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Graphene-polymer composites

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2012 IOP Conf. Ser.: Mater. Sci. Eng. 40 012018
(http://iopscience.iop.org/1757-899X/40/1/012018)
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International Conference on Structural Nano Composites (NANOSTRUC 2012)
James Njuguna

International Conference on Structural Nano Composites (NANOSTRUC 2012)

IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012018
doi:10.1088/1757-899X/40/1/012018

Graphene-polymer composites
G Carotenuto1, V Romeo1, I Cannavaro2, D Roncato2, B Martorana2 and
M Gosso2
1

Institute of Composite and Biomedical Materials. National Research Council.

Piazzale Tecchio, 80 80125 Napoli. Italy.
2
Centro Ricerche Fiat. Strada Torino, 50 10050 Orbassano (TO). Italy.
Corresponding authors e-mail address: giancaro@unina.it
Abstract. Graphene is a novel nanostructured material that can be conveniently used as filler
for thermoplastic polymers or thermosetting resins, and the resulting nanocomposite material
has unique mechanical and chemical/physical properties. Industrial production of
graphene/polymer materials requires the availability of a chemical route to produce massive
amount of graphene. Natural graphite flakes can be the best starting material for a bulkproduction of graphene to be used in the polymeric nanocomposite preparation.

1. Introduction
Graphene is a rigid planar nanostructure made of a single layer of carbon atoms arranged in an
hexagonal crystal lattice [1,2]. Graphene can be also considered as a sort of two-dimensional
macromolecule, where benzene is the repeating structural unit. In particular, this molecular structure is
made of sp2-hybridized carbon atoms involved in both and C-C covalent bonds delocalized to the
full molecular structure. The graphene nanostructure can be advantageously used as a filler for
thermoplastic polymers and thermosetting resins since it provides polymers of a number of functional
characteristics which are not accessible by using other types of fillers [3-24].
The main characteristic of this special type of filler is the unique aspect ratio (the height of a
graphene plane is of only a few Angstroms while the other two dimensions are of hundred of microns).
Graphene has a number of unusual characteristics, for example its molecular structure is not
permeable also to very small molecules like H2. and noble gasses [25], it is characterized by the best
mechanical properties known for a solid material (better than carbon nanotubes and steel), high
electrical/thermal conductivity (for the absence of electron scattering phenomena), it shields
electromagnetic waves (ultraviolect, visible, infrared and microwaves), etc. Some of these very
interesting characteristics of the graphene molecule are given in Table I. As a consequence, graphenepolymer composites are unique materials that can be exploited for both functional and structural
applications in different technological fields.
The graphene molecules have been synthesized by chemical vapor deposition (CVD) and epitaxial
growth on nickel or SiC substrates, however high-quality graphene and graphene-based materials (e.g.,
graphene-polymer composites, grafene intercalated by metal nanoparticles or other nanostructures like
fullerene and/or CNTs) can be simply obtained starting from natural graphite.
There have been a number of efforts to make very thin films of graphite by mechanical exfoliation
(starting from 1990 and continuing until after 2004) but nothing thinner than 50 to 100 layers was
produced during these years. A key advance in the science of graphene came when Andre Geim and

Published under licence by IOP Publishing Ltd

International Conference on Structural Nano Composites (NANOSTRUC 2012)

IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012018
doi:10.1088/1757-899X/40/1/012018

Kostya Novoselov at Manchester University managed to extract single-atom-thick crystallites

(graphene) from bulk graphite in 2004. The Manchester researchers pulled out graphene layers from
graphite and transferred them onto thin SiO2 on a silicon wafer in a process sometimes called
micromechanical cleavage or, simply, the Scotch tape technique. The SiO2 electrically isolated the
graphene, and was weakly interacting with the graphene, providing nearly charge-neutral graphene
layers. However, graphite micromechanical exfoliation cannot be used for bulk-scale graphene
production and approaches based on the production of colloidal suspensions must be used.
2. Graphene bulk-production
Weak physical interactions (Van der Waals forces) are involved in the natural graphite, and material
cohesion is possible only because of the very large number of interactions simultaneously acting
among neighbor carbon sheets. Therefore, the graphite structure is made of perfectly piled flat carbon
sheets touching each other to allow induction of instantaneous dipoles among the neighbor carbon
planes. Such a well-ordered structure is the basic condition for cohesion in graphite and the
disordering of this piled structure significantly decreases the material cohesion.
Owing to the high thermodynamically stable chemical structure graphite is an inert substance, and
only a few chemical reactions are possible using graphite as a reactant. Graphite flakes can be
chemically modified by treatment with very strong oxidizing species leading to a chemical compound
known as graphite oxide [26-36]. A mixture of sulfuric acid (H2SO4), fuming nitric acid (HNO3), and
potassium permanganate (KMnO4), or a mixture of sulfuric acid, fuming nitric acid and a perchlorate
salt (e.g., KClO3), or simply fuming nitric acid and a perchlorate salt system are just some of the
oxidizing conditions that can be used to transform mineral graphite flakes into graphite oxide (other
oxidizing species used for the graphite oxide production are: CrO3, K2Cr2O7, (NH4)2S2O8, H2O2, O3,
etc.). These oxidizing mixtures contains a very low amount of water (less than 1% by weight) and
therefore are extremely active and able to produce graphite oxide species with a carbon/oxygen ratio
of 2-4, depending on the applied reaction conditions (treatment time and temperature). When graphite
is treated by so strong oxidizing chemical species, oxygen atoms in form of hydroxyls groups (OH),
ether bridges (-O-), carbonyls (-CHO), and carboxylic groups (-COOH) appear everywhere in the
carbonous structure. The formation of such functional groups involves the full graphite structure.
Sulfuric acid is used as a solvent in these oxidative mixture, since it easily penetrates (intercalate) in
the graphene structure, thus facilitating the oxidation process. Typically -OH, -CHO, epoxy (ether
bridges), and -COOH groups are bonded to the partially unsaturated graphite network both at edges
and the inner regions of the plane. However, the treatment of mineral graphite flakes with some less
aggressive liquid oxidizing mixture (for example, an aqueous solution of sulfuric and nitric acid,
H2SO4/HNO3(sol. 65%) in the ration of 9:1 by volume) allows to achieve a special type of graphitic
material known as expandable graphite, which is a graphite oxide with a C:O atomic ratio higher than
the ordinary graphite oxide. Expandable graphite is a black material quite similar to the original
graphite powder, while graphite oxide is a colored (from yellow to dark-green, depending on the
oxidation level) water-soluble material. This type of graphite oxide can be conveniently used to
prepare graphene with good thermal and electrical conductivity.
The presence of these oxygenated groups reduces the extension of the conjugation in the
expandable graphite, therefore making this type of graphite a chemical species less thermodynamically
stable than the starting graphite. When expandable graphite is heated at a convenient temperature
(higher than 200C) the organic structure eliminates the oxygenated groups in form of small molecules
(H2O, and CO2), thus restoring the more thermodynamically stable (aromatic) structure. When water
and carbon dioxide are released, the high ordered structure of graphite is completely destroyed and a
foam-like material, named expanded graphite, is obtained. In this new type of graphite structure,
cohesion is very low and the carbon sheets can very easily move away from each other by application
of some thermal or mechanical energy. Therefore, during the expansion process the oxidized carbon
planes are thermally reduced to graphite sheets and only a limited percentage of residual ether-bridges
leaves in the final compound (expanded graphite). Such residual epoxy groups can be eliminated by

International Conference on Structural Nano Composites (NANOSTRUC 2012)

IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012018
doi:10.1088/1757-899X/40/1/012018

chemical reduction (for example with hydrazine, dimethyl-hydrazine, hydroquinone, NaBH4, etc.) or
by treatment with strong alkaline solution (KOH, NaOH, etc.). The extension of graphite foaming, and
therefore the lowering of the material cohesion, depends on the rate of the H2O and CO2 molecule
release, therefore it is of a fundamental importance to apply a significant thermal shock to the material.
Faster is the graphite oxide heating process lower is the residual cohesion in the thermally-reduced
product. The combination of oxidation and thermal reduction treatments allows to deeply disorder the
graphite structure, thus decreasing the physical interactions among the carbon sheets. Carbon sheets in
the expanded graphite can be separated each other by simply applying some thermal or mechanical
energy to this material. In particular, expanded graphite needs to be wet by an adequate organic
medium that allows to uniformly apply mechanical energy to the full mass and the obtained liquid
suspension can be heated under stirring or some mechanical energy can be applied by a piezoelectric
generator of ultrasounds. The elastic wave propagate to the foam structure (expanded graphite) and the
resulting oscillations of the carbon planes quickly disaggregates the low coherent solid structure.
When heat is applied, the thermal vibrations of carbon atoms are involved in the separation of carbon
planes in the low coherent solid structure, however such mechanism is less effective than the
sonication treatment and therefore a combination of heat and sonication is the most effective process.
Heat has also the important role to prevent recombination of graphen planes after the exfoliation
process.
Also the nature of the sonication medium has an important role in strongly solvating the carbon
sheets and avoid their recombination. In particular, thermally reduced graphite has an anphiphilic
nature (both non-polar regions and polar functional groups are present in the molecular structure),
consequently the best sonication medium should be made of molecules containing both a non-polar
part able to interact with carbon planes by Van der Waals interactions and a polar group that may
interact with residual oxygenated groups present in the carbon structure. Alcohols, glycols and polyols
represent the best choice for the presence of hydroxyl groups and aliphatic hydrocarbon segments in
their molecular structure, but also other liquids phase can be conveniently used (e.g., Nmethylpyrrolidone, dimethyl-formammide, etc.). For a complete exfoliation of the expanded graphite,
the sonication should be applied to a very dilute system in order to reduce the importance of the
graphene sheets recombination process (dilution increase the average inter-plane distance during the
sonication treatment, thus making difficult the recombination of carbon planes).
When sonication is removed the graphene sheets may slowly recombine, settling at container
bottom, however these planes are solvated by molecules of the liquid dispersing medium and therefore
they can be fully redispersed by applying again ultrasounds. To avoid recombination of the carbon
sheets it is required to intercalate them by some intercalantes. Polymers soluble in alcohols can be
dissolved in the colloidal suspension and the system allowed to concentrate by solvent evaporation.
When the solvent (alcohol, N-methylpyrrolydone, etc.) has been completely removed by evaporation,
the carbon planes are separated by the enveloping polymer molecules and their recombination to form
graphite cannot take place anymore. In the case of non-polar polymers the liquid sonication medium
must be selected among the compounds acting as solvents for the polymer. Frequently chloroform and
ethers (e.g., dioxane) are used. Such new type of discontinuous composite materials allows the
fabrication of several devices for future carbon-based nanoelectronics.
3. Graphene in automotive application
Graphene has been investigated with great interest for use as electrode material in electrochemical
supercapacitors in electrical/hybrid automobiles because of their unique combination of properties
such as high surface area, lightweight, good electrical conductivity, compatibility with other materials,
and controlled pore size distribution [37-44]. This material has recently been used in supercapacitor
devices to replace conventional carbon electrodes and have shown very good performance[45-49].
Typically, graphitic carbon-based materials are randomly oriented with respect to the current
collectors in a conventional stacked geometry in supercapacitors leading to a lower utilization of the
electrochemical surface area of graphene layers and consequently limits the extent of the

International Conference on Structural Nano Composites (NANOSTRUC 2012)

IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012018
doi:10.1088/1757-899X/40/1/012018

EDL(electrical double layer) formed at the interface. Most recently, Yoo et al.[50] demonstrate the
utilization of pristine and multilayer graphene as electrodes in an in-plane device geometry for use
in supercapacitors in order to offers new opportunities for the electrolyte ions toenhance interaction
with all the carbon layers with a full utilization of the high surface area offered by graphene layers.
4. Conclusion
The mild oxidation treatment of natural graphite flakes by a H2SO4/HNO3 aqueous solution combined
with thermal expansion at very high temperature and exfoliation by applying sonication in liquid
dispersing medium represents a very convenient approach for a massive graphene production. In
addition, polymer intercalation in liquid phase is also an adequate way to avoid recombination of the
single graphene sheets produced during the exfoliation stage. The resulting isoorientation of grafene
sheets in the polymer matrix is an important characteristic and most physical properties of this new
type of material originates from such special topological characteristic.
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doi:10.1088/1757-899X/40/1/012018

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doi:10.1088/1757-899X/40/1/012018

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