Course title: Nanoscience
Course Code: CH-10005
L-T-P Structure: 2-0-0
Dr. Pratap Kumar Deheri
Assistant Prof.
School of Applied Sciences, Department of Chemistry
Kalinga Institute of Industrial Technology (KIIT)
Textbook of Nanoscience and Nanotechnology: B S Murty, P Shankar, Baldev Raj, B B Rath and James Murday, Edited by Baldev Raj, Springer, 1st ed.,
ISBN-13: 978-3662509128
Introduction to Nanoscience and Nanotechnology, An Indian Adaptation: Charles P. Poole Jr., Frank J. Owens, Wiley, 3rd ed., ISBN-13: 9354240201-978
Outline of the Lecture
• What is Nano scale Science?
• Actual physical dimensions relevant to Nano systems.
• Properties of Nanomaterial.
• Size & Shape Dependent Properties – at Nano scale
Nanomaterials are not new
17th Century -Damascus sabers contain carbon nanotubes
The Lycurgus cup
The glass appears green in reflected light (A) and
red-purple in transmitted light (B).
Plasmonic nanocomposites
contains metallic (Ag, Au) spherical nanoparticles (40-80nm)
dispersed in a complex way in the glaze, which gives rise to
special optical properties (scattering) transmission electron microscopy images of carbon
nanotubes in a genuine Damascus sabre
Nanoscience to Nanotechnology
“There is plenty of room at
the bottom”
Richard Feynman
American Physical Society, Gordon Moore
1959 Co-founder of the Intel Corporation
Moore's first law says that the amount of space required to install a transistor on a chip shrinks by roughly
half every 18 months.
Actual physical dimensions relevant to
Nanosystem
Nanoscience
0.1nm 1nm 10nm 100nm 1m 10 m
Size and shape dependent
properties
Nanometer scale : The length scale where corresponding
property is size & shape dependent.
Comparing the size
Length Scale
• Bohr radius = 0.5292Å ≈ 0.05 nm
• C atom (VdW radius)=0.17 nm
• In a 1nm line: 3C atoms
• In a 1nm x 1nm surface: 9C atoms
• In a 1nm x 1nm x 1nm cube: 27 C
atoms
• In a 100 nm x 100 nm x 100 nm cube:
2.7 x 107 C atoms
• In a 1m x 1m x 1m cube: 2.7 x 1028 C atoms
Typical nanosystems may contain from hundreds to tens of
thousands of atoms.
The reason for strange properties of nanomaterials
Nanomaterials show unique properties at the nanoscale compared to its bulk counterparts. There are two
fundamental reasons for this behavior of nanomaterials: surface effects and quantum effects
As surface to volume ratio increases
• A greater amount of a substance comes in contact
with surrounding material.
• This results in better catalysts, since a greater
proportion of the material is exposed for potential
reaction.
Nanosystems: % of Surface atoms
Example of Gold Nano particle:
➢ Sphere of radius 12.5 nm contains total approx. 480,000 atoms.
surface contains approx. 48,000 atoms.
So, approx. 10% atoms are on the surface.
➢ Sphere of radius 5 nm contains total approx. 32,000 atoms.
surface contains approx. 8000 atoms.
So, approx. 25% atoms are on the surface.
Surface atoms have unused electrons – so very reactive
(can be used for catalysis)
Nanosystems: Surface Energy
Example of Gold Nano particle:
Eb(d) stands for the energy per bond
surface atom n- surface
undisturbed bulk material n-bulk
na = number of atoms per unit area on the surface
nb = number of bonds broken per atom
Nanosystems: Size vs. reactivity
are thermodynamically and kinetically unstable in solution
Dangling Bonds of Nanoparticles
high surface energy exhibit a dual nature: poor stability and high reactivity
due to the high reactivity of nanomaterials, they can be easily
processed into desired functional nanomaterials by suitable
chemical transformations
Atoms in materials generally exhibit two different bonding
environments: saturated internal atoms and unsaturated
surface atoms. Different from the saturated internal atoms, the
unsaturated surface atoms leave some chemical bonds
“dangling” on the outside, i.e., dangling bonds
Nanosystems:
Quantum effect
• Quantum confinement
occurs when the particle size
of the material is too small to
be comparable to the Bohr
excition radius, thus
confining the electron
mobility
Classifications-
Nanomaterials are materials with at least one external dimension that measures 100 nanometers (nm) or less
0 D : all three dimensions in the nanoscale (nanoparticles, 10nm)
1 D : one dimension in macroscale and other two in nanoscale ( nanofibers, nanowires)
2 D : two dimensions in macroscale and the other in the nanoscale ( nano sheets, thin films)
3 D : no dimensions at the nanoscale, all are in the macroscale (nanostructures within -materials)
Nanosystems: Quantum effect
Photoluminescent
The color or mission wave length is size dependent
Nanosystems: Quantum effect
Length scale corresponding to quantum confinement
regime is 1–25 nm
increase of the bandgap (or HOMO–LUMO energy gap)
and the appearance of discrete energy levels near the
band edges with decreasing NC dimensions
colours are determined by the size and shape of gold nanoparticles
Nanosystems: size vs color
The localized surface plasmon resonance
(LSPR) phenomenon on the surface of
gold nanoparticles under irradiation at
specific light wavelengths
Nanosystems: Surface plasmn effect
Localized Surface Plasmon Resonance (LSPR): free electrons in the metal NP are driven
into oscillation due to a strong coupling with a specific wavelength of incident light.
Nanosystems: Size vs Color
Paul Karason gradually got blue skin after he took a
homemade silver chloride in an attempt to treat problems
with his sinuses, dermatitis and other issues. This condition
is called Argyria
mixtures of silver sulfide (Ag2 S) and silver selenide (Ag2 Se)
Nanosystems: catalyst
Catalysis contributes the mechanism by which chemical transformations take place
effect of atomic coordination decrease is huge and it brings together the exhibition of a surface in a nano-catalyst
Difference between homogeneous, heterogeneous and nano-catalysts
Nanosystems: catalyst
Fischer–Tropsch process involves a series of chemical reactions
that produce a variety of hydrocarbons
Alumina loaded with nano-iron oxide and cobalt
Biodiesel
Photocatalysts
Nanosystems: Size vs physical properties
Melting point of solid particles vary
inversely with radius
𝑇𝑚 𝑀𝑒𝑙𝑡𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑙𝑢𝑠𝑡𝑢𝑟𝑒 𝑤𝑖𝑡ℎ 𝑟𝑎𝑑𝑖𝑢𝑠 𝑟
𝑇0 Melting point of bulk
melting point of gold 1064
𝑉𝑚(𝑙) 𝑀𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑
𝛾𝑠𝑙 Interfacial surface tension between solid liquid
∆Hm Bulk latent heat of melting
the number of gold atoms on the surface roughly equals the bulk gold atoms inside
This surface-to-bulk atomic volume ratio is a significant contributing factor to the melting point depression
observed in gold and other pure metals
Nanosystems: Size vs physical properties
electronic, optical, and chemical properties
While bulk materials have constant physical properties
Transparent alumina,,,,,,ZnO
regardless of size, the size of a nanoparticle dictates its physical
and chemical properties
Nanosystems: In nature
Bone is a composite of collagen fibers reinforced with calcium
phosphate nanocrystals arranged in a semi-regular pattern
Nanosystems: In nature
A close-up look at the wings of the Rajah Brooke's birdwing butterfly with a scanning electron microscope reveals tiny
structures in their wing scales that trap light so that virtually none escapes
Butterfly wings look smooth to the naked eye, but magnification shows that they are covered in scales with a mesh-like surface
of ridges and holes that channel light into the scale’s spongy interior. Inside the scales, pillar-like beams of tissue scatter light
until it is absorbed…………………………. Ultrablack Coloration
Nanosystems: In nature
The beautiful color patterns of peacock feathers are also known
to be due to the cross-sectional arrangement of their feather
frills
cells in which optical nanocrystals are found, called iridophores
swell when the animals get excited
causes the crystals to become spaced further apart, a
configuration that leads them to "reflect longer wavelengths [of
light], such as yellow, orange or red
Nanosystems: In nature Lotus effect
This effect is the combination of the chemical make-up of the surface
and the micro-and nano-projections on the surface
Air is trapped in the micro bumps and waxy nano particles
This cuts water-surface contact area making the water droplet to float
has self-cleaning characteristics due to the ultra-hydrophobicity
Water’s high surface tension results in droplets turn into an almost spherical shape. As minimal surface
area is contained by the sphere, this shape reduces the solid-liquid surface energy. When liquid contacts
with the surface, the surface gets wet due to the adhesion forces. The droplet's fluid tension and surface's
structure determines whether the wetting is incomplete or complete
Nanosystems:
Mollusks create nacre by depositing amorphous calcium carbonate (CaCO3) onto porous
layers of polysaccharide chitin. The mineral then crystallizes, producing stacks of
CaCO3 that are separated by layers of organic material. Its strength is due to the brick-like
assembly (interlocked) of the molecules. Researchers at many universities are synthesizing
biomimetic nanocomposites to create strong materials for use in light-weight armor
systems
Nanosystems: Spider web/silk
Silk is a hierarchical structure
comprised of a protein, which folds
into sheets and forms crystals. These
hard protein crystals are
interconnected by softer, amorphous
chains
spider silk fibre has temperature adaptibility, high specific
strength, excellent elasticity, and super toughness
Nanosystems: In Textile
SiO2 agglomeration of cotton fiber
Ionic silver has a strong affinity to sulphur. It is therefore able to
bind to thiol (-SH) groups in enzymes and inactivates them
NanoMaterials Classifications
For the better understanding, nanomaterials are again organized into four types
(i) Carbon based materials (ii) Metal/Metal Oxide based materials (iii) Dendrimers (iv) Composites
Hyperbranched macromolecules commonly referred to as dendrimers
NanoMaterials -Composites
Composites are engineered or naturally occurring solid materials which results when two or more different
constituent materials, each having its own significant characteristic (physical or chemical properties) are
combined together to create a new substance with superior properties than original materials in a specific
finished structure
➢Stiffness and strength
➢Low coefficient of expansion
➢Resistance аgаinst fatigue
➢Ease in manufacturing complex shapes
➢Simple repair of damaged structures
➢Resistance to corrosion
NanoMaterials -Composites
the implementation of polymer/CNT nanocomposite in a space shuttle and
commercial aircraft
flexible and stretchable polymer/CNTs composites
Classifications-composition based
(1) inorganic-based nanomaterials; (2) carbon-based nanomaterials; (3) organic-based nanomaterials;
and (4) composite-based nanomaterials.
NanoMaterials- Carbon based
The schematics of the representative carbon-based nanomaterials
Diamond Nanostructures
In diamond, the sp3 - hybridized carbon atoms are bonded covalently to
other four nearby carbon atoms resulting in the tetrahedral structure
NanoMaterials- Carbon based
The fullerenes (allotropes of carbon) are graphene sheets rolled into spheres. It is a cage like molecule
Fullerenes composed of atomic C n clusters (n > 20)
In C60-fullerene carbon atom joined together by single and double bonds to form a hollow sphere
with 20 hexagonal and 12 pentagonal faces (a design that resembles a football).
C60 is the most common and best-investigated fullerene.
NanoMaterials- Carbon based
graphene, carbon atoms exhibit sp2-hybridization connected by σ- and π-
bonds in a two-dimensional hexagonal crystal lattice with a distance of
0.142 nm between neighboring atoms of carbon hexagons. Graphene also
represents a structural element of some other carbon allotropes, such as
graphite, carbon nanotubes and fullerenes
SWCNTs have a diameter around 1–3 nm and a length of a few
micrometers
Multi-walled CNTs have a diameter of 5–40 nm and a length around 10 μm
NanoMaterials- Carbon based
Three distinct tubular structures caused by the orientation of rolling up a graphene sheet
can be identified: armchair, zigzag and chiral
The armchair CNTs share similar electrical properties to metals, while the zigzag and chiral CNTs present similar
properties to semiconductors
https://www.youtube.com/watch?v=l3lRDG1HAmA&t=109s
CNT-preparation
Potential applications of carbon-based nanomaterials in
environmetal and agricultural sectors. See text for details
Schematic representation of chemical vapor deposition
(CVD) process. a Simplified scheme of a CVD reactor for high tensile strength, they are incorporated into polymers and
CNTs synthesys; b base-growth model of CNT growth other materials in order to create structural and composite
mechanism; c tip-growth model of CNT growth mechanism materials
Activated carbon (AC) has been widely used as a sorbent for conventional wastewater treatment due to its large
surface area and ability to adsorb a broad spectrum of organic and inorganic contaminants
NanoMaterials- Clay based
Nano-structured clay exists in nature by its own. If the clay
microstructure is analyzed closely, one can find the bulk clay is agglomerations of nano-
structured units like rods, tubes and plates. With little effort these agglomeration can be
breaks
into individual nano-structures to exploit the nano-properties to its fullest
nanosilicate sheet
Vermiculite
Mica clay structure
Kaolinite and Halloysite clay structure
NanoMaterials- Clay based
The polymer/clay composites are broadly divided into three
categories.
➢clay materials are just mixed with polymer matrix
The individual clay particles are called tactoids
➢Second one is intercalated nanocomposites; polymer
molecules get into clay inter-layer and are sandwich in between
clay platelets
➢The third one is exfoliatednanocomposites; individual 1 nm
thick clay layers are separated in the continuous polymer/matrix
NanoMaterials- Metal based
➢ Photothermal therapy
AuNP absorbs near-infra-red (NIR) light, absorbed light is converted into heat
➢ Targeted drug delivery
High efficacy of antitumour agents and also antibiot-ics conjugated with AuNPs
NanoMaterials- metal based
sodium borohydride (NaBH4)
Antimicrobial Activity-release silver ions, and it involves adhesion and destruction
of the cell wall or microbial membrane
Sensing – enhanced fluorescence,
Pollution Degradation-photocatalytic degradation of pollutants
NanoMaterials- Metal Oxides based
nanoparticles of CuO, ZnO, SnO2, Al2O3, MgO, ZrO2 AgO, TiO2
applications of titanium dioxide and zinc oxide nanoparticles are highlighted in skin care products
Protects Skin From Sun Damage
Healing Of Skin
Prevents Bacterial Infection
NanoMaterials- Bioorganic based
Dendrimers, micelles, liposomes and ferritin, etc. are
commonly knows the organic nanoparticles
Ferritin, hollow nanocage with multiple metal–protein interactions
the primary iron storage protein
