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Lecture: Carbon Nano Materials
AME57201
Prof. Zonghoon Lee
M t i l S i d E i i P Materials Science and Engineering Program
School of Mechanical and Advanced Materials Engineering
U N I S T
W1_Friday 2013-11-29
Whatisseenwasnotmadeoutofwhatwasvisible(Hebrew11:3)
What Color is Carbon?
A f t i ti t
Lets start talking about what you know about carbon.
An answer from someone, not a scientist:
Carbon has different forms (allotropes). It can be diamond, graphite,
or substances known fullerenes. Graphite is black, diamonds are
clear (colored diamonds are because of impurities). Bulk fullerenes
look black, but I am not sure if this changes depending on size or
manufacturing technique.
* Color of diamonds: diamond blue (boron), yellow (nitrogen), brown (lattice defects),
green, purple, pink, orange or red.
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What is the Most Abundant Element on Earth?
The 8 most common elements in Earths crust (by mass):
46.6% Oxygen (O) yg
27.7% Silicon (Si)
8.1% Aluminum (Al)
5.0% Iron (Fe)
3.6% Calcium (Ca)
2.8% Sodium (Na)
2.6% Potassium (K)
2.1% Magnesium (Mg)
.
.
98.5%
.
.
15
th
Carbon (C)
wikipedia.org
What is the Most Abundant Element on
the Earths Upper Continental Crust?
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What is the Most Abundant Element in the Universe?
3/4 of all matter Hydrogen
25% Helium
3
rd
Oxygen 3 Oxygen
4
th
Carbon
Nitrogen
Silicon
Magnesium
Iron
Sulfur
other are relatively rare.
Google Abundance of the chemical elements
What is the Most Abundant Element in the Universe?
Abundances of the chemical elements: Solar system abundances.
Hydrogen and helium are most common from the Big Bang.
The next three elements (Li, Be, B) are rare because they are poorly synthesized in the Big Bang and also in stars.
The two general trends in the remaining stellar-produced elements are: (1) an alternation of abundance in
elements as they have even or odd atomic numbers, and (2) a general decrease in abundance, as elements
become heavier.
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What is the Most Abundant Element in Human Body?
Element Percent by mass
Oxygen 65
Carbon 18
Hydrogen 10
Nitrogen 3
Calcium 1.5
Phosphorus 1.2
Potassium 0.2
Sulfur 0.2
Chlorine 0.2
Sodium 0.1
Magnesium 0.05
Iron, Cobalt, Copper, Zinc, Iodine <0.05 each
Selenium Fluorine <0 01 each Selenium, Fluorine <0.01 each
By mass, human cells consist of 65-90% water (H
2
O) and
A significant portion is composed of carbon-containing organic molecules.
Facts about Carbon
Symbol C
Atomic number 6 (Atomic weight 12)
A member of group 14 (or IV) g p
Nonmetallic
Tetravalent (4 electrons for covalent bonds)
(a) sp
3
- Hybrid orbitals of carbon, (b) nickel tetracarbonyl,
(c) mesomerism of the aromatic compound benzene.
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On the Periodic Table
Due to its mid position in the periodic system and its associated
ability to form stable substances with more electropositive and more
electronegative reaction partners. (various bonding possibilities)
Theoretical Phase Diagram of Carbon
The state of matter for varying temperatures and pressures.
The hatched regions indicate conditions under which one phase is
metastable, so that two phases can coexist.
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Structure and Bonding
Electron configuration: 1s
2
, 2s
2
, 2p
2
(preferred tetravalence hybridization model)
(a) Diagram of atomic orbitals and sp
3
- hybridization,
(b) hybrid orbitals of carbon.
Graphene
Basic form of building block
Andre Geim and Konstantin Novoselov
the 2010 Nobel Prize in Physics for their work on graphene.
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Schematic of Electron Microscopy
Ernst Ruska, a German physicist.
the Nobel Prize in Physics in 1986 for his work in electron optics,
including the design of the first electron microscope.
Structure and Bonding
Electron configuration: 1s
2
, 2s
2
, 2p
2
(preferred tetravalence hybridization model)
(a) Diagram of atomic orbitals and sp
3
- hybridization,
(b) hybrid orbitals of carbon.
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Carbon Allotropes: Properties
Synthetic nanocrystalline diamond is
the hardest material known
Graphite is one of the softest materials known.
The system of carbon allotropes spans a range of extremes:
the hardest material known.
Diamond is the ultimate abrasive. Graphite is a very good lubricant.
Diamond is an excellent electrical insulator. Graphite is a conductor of electricity.
Diamond is the best known naturally
occurring thermal conductor.
Some forms of graphite are used for thermal
Insulation. (i.e. firebreaks and heat shields)
Diamond is highly transparent. Graphite is opaque. g y p p p q
Diamond crystallizes in the cubic system. Graphite crystallizes in the hexagonal system.
Amorphous carbon is completely isotropic.
Carbon nanotubes are among the most
anisotropic materials ever produced.
Allotrope Modification
1928, C
8
K, the first preparation of a graphite
intercalation compound
1929,
12
C and
13
C isotopes (mass number difference)
1936,
14
C (radioactive)
1985, the first observation of fullerenes
1991, carbon nanotubes were presented
as another new allotrope modification
2004, the first isolation of graphene
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Natural Diamond
Diamond, whose name is derived from the Greek words diaphanes (translucent)
and adamas (invincible), has also been known for long.
It was first discovered in India around 4000 BC. The oldest, and at the same time
one of the biggest diamonds surviving to our days (105 carat, 21.6g) is the Koh-I-
Noor. It was presumably found in India about 3000 BC.
British Crown Jewel
The Hope Diamond is a large, 45.52 carats (9.10g),
deep-blue diamond, housed in the Smithsonian
Natural History Museum in Washington, D.C.
The Hope Diamond is blue to the naked eye
because of trace amounts of boron within its
crystal structure, but it exhibits red
phosphorescence after exposure to ultraviolet light.
Synthetic Diamond
Numerous claims of diamond synthesis were documented between 1879
and 1928; most of those attempts were carefully analyzed but none were
confirmed.
In the 1940s, systematic research began in the United States, Sweden
and the Soviet Union to grow diamonds using CVD and HPHT processes.
The first reproducible synthesis was reported around 1953. Those two
processes still dominate the production of synthetic diamond.
A third method, known as detonation synthesis, entered the diamond
market in the late 1990s. In this process, nanometer-sized diamond
grains are created in a detonation of carbon-containing explosives. A
f th th d t ti hit ith hi h lt d h b fourth method, treating graphite with high-power ultrasound, has been
demonstrated in the laboratory, but currently has no commercial
application.
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Synthetic Diamond
General Electric (GE) diamond project, 1955.
The age of industrial diamond began when GE started the first
larger-scale production in US larger-scale production in US.
Synthetic Diamond
The original GE invention by Tracy Hall uses the belt press wherein
the upper and lower anvils supply the pressure load to a cylindrical
inner cell. This internal pressure is confined radially by a belt of
pre stressed steel bands The anvils also serve as electrodes
HPHT (High Pressure High Temperature): the mass-production of high-quality diamond crystals
pre-stressed steel bands. The anvils also serve as electrodes
providing electrical current to the compressed cell.
(10 GPa and temperatures above 2000 C)
CVD (Chemical Vapor Deposition): thin film form as surface coating
Chemical vapor deposition is a method by which diamond can be
grown from a hydrocarbon gas mixture. Since the early 1980s, this
method has been the subject of intensive worldwide research.
Whereas the mass production of high quality diamond crystals Whereas the mass-production of high-quality diamond crystals
make the HPHT process the more suitable choice for industrial
applications, the flexibility and simplicity of CVD setups explain the
popularity of CVD growth in laboratory research. The advantages of
CVD diamond growth include the ability to grow diamond over
large areas and on various substrates, and the fine control over the
chemical impurities and thus properties of the diamond produced.
(Methane + Hydrogen, less than 27kPa, 800 C)
Will learn more later
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Synthetic Diamond
HPHT (High Pressure High Temperature): the mass-production of high-quality diamond crystals
Synthetic Diamond (most recent)
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Synthetic Diamond
Figure 2: Structure of a single nanodiamond particle.
Graphite
The term graphite reflects its use as a pigment.
It derived from the Greek word graphein, meaning to write.
Most pencil cores are made of graphite
mixed with a clay binder
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Structure and Bonding
Electron configuration: 1s
2
, 2s
2
, 2p
2
(preferred tetravalence hybridization model)
(a) Diagram of atomic orbitals and sp
3
- hybridization,
(b) hybrid orbitals of carbon.
Structure and Bonding
From each C-atom From each C atom,
thee bonds:
Leading along the hexagons edges,
Correspond to sp
2
hybridization
The streaming electrons, contained
in the p
z
-orbitals, do also interact:
they form a cloud that is delocalized
over the entire graphene layer.
-anisotropic properties (anisotropic
electrical conductivity) y)
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Graphite and Its Structure
The structure of graphite: elucidated from 1917 by Debye, Scherrer, Grimm, Otto and Bernal
Characterized by a succession of distinct graphene layers that spread over an xy-plane. They are
stacked in a z-direction, and there are only weak van der Waals interaction among them.
1.4 (141.5pm)
3.4 (335.4pm)
-graphite -graphite
Hexagonal unit cell:
containing 4 carbon atoms
2.456 x 2.456 x 10.062
The sequence of layers in hexagonal (normal &
more stable): Bernal-stacked trilayers (a) and
rhombohedral graphite (b).
( p )
weak van der Waals interaction
layer easily shifted in parallel
Graphite and Its Structure
-graphite -graphite
milling
Heating >1025 C
The enthalpy of formation is
just about 0.06kJ/mol higher.
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Graphite and Its Structure
In reality,
The interplanar distance is about 344pm due to stacking disorder.
There is virtually no more interaction between the layers, and
The orientation of individual planes no longer has an influence on The orientation of individual planes no longer has an influence on
the effective forces.
Usually the layers are irregularly turned around the z-axis and
shifted against each other in the xy-direction.
These structures are called Turbostratic.
Graphite and Its Structure
Turbostratic microstructure of primary carbon particles. TEM micrographs showing the turbostratic
microstructures, consisting of concentric carbon layers surrounding a) several nuclei in vehicle exhaust
(arrows), or b) a single nucleus in wood smoke (arrow). The inset shows a SAED pattern from a wood
smoke particle. The arrowhead points at the ring corresponding to the 002 spacings in the turbostratic
microstructure.
Kocbach et al. Particle and Fibre Toxicology 2006 3:1 doi:10.1186/1743-8977-3-1