
, pp. 1170
–1177
.43.
Prasher
, R. S.
, Chang
, J. Y.
, Sauciuc
, I.
, Narasimhan
, S.
, Chau
, D.
, Chrysler
, G.
, Myers
, A.
, Prstic
, S.
, and Hu
, C.
, 2005, “Nano and Micro Technology-Based Next-Generation Package-Level Cooling Solutions
,” Intel Technol. J.
, 9
, pp. 285
–296
.44.
Lin
, C. G.
, and Chung
, D. D. L.
, 2009, “Rheological Behavior of Thermal Interface Pastes
,” J. Electron. Mater.
, 38
, pp. 2069
–2084
.45.
Abadi
, P. P. S. S.
, Leong
, C. K.
, and Chung
, D. D. L.
, 2009, “Factors That Govern the Performance of Thermal Interface Materials
,” J. Electron. Mater.
, 38
, pp. 175
–192
.46.
Wakharkar
, V.
, Matayabas
, C.
, Lehaman
, E.
, Manepalli
, R.
, Renavikar
, M.
, Jayaraman
, S.
, and LeBonheur
, V.
, 2005, “Materials Technologies for Thermomechanical Management of Organic Package
,” Intel Technol. J.
, 9
, pp. 309
–323
.47.
Leong
, C. K.
, and Chung
, D. D. L.
, 2003, “Carbon Black Dispersions as Thermal Pastes That Surpass Solder in Providing High Thermal Contact Conductance
,” Carbon
, 41
, pp. 2459
–2469
.48.
Xu
, Y. S.
, and Chung
, D. D. L.
, 2000, “Increasing the Thermal Conductivity of Boron Nitride and Aluminum Nitride Particle Epoxy-Matrix Composites by Particle Surface Treatments
,” Compos. Interfaces
, 7
, pp. 243
–256
.49.
Xu
, Y. S.
, Chung
, D. D. L.
, and Mroz
, C.
, 2001, “Thermally Conducting Aluminum Nitride Polymer-Matrix Composites
,” Composites, Part A
, 32
, pp. 1749
–1757
.Copyright © 2011
by American Society of Mechanical Engineers
You do not currently have access to this content.
