Graphene : a general

review

In this paper we first look at the early history of

Graphene, how it was synthesized, followed by its
applications etc. We also talk about some of its
remarkable properties. Then we look at how it’s used with
other materials to make nano-composits: We look at its
various methods and study different properties of
graphene based nano composits.

INTRODUCTION

Before we understand graphene, it is important to know

that before we reached the stage of graphene, first it was
graphite that was observed & studied followed by
graphite oxide paper.
The Structure of graphite as super imposed layers of
carbon was identified in 19161 by the related method of
powder diffraction2, although even earlier, in 1859
Benjamin Collins Brodie became aware of the highly
lamellar structure of thermally reduced graphite oxide3.

Then in 1918, Kohlschutter and Haenni described the

properties of graphite oxide paper4, which is a material
fabricated from graphite oxide. These are micrometer
thick films of graphite oxide with two dimensional
graphene backbone and an interwoven layer structure.

The earliest TEM images of few-layer graphite were

published by G. Ruess and F. Vogt in 1948.5 Later, single
graphene layers were observed directly by electron
microscopy.6
Starting in the 1970s single layers of graphite were grown
epitaxially on top of other materials.7 Epitaxy refers to the
deposition of a crystalline overlayer on a crystaline
substrate. This "epitaxial graphene" consists of a single-
atom-thick hexagonal lattice of sp2-bonded carbon
atoms, as in free-standing graphene. However, significant
charge transfers from the substrate to the epitaxial
graphene, and in some cases, the d-orbitals of the
substrate atoms hybridize with the π orbitals of
graphene, which significantly alters the electronic
structure of epitaxial graphene.

Single layers of graphite were observed by TEM within

bulk materials, in particular inside soot obtained by
chemical exfoliation. Efforts to make thin films of graphite
by mechanical exfoliation started in 1990,[23] but nothing
thinner than 50 to 100 layers was produced before 2004.

In 2004 Geim and Novoselov extracted single-atom-thick

crystallites from bulk graphite.8 They pulled graphene
layers from graphite and transferred them onto
thin silicon dioxide (SiO2) on a silicon wafer in a process
 called either micromechanical cleavage or the Scotch
tape technique. The SiO2 electrically isolated the
graphene and weakly interacted with it, providing nearly
charge-neutral graphene layers.

SOME EXCEPTIONAL PROPERTIES OF GRAPHENE

Flexible

Graphene's flexibility could be used in emerging technologies

such as rollerball computers, heat sensitive clothing and flexible
phones.
Conducts

Graphene can conduct electricity even better than copper and

this gives graphene endless applications including conductive
paints and inks, next generation electronics and more efficient
batteries.

Transparent
Graphene is transparent, meaning that we could see TV's built
into windows and Sat Navs built into car windscreens in the
future of electronics.

Thin

One of graphene's most dynamic properties is its remarkable

thinness. At just one atom thick, graphene is one million times
thinner than the diameter of a human hair.

Strong
Graphene is the strongest material known to man. It is over 200
times stronger than steel. The strength of graphene could be
used in composites...

Thermal

Graphene has the highest thermal conductivity known to man.

SYNTHESIS OF GRAPHENE

In recent years, various techniques have been

established for graphene synthesis. However,
mechanical cleaving (exfoliation) 9, chemical exfoliation10,
chemical synthesis11, and thermal chemical vapor
deposition (CVD)12 synthesis are the most commonly
used methods today. Some other techniques are also
reported such as unzipping nanotube (as shown in page
2) and microwave synthesis.

Although mechanical exfoliation using AFM cantilever

was found capable of fabricating few-layer graphene,
the process limitation was thickness of graphene varies
to ~10 nm, which is comparable to 30-layer graphene.

Mechanical exfoliation mechanism: graphene is prepared

by exfoliating graphite. In this process, the ideal case is
that graphene can be peeled from the bulk
graphite layer by layer. The resistance to overcome is the
van der Waals attraction between adjacent
graphene flakes.13
Chemical exfoliation method: Solution dispersed
graphite is exfoliated by inserting large alkali ions
between the graphite layers.

Chemical synthesis: Similar process which consists of the

synthesis of graphite oxide, dispersion in a solution,
followed by reduction with hydrazine.

Thermal chemical vapour deposition: Thermal CVD (or

vapor plating) is the deposition of atoms or molecules by
the high temperature reduction or decomposition of a
chemical vapor precursor species, which contains the
material to be deposited.14

In other words, hydrocarbons are decomposed and

catalyzed to form sp2 hybridized carbon for lateral
growth on a substrate. Graphene can be synthesized with
desired structures depending on the CVD process,
catalyst substrates, nature of precursors, base pressure,
and gas composition.
CVD process is one of the most prominent
approaches for the synthesis of high quality graphene
with a controlled number of layers in large area.

Synthesis of planar nanographene (PFLGs) was

demonstrated by Somani et al. by a simple CVD
technique. The graphitic structure included about ~35
layers of graphene, due to high segregation of carbon
atoms on the Ni foil. The process was further developed
to achieve control growth of monolayer, bilayer, and few
layer graphene on the Ni-deposited SiO2/Si and Ni foil
[32, 33]. The main challenge of CVD graphene structure
is to remove and transfer on an insulating substrate for
physical properties characterization. In the later stage,
transfer process of CVD graphene onto an arbitrary
substrate without disturbing the intrinsic properties has
been developed. Transferring of a CVD graphene can be
achieved by wet or dry etching of the catalytic layer and
placing on a desirable substrate surface. The CVD
process has been significantly explored to grow large size
single crystals and high quality wafer-scale monolayer
and bilayer graphene. In this prospect, the nucleation
and growth mechanism of graphene on a catalytic
substrate play the fundamental role in the formation of
large domains and number of layers. The transition
metals, alloys, and liquid metals have been recognized as
the catalyst for growth of monolayer and bilayer
graphene, where the surface composition of solid catalyst
substrates also plays critical role on graphene growth.
The thermodynamic and kinetic parameters are also
crucial in graphene growth process, where pressure and
temperature are both key factors.15

Synthesis of graphene-based
polymeric nanocomposites16
Due to Excellent properties of graphene, techniques are
developed to employ the outstanding properties of
graphene in different areas, including biosensors, drug
delivery, transistor devices, nanoelectronics, and polymer
nanocomposites17.A prerequisite for this is Chemical
functionalization, also known as surface modification of
graphene.

To enhance the physiochemical properties of

nanocomposites, the use of surface-modified graphene
as a reinforcing filler has been investigated in detail18.
Chemically functionalized graphene can be prepared
directly from graphite or from GO. In both the cases,
presence of surface modifiers prevents the
agglomeration of graphene sheets and thus assists the
dispersion of grapehene sheets in various organic
solvents and polymers.
Methods of fabrication of graphene-based polymer
composites:

The three most common methods of fabricating

graphene-based polymer composites are described
below.

1. Solution blending: In the solution-blending process,

the polymer is dissolved in suitable solvents and is then
mixed with a solution of dispersed-graphene
suspension19. Graphene or modified graphene is easily
dissolved in a suitable solvent with its sheets delaminated
owing to the weak forces. The polymer is then absorbed
into the sheets. After the solvent evaporates, the sheets
reassemble and sandwich the polymer to form
nanocomposites20.

If the polymer is readily soluble in common aqueous and

organic solvents including water, acetone, DMF, THF,
chloroform, or toluene, then it is the most common
technique of synthesizing graphene-polymer composits.
This method allows the synthesis of nanocomposites with
polymers of low or even zero polarity. The issue lies in
the homogeneous dispersion of graphene sheets and the
evaporation of solvents. Ultrasonication can be used to
homogenize the dispersion of graphene sheets and thus
create a metastable suspension. However, long-term
exposure to high-power ultrasonication can induce
defects in graphene sheets resulting in poor properties in
the nanocomposites. Functionalization of graphene
sheets may help in better dispersion in water or other
organic solvents. During slow solvent evaporation, GO
and RGO sheets tend to agglomerate, thus creating
inhomogeneous dispersion of sheets in polymer matrix.
Spin coating or drop casting can be used to control the
evaporation time to achieve an improved distribution.
Polymer nanocomposites based on PVA/graphene21 and
polyethylene-grafted maleic anhydride (PE-g-
MA)/graphite22 have been produced by this method.
2. In situ intercalative polymerization: In this process,
GO or RGO is dispersed in the liquid monomer. A
suitable initiator is then diffused and either heat or
radiation initiates polymerization. Similar to solution
blending, functionalized graphene and GO sheets can
improve the initial dispersion in the liquid monomer and
the resulting composites. Both covalent-bonded and
noncovalent-bonded composites have been synthesized
using the in situ polymerization technique. Figure 1 shows
the fabrication of PP/GO nanocomposites by an in situ
ZiegelereNatta polymerization technique using graphene
sheets for Mg/Ti catalysis support. In situ polymerization
exfoliates the layered structure of graphite into graphite
nanoplates by the intercalation of monomers that, after
polymerization, produce well-distributed graphene
composites

Epoxy-based nanocomposites have been produced by

dispersing graphene sheets into the resin followed by the
addition of hardener and curing23.
Figure 1 Fabrication of PP/GO nanocomposites by in situ
ZieglereNatta polymerization. Reproduced from Huang et al.
(2010) with permission from American Chemical Society.

3. MELT MIXING: In this technique, graphene, graphite,

or modified graphene is dispersed with the molten
polymer matrix. Using manufacturing methods like
extrusion and injection molding, a thermoplastic polymer
is mixed with graphene at elevated temperatures using
mechanical shear forces. The polymer chains are then
intercalated or exfoliated to form polymeric
nanocomposites. This technique is particularly suitable for
thermoplastic polymers at large scale. No toxic solvent is
required in this process, and can be used for both polar
and nonpolar polymers.
Properties of polymer/graphite/graphene
nanocomposites

Now we mechanical, electrical, and thermal properties of

graphene nanocomposites.

Mechanical properties

Remarkable mechanical properties (Young’s modulus and

tensile strength) of graphene have attracted researchers
to use graphene as filler in polymer nanocomposites for
improving their stiffness and strength. Considerable
improvement in the properties of graphene-polymer
nanocomposites have been achieved even with very low
filler loadings as compared to what can be achieved
using conventional composites or neat polymers. The
amount of enhancement is directly related to the amount
of filler, filler aspect ratio, degree of dispersion of the filler
in polymer matrix, and interfacial bonding between the
two. Folds and wrinkles of graphene sheets can also have
a detrimental effect on the mechanical properties of
nanocomposites. Figure 2 shows the enhancement of the
Young’s modulus and the tensile strength of
PS/graphene nanocomposite film with the increase in the
graphene concentration24 . The figure shows that for a
graphene concentration of 0.9 wt%, the increases in
Young’s modulus and the tensile strength of the
nanocomposite film are 57.2% and 69.5%, respectively,
with respect to those of pristine PS. Presence of
functional group on GO surfaces enhances its dispersion
in polar solvents and water. This enhanced polymer/GO
interaction, in effect, led to an increase of 76% and 62%
in the Young’s modulus and tensile strength, respectively,
25
for PVA/GO nanocomposite with 0.7 wt% GO sheets .
In contrast, it has been reported that the presence of
defects in carbon lattice produced by chemically reduced
GO and thermally reduced GO are detrimental to the
mechanical properties26.
Figure 2 (a) Stresse-strain curves of pristine polystyrene (PS)/graphene nano-
composite films for various contents of graphene sheets. (b) Increase of the Young’
s modulus and the tensile strength of nano-composite films with increasing
graphene content is shown.

Electrical properties

Because of the excellent electrical conductivity and

electron-transport properties27, graphene has become
attractive filler for insulating polymer matrix for
synthesizing electrically conductive composites.
Theoretically, pristine graphene has the highest electrical
conductivity, 15e19 times higher than that of the polymer.
However, the difficulty in producing a substantial amount
of graphene using mechanical exfoliation limits its use as
filler. This has led to the use of chemically and thermally
reduced graphene, which introduces other issues. The
major issue is that GO is electrically insulating. Thermal
reduction partially restores the electrical conductivity by
eliminating the oxygen functional group and thus makes
RGO suitable filler for conductive composites, provided
the filler concentration is above the percolation
threshold. It has been reported that nanocomposites
made using thermally reduced graphene have the
highest electrical conductivity compared to that obtained
using chemically reduced graphene28. Stankovich and co-
workers have shown that hydrazine PS-isocyanate-
treated GO mixture has the lowest electrical percolation
threshold with 0.1 vol% of graphene in which a
conductive path is formed for electron flow29. Apart from
the effects of the exfoliation method, the presence of
functional groups, aspect ratio of graphene sheets,
processing methods, and dispersion in the matrix,
wrinkles, and folds also significantly affect the
conductivity of the composites.
Thermal conductivity
Researchers have attempted to improve the thermal
conductivity of nanocomposites using 2D graphene as
filler due to its exceptional thermal conductivity (w5000
W/m/K)30. Nanocomposites with good thermal
conductivity have potential applications in lightweight
thermal management systems, electronic circuit boards,
and heat sinks. Enhanced thermal conductivity has been
obtained for various polymer matrices including
31
epoxy/graphene nanoplatelets , epoxy/exfoliated
graphite32, PVC/graphene33, and PP/graphene
nanoplatelets34. However, the observed improvement in
thermal conductivity of nanocomposites is not that
significant35, primarily because the (1) ratio of thermal
conductivity of graphene and polymer is about four, and
(2) high interfacial thermal resistance between graphene
sheets and polymer matrix due to string-phonon
scattering. Other factors that influence thermal transport
properties include the aspect ratio, dispersion, and
orientation of graphene sheets. Other impressive
properties include reduced gas permeability of graphene
nanocomposites36, improved EMI shielding 37
, and
enhanced thermal stability38.

Conclusions and future trends

Exceptional mechanical properties along with
remarkable electronic transport properties and thermal
conductivity have made graphene the best carbon filler.
Significant enhancement in mechanical properties of
graphene-based polymer nanocomposites has been
found (even with lower concentration) compared to
those of the neat polymer and conventional graphite-
based composites. Moreover, graphene/polymer
nanocomposites exhibit several-fold increase in electrical
conductivity and thermal conductivity. The conductive
networks formed by graphene sheets result in
considerable increase of the electrical conductivity and
thermal conductivity of nanocomposites.

Property enhancements vary depending on the type of

polymer matrix, filler type, concentration, and processing
method. Apart from these factors, homogeneous
dispersion of graphene in polymer matrix and interfacial
bonding between graphene and the matrix play crucial
roles in dictating the final properties of the
nanocomposites. The difficulty lies in finding correlations
between the properties and these factors. As explained in
this chapter, various surface modifications of graphene
including functionalization of graphene have been
employed by different researchers to improve the
dispersion of graphene in polymer matrix and the
interfacial bonding between the two. These
enhancements in mechanical properties and electrical
conductivity will draw more attention from researchers
and broaden the applications of graphene/polymer
nanocomposites in the near future.

SOME OTHER APPLICATIONS

1. Graphene was synthesized chemically by Hummers

and Offeman method and the graphene-modified
electrode was applied in selective determination of
dopamine with a linear range from 5 μM to 200 μM in a
large excess of ascorbic acid. Selective detection was
realized in completely eliminating ascorbic acid, different
from the methods based on the potential separations. π
–π stacking interaction between dopamine and
graphene surface may accelerate the electron transfer
whereas weaken the ascorbic acid oxidation on this
graphene-modified electrode. The resulted graphene-
modified electrode also showed a better performance
than multi-walled carbon nanotubes-modified electrode.
The phenomena were considered from the elusive two-
dimensional structure and unique electronic properties of
graphene.39
2. Graphene exhibited great potential to be an adsorbent
in analytical sample preparation due to its exceptional
properties (e.g., large surface area, π-electron-rich
structure, and good thermal and chemical stability).

References

1- Debije, P; Scherrer, P (1916). "Interferenz an regellos

orientierten Teilchen im Röntgenlicht I". Physikalische
Zeitschrift (in German).

2- Hull, AW (1917). "A New Method of X-ray Crystal

Analysis". Phys. Rev. 10 (6): 661–696.

3- Kohlschütter, V.; Haenni, P. (1919). "Zur Kenntnis des

Graphitischen Kohlenstoffs und der Graphitsäure".
Zeitschrift für anorganische und allgemeine Chemie (in
German). 105 (1): 121–144.

4- Ruess, G.; Vogt, F. (1948). "Höchstlamellarer

Kohlenstoff aus Graphitoxyhydroxyd". Monatshefte für
Chemie (in German). 78 (3–4): 222–242.

5- Roth, S. (2007). "The structure of suspended graphene

sheets". Nature. 446(7131): 60–63.
6- Oshima, C.; Nagashima, A. (1997). "Ultra-thin epitaxial
films of graphite and hexagonal boron nitride on solid
surfaces". J. Phys.: Condens. Matter. 9(1): 1–20.

7-Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.;

Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A.
(22 October.

8- Novoselov, K.S., Geim, A.K., Morozov, S.V., Jiang, D.,

Zhang, Y., Dubonos, S.V., Grigorieva, I.V., Firsov, A.A.:
Electric field effect in atomically thin carbon films. Science
306(5696), 666–669 (2004).

9- Allen, M.J., Tung, V.C., Kaner, R.B.: Honeycomb

carbon: a review of graphene. Chem. Rev. 110(1), 132–145
(2010).

10- Park, S., Ruoff, R.S.: Chemical methods for the

production of graphenes. Nat. Nanotechnol. 4, 217–224
(2009)

11- Reina, A., Jia, X.T., Ho, J., Nezich, D., Son, H., Bulovic,
V., Mildred Dresselhaus, S., Kong, J.: Large area, few-layer
graphene films on arbitrary substrates by chemical vapor
deposition. Nano Lett. 9(1), 30–35 (2009).
12- Min Yi*ab and Zhigang Shen*a A review on
mechanical exfoliation for the scalable production of
graphene, journalof material chemistry A(issue22,2015)

13- Donald M. Mattox, in Handbook of Physical Vapor

Deposition (PVD) Processing (Second Edition), 2010

14- Golap Kalita and Masaki Tanemura (May 17th 2017).

Fundamentals of Chemical Vapor Deposited Graphene
and Emerging Applications, Graphene Materials -
Advanced Applications, George Z. Kyzas and Athanasios
Ch. Mitropoulos, IntechOpen, DOI: 10.5772/67514

15- Fillers and Reinforcements for Advanced

Nanocomposites,Woodhead Publishing Series in
Composites Science and Engineering: Number 60

16- (Valles et al., 2008; Park and Ruoff, 2009; Kuila et

al., 2010a; Loh et al., 2010

17- Kuila et al., 2010a; Loh et al., 2010

18- Stankovich et al., 2006)

19- (Lee and Im, 2007)

20- (Liang et al., 2009; Jiang et al., 2010)

21- (Hussain et al., 2006)

22- (Rafiee et al., 2010)

23- Fang et al., 2009)

24- (Liang et al., 2009)

25- (Kim and Macosko, 2008; Liang et al., 2009)

26- (Novoselov et al., 2004, 2005.

27- Singh et al., 2011)

28- (Stankovich et al., 2006)

29- (Balandin et al., 2008)

30- (Yu et al., 2007)

31- (Ganguli et al., 2008)

32- (Vadukumpully et al., 2011)

33- (Kalaitzidou et al., 2007b)

34- (Singh et al., 2011)

35- (Kim and Macosko, 2008, 2009; Jiang and Drzal,

2009; Compton et al., 2010)

36- (Lianga et al., 2009)

37- (Salavagione et al., 2009)

38- Ying Wang, Yueming Li Longhua Tang Jin Lu
Jinghong Li, “Application of graphene-modified electrode
for selective detection of dopamine”, Electrochemistry
Communications, Volume 11, Issue 4, April 2009, Pages
889-892.

PROJECT
ON
GRAPHENE
ABDULLAH ZAMAN

ROLL NUMBER: 16-ICB-021

ENROLL NO: GJ5669

B. SC. INDUSTRIAL CHEMISTRY 6TH SEMESTER

CONTENTS