Carbon Nanomaterials

Allotropes of Carbon
Diamond
Graphite
Amorphous
Graphene
Fullerenes (Buckyballs)
Glassy Carbon
Diamond Like Carbon
Carbon Nanotubes/Nanofibers
Four Carbon Families:
A. Graphite (Rhombohedral and Hexagonal)
The structure of rhombohedral graphite
can be best considered as an extended
stacking fault in hexagonal graphite.
Rhombohedral graphite can not be
isolated in pure form (natural graphite
and laboratory preparations contain less
than 40% of rhombohedral graphite in
combination with hexagonal graphite).
It is produced by shear deformation of hexagonal graphite and transforms to the
hexagonal (ABAB) modification on heating above 1600 K.
B. Fullerene Family (C60, C70, C 240, C 540)
C. Diamond Family
(Basic tetrahedral, Cubic, and Hexagonal diamond structures)

D. Carbyne Family
(sp hybridized carbon atoms bound linearly to form chains that associate together by
van der Walls interactions between pi electrons)
 Hybridization States of Carbon

sp hybridization (Diamond)
sp hybridization (Graphite)
Other than Diamond, carbonaceous materials can be divided into graphitizing and
non-graphitizing carbon. (Franklin, R. Proceedings of the Royal Society (1951)
Graphene
High-magnification TEM images of (a) a bi-layer graphene
sheet, (c) a graphitic particle and (e) a bulk graphite structure
synthesized at 250 W and a plasma gas flow rate of 1.7 lpm.
Scale bars: 2 nm.
Dato, A. et al. 2010, New J. Phys.
 Atomic Resolution Imaging of Graphene Membranes

TEM image of a few-layer graphene membrane near its edge, where the number of dark
lines indicates the thickness of two to four layers. The atomic-resolution imaging was
achieved by using FEI Titan at an acceleration voltage of 300 kV. Scale bar, 1 nm.
Meyer, J.C. et al., 2007, Nature Letters
 Graphene Films

Novoselov, K.S. et al., 2004 (Science)

(A) Photograph (in normal white light) of a relatively large multilayer graphene flake with
thickness ~3 nm on top of an oxidized Si wafer. (B) AFM image of this flake near its edge.
Colors: dark brown, SiO2 surface; orange, 3 nm height above the SiO2 surface. (C) AFM
image of single-layer graphene. Colors: dark brown, SiO2 surface; brown-red (central area),
0.8 nm height; yellow-brown (bottom left), 1.2 nm; orange (top left), 2.5 nm. Notice the
folded part of the film near the bottom, which exhibits a differential height of ~0.4 nm.
 Structure of Suspended Graphene Sheets

Suspended graphene membrane. Bright-field TEM image of a suspended graphene

membrane. Its central part (homogeneous and featureless region indicated by arrows) is
monolayer graphene. Electron diffraction images from different areas of the flake show that
it is a single crystal without domains. We note scrolled top and bottom edges and a strongly
folded region on the right. Scale bar, 500 nm.
Meyer, J.C. et al., 2007, Nature Letters
 Large Area Synthesis of High-Quality and Uniform
Graphene Films

Li, X. et al. (2009),, Science

(C and D) Graphene films transferred onto a SiO2/Si substrate and a glass plate, respectively
 HRTEM images
of graphene layers
The Rise of Graphene...by A.K.Geim and K.S.Novoselov
Electronic structure rapidly evolves with the number of layers, approaching the 3D
limit of graphite in 10 layers.
Only up to bi-layer graphene is zero-gap semiconductors with one type of electrons and
one type of holes.
Synthesis of single and few layer graphene has been achieved by epitaxy by chemical
vapor deposition of hydrocarbons on metal substrates.
Recently, bi-layer graphene was obtained on SiC.
Graphene shows extremely high-mobility charge carriers and thus has potential
applications in electronics.
Still, most of the researchers use graphene samples obtained from micromechanical
cleavage of bulk graphite.
At a time when Si based technology is approaching its fundamental limits, any new
candidate materials to take over from Si is welcome, and graphene seems to offer an
exceptional choice.
 The Rise of Graphene...
by A.K.Geim and K.S.Novoselov

Major Challenges:
High quality graphene suitable for large scale applications
Reproducibility in their properties for their use on devices
Graphene based microprocessor are unlikely to appear for next 10 years.
However graphene finds its use in composites, energy storage devices, field
emission devices, sensors, hydrogen storage etc.
 Fullerene (Buckyballs)

Geodesic Domes

C60 has been the most thoroughly studied

member of fullerene family. It has
symmetrical structures and shows
inertness under mild conditions.
Electronically, C60 is described as having a
The Biosphre is a museum in
closed shell configuration consisting of 30
Montreal dedicated to the
bonding molecular orbitals with 60 p environment.
electrons.
The skeleton of C60 consists of 20
hexagonal and 12 pentagonal rings fused
all together.
The van der Waals diameter of a C60 molecule is about 1.1 nm. The nucleus to nucleus
diameter of a C60 molecule is about 0.71 nm.
 Formation of Fullerenes

Kroto, H. , Science 1988

 Formation of Fullerenes
Fullerene was fist synthesized by a team of researchers from Rice University
led by H.W.Kroto, R.F.Curl and R.E.Smalley.
(C60: Buckminsterfullerene, Nature Letters, Vol. 318, 1985)

Solid graphite block was ablated by pulsed laser in the presence of highly
dense helium environment to yield buckyballs.

Other names considered at the time of first synthesis were: ballene, spherene,
soccerene, carbosoccer

Discovery of fullerene was awarded with Nobel Prize in 1996.

CARBON NANOTUBES
 Synthesis of Carbon Nano Tubes (CNTs)
1. Thermal CVD
2. PECVD
3. LPCVD
4. Electric Arc Discharge Method
5. Laser Ablation
6. Flame Synthesis
CNT were first noticed in the graphitic soot deposited on the negatively charged
electrode used in the arc-discharge synthesis of fullerenes.
Growth of aligned CNT were first demonstrated by CVD directly on Fe
nanoparticles embedded in mesoporous silica.
In 1985 a new allotrope of carbon: fullerene was discovered by Kroto et al.
Subsequently, carbon nanotube (CNT) was discovered by Iijima in 1991. Two
years later, in 1993, CNTs consisting of a single graphene layer were reported by
two groups: NEC and IBM.
After that CNTs were classified into two kinds: single-wall carbon nanotubes
(SWCNTs) and multi-walled carbon nanotubes (MWCNTs). Under this
nomenclature, the first CNTs discovered in 1991 (containing two, five and seven
coaxial cylinders) were MWCNTs.
 CNTs: MORPHOLOGY and STRUCTURE

SWCNT: 0.3 nm to 5 nm with

length up to 50 to 100 micron.
Specific surface area: up to
1315 m2/g

MWCNT: Outer diameter from

2.5 nm to several tens of nm.
Specific surface area: up to 900
m2/g

Schematic representation showing the relation

between the carbon nanotube and graphene
 Chirality and CNT

A 2-D graphene sheet showing chiral vector C and chiral angle

Chirality and CNT
 HRTEM images of SWNT and MWNT

The separation between the closely spaced fringes in the MWNTs

is 0.34 nm, close to the spacing between graphite planes.
Reference: P.M.Ajayan et al., Nature 1997
 High Resolution STM image showing the lattice structure of a
SWNT that is close to an armchair tube
Ref.: P.M.Ajayan in Handbook of Nanostructured Materials and Nanotechnology (Picture was
provided by Dr. C.Dekker)
Growth Mechanism

Capped Growth of CNTs

PURIFICATION OF CNTs
Oxidation
By oxidation we can partially purify CNTs from impurities ( time and temperature of
exposure of the process are very important) .
While oxidation COOH or OH groups are generated which help the attachment of
organic or inorganic material to increase solubility.
Best way is to mildly oxidize them with H2O2 and H2SO4 which only causes oxide
defects.

Acid treatment
By acid treatment mostly metal catalysts are removed by the reaction with Nitric acid or
Sulfuric acid or a mixture of both.

Annealing
In this method a very high temperature is applied (800-1800 C) in a vacuum atmosphere
which caused CNT atoms to rearrange and form a perfect CNT
very high temperature ,metal is melted and also can be removed from the reaction

Ultrasonication
Ultrasonic created a low pressure and high pressure waves in the liquid and it improves the
reaction and causes reactants to be mixed it forces particles to vibrate and disperse in the
liquid evenly.
PURIFICATION OF CNTs
Magnetic Purification

Ultrasonic while ferromagnetic catalyst will be removed from SWNT.

Suspension is mixed with Zirconium Dioxide (ZrO2) or Calcium Carbonate (CaCO3) and
the bath is trapped among a magnet

Micro filtration
By this method while we have a mixture of materials along with carbon nanotubes by
using a membrane.

Purification step
1. Purification process sample was used in HCl, Acid Nitric HNO3, and Hydrofluoric Acid
HF
2. Sonication (Ultra Sonication) in HF for 30 minutes and filtrated by polycarbonate
3. Immersed in HCl and HNO3 solution
4. Washed in pure water
5. Put in 600 C pure air to remove amorphous carbon
Opening of CNTs
Simplest way to open the end of
nnotubes is their oxidative treatment.
Liquid or gaseous chemical agents are
used as oxidants.
Refluxing, sonicaion or microwave
digestion in conc. Acids, such as nitric
acid or sulphuric acid are most popular
methods for oxidation.
However prolonged treatment of
SWCNTs leads to amorphization and
complete destruction of tubes.
Functionalization/Modification of CNTs

CNTs have high mechanical strength, thermally and electrically conductive,

extremely light with low mass and high aspect ratio (surface to volume ratio).

To use these phenomenal properties homogeneously dispersed in

nanocomposites to preserve their characteristics.

As CNTs have a hydrophobic structure and agglomerate because of vander

Walls forces, they do not disperse evenly in the liquid .

Need to align CNTs and prevent them from agglomerating so that they can be
even evenly distributed in nanofluids.

Functionalization is done for their extended use.

 Functionalization of CNTs
Endohedral Functionalization
Modification of CNT by putting nanoparticles inside the tube.

Change the hydrophobic structure to hydrophilic and make them as solvents.

Filling Nanotubes with nanoparticles to add the characteristics of the Nanoparticles
inside the Carbon Nanotubes to fantastic phenomenal of CNT.

This method itself is sub categorized to two methods:

1. Putting CNT inside the suspension containing nanoparticles so that it can

penetrate the tube internal site and stay inside the CNT
Depends on surface energy(surface tension ) of the liquid.
Experiments show that if surface tension of the liquid is more than 200 mN/m,
liquid can fill the Nanotubes

2. CNTs are filled with a material which reacts with it and then produces
nanoparticles which are trapped
 Functionalization/Modification of CNTs

Exohedral Functionalization
is modification of external
part of CNTs like side walls

a) Aromatic molecules can be appended to CNTs using certain non-covalent

interactions (known as - interactions);
b) Non-covalent interactions (including - interactions, van der Waals forces and
charge-transfer interactions) can be used to encapsulate/wrap polymers around
surfaces of CNTs;
c) Chemical groups can be covalently attached to CNTs.