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