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³³Principles of Principles of NanoNano ChemistryChemistryandand NanoNano TechnologyTechnology´́
Associate ProfessorAssociate Professor in Chemistryin ChemistryP.G. and Research Department of P.G. and Research Department of
ChemistryChemistryA.V.V.M SriA.V.V.M Sri PushpamPushpam College,College, PoondiPoondi,,
ThanjavurThanjavur DtDt,,
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there is an important message here for all of
us to nurture young talent for all scientific
research work, particularly in nanoscience and
nanotechnology. With 540 million youth inIndia, we have to hone skills of youth at the
graduate, post-graduate and Ph.D levels, " Mr.
Kalam said.
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- He rued that despite doing exceedinglywell in the field of research in advanced
topics right from the late 1950s, Indialagged behind in implementing the
research findings on a commercial level.
"This should not happen vis-à-vis areas like
nanotechnology ..
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History
China- 1000 years ago ± gold nano
particles as inorganic dye to
introduce red color in ceramic
porcelains
Faraday ±1857- electrolysis ± gold
nano particles ± colloid.
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Contd
Colloidal gold was and is still used for medical
treatment of arthritis.
Number of diseases were diagnosed by
sending colloidal gold with the spinal liquid.
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Diffrence between nano and bulk?
Nano ± Particles of size between 1nm to 50
nm
Bulk ± Particles of size larger than 60nm
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Nano-science & Nano-technologyNanoscience is actually Materials Science at atomic level.
Nano-technology is Controlled manufacturing and
characterization of materials with predetermined and artificially
modified atomic and molecular structure.
To accomplish that one needs to manipulate with atoms and
molecules at nanoscale.
The word ³nano´ relates to the dimension scale comparable
with 1 nm = 10-9m.
Typical size of nano-objects ranges from 1 to 100 nm
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Less than a
nanometer
Individualatoms are up
to a few tenths
of a nanometer
in diameter
Nanometer
Ten shoulder-
to-shoulder hydrogen
atoms (blue
balls) span 1
nanometer.
DNA
molecules are
about 2.5nm
wide
Thousands of
nanometers
Biologicalcells, like
these red
blood cells,
have
diameters in
the range of
thousands of
nanometers
A million
nanometers
An ant ismillions of
nanometers
across
Billions of
nanometers
A two meter tall male is two
billion
nanometers
tall
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Characteristics of Nanoscalar materials: <L> <<100nm!
Size : 10-9m
Area : 10-18 m2
Volume : 10-27 m3
Mass : 10-24kg
Specific surface area : 106 m2/kg
% of chemical bonding sites on the surface : 20-50
Large Gibbs Free Energy : Ease of sintering/
Ease of dissolution
Surface forces and Brownian motion become increasingly
significant
You cannot see or touch discrete nanoscalar materials
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Nano-synthesis Technology
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Research
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Top-down versus Bottom-up
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Physical Properties1. Refractive index
2. Melting & boiling points
3. Density
4. Surface Area
Chemical properties1. Catalytic properties
2. Solubility
3. Stability
4. Reactivity
Properties
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Examples of material creation
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Size Dependent
Absorption
Absorption spectra of particles with different sizes: with a decrease in particle size, thewavelength of the absorption maximum shifts to lower wavelength.
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Size Dependent Emission
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Surface Area
Surface area to volume ratioincreases in nanomaterials
A large particle, when dividedinto many small particles,results in exposure of moresurface, thus increasing thesurface area to volume ratio
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Types of nanomaterials
0 D Sphere
1 D Nanorods
2 D Sheets 3 D Crystals, cubes
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Carbon The Magic Element
One of the first elements known to mankind Latin word "carbo" meaning "charcoal "
llotropes of Carbon Amorphous carbon, Graphite
and Diamond
Graphite Diamond
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What are Carbon Nanomaterials?
Fullerenes, carbon nanotubes, Graphite whiskers,
Cones and Nanocrystalline diamond
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Fullerenes Basics
Discovery ± 1985 ± Kroto, Smalley and Curl ±
Nobel Prize in Chemistry in 1996
Fullerenes are large carbon-cage molecules. Byfar the most common one is C
60-- also called a
"buckyball"-- but some other relatively
common ones are C70, C76, and C84 (there areplenty of others too)
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History of Fullerenes
Truncated icosahedron was known for more than 500 years
1960s soccer-shaped Corannulene was synthesized
1970 Eiji Osawa proposed that a molecule made up of sp2
hybridized carbons could have the soccer structure
1973 - Russian scientists independently proposed the structure
of C60 and predicted some properties and also of C20 the
smallest fullerene
Corannulene ± Buckybowl ± C20H10
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Fulleren pentagon and hexagon
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An international collaboration
Harry Kroto (U Sussex),
synthesis of interstellar
molecules
Bob Curl (left) and Richard Smalley
(right) (Rice U, Texas),Cluster chemistry
from a laser-supersonic vaporization
beam
Together, the two groups attempted to simulate the
generation of C-containing molecules in the stars. In
1985, they discovered C60, a new allotrope of carbon.
The compound was very stable and accompanied by
amounts of C70 (m/z 840).
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C60, high symmetry,fused pentagon &
hexagons
Smalley¶s paper model,Kroto & Curl add C=C¶s
Single bonds in red,C=C in yellow
Fullerene ± Structure
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Curl
Smalley
O¶Brien
Kroto
Heath
Discovery of Fullerenes
Nobel Prize in Chemistry in 1996
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Why ³Bucky Ball´ or buckminsterfullerene?
R. Buckminster Fuller
1895-1983
Key thinker, visionary, inventor of the 20th
century, impacting architecture, math, art,
philosophy, religion, physics, literature,
urban development & design, industry &
technology.
Inventor of the
geodesic dome
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Buckyball Structure
Fullerenes are polyeders built up by coordinated
carbon atoms with 12 pentagons and (n)
hexagons, where the minimum for n is 20.
Fullerenes fulfil the EULER's theorem, where a
polyeder built up from pentagons and
hexagons has to contain exactly 12 pentagons,
to build a closed structure. Following this rule,the dodekaheder with 20 carbon atoms is the
smallest possible fullerene.
For the stability of the structure, it is important that no pentagons
are side by side. This is described by the Isolated Pentagon Rule(IPR). If two pentagons are adjacent, the tension of the binding is
increasing and the structure is not any more energetically stable.
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Discovery of CNT
Discovered by Dr.Sumio Ijima,NEC, Japan in 1991
Discovery accidental during the synthesis of
f ullerenes(C60)
Rapid increase in publications in the last 15years ²More than 15000 publications involvingCNTs in the literature
Generated great interest in several applicationsincluding field emission devices, nanoscaletransistors, tips for scanning microscopy or
components for composite materials
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What are carbon nanotubes?
CNT is a new molecular form of carbon andconfigurationally equivalent to twodimensional graphene sheet rolled into a tube
Quite distinct from diamond and graphite
Novel nanostr uctures and the most commonlyused building blocks of nanotechnology
Two Types
Single - wall CNT (SWCNT)
Multi-wall CNT (MWCNT)
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SWCNT Single-wall carbon nanotube (SWCNT) ²
consist of a single tube of graphite formed byrolling a sheet of graphene into a cylinder along an (m,n) lattice vector in the grapheneplane.
The (m,n) indices determine the diameter andchirality ² the key parameters of CNT
Depending on the chirality, CNTs can beeither metals or semiconductors
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Some SWCNT with different
chiralities
Armchair
Zigzag
Chiral
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MWCNT
Multi-wall carbon nanotube (MWCNT) ² consist
of several concentric tubes of graphite fittedone inside the other
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Some special properties of CNTs
High surface area
Extraordinary mechanical properties - Tensilestrength is one hundred time more thansteel.Young·s modulus is over 1 Tera Pascal. It
is stiff as diamond. The estimated tensilestrength is 200 Gega Pascal.
Thermal conductivity is higher than diamond
Electrical conductivity similar to copper
Can be metallic or semiconducting
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Applications:
Catalysis
It binds to HIV
Antibacterial activity-Destroy the cell wallsof bacterium
Envirmental - odour removal
Surface enchanced Raman spectra
Coloring agents ²ancient days
Drug delivery , unknown action in the body.
To destroy cancer cells
Electronics
optics
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Metallic Nanoparticles
Synthesis
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Other applications
Solar cells
Sun screen lotions
Paints TiO2
Pt-Ru electrocatalyst for fuel cell
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Thank
You All !