Unit I

Introduction to
Nanomaterials and its
properties
 Introduction to Nanomaterials and its properties
Nanotechnology
The branch of technology that deals with dimensions of less than 100 nanometres,
especially the manipulation of individual atoms and molecules.

Nanomaterials
Material having particles or constituents of nanoscale dimensions in any one dimensions.
 Introduction to Nanomaterials and its properties

ANCIENT NANOWONDERS
Ancient periodical evidences have proven the use of nanomaterials for various materials
like,
 Lycurgus Cup
 Damascus steel swords
 Stained window glasses, etc…

DAMASCUS SWORDS
from the Middle East were made between AD300 and
AD1700 and are known for their impressive strength, shatter
LYCURGUS CUP resistance and exceptionally sharp cutting edge. The steel
reveals a brilliant red when light passes blades contain oriented nanoscale wire-and-tube-like
through its sections of glass containing structures, which almost certainly enhanced the material's
gold-silver alloyed nanoparticles. properties.

Silver nano-colloids were used by Persians,

Babylonian and Greek civilizations as antibiotics Deruta ceramicists produced
dramatic iridescent or metallic
glazes, which, during the
fifteenth and sixteenth
centuries, were in demand
throughout Europe. To achieve
the red and gold luster effects,
particles of copper and silver
metal between 5 and 100
Silver Nanoprisms Gold spheres Gold spheres Silver spheres Silver spheres Silver spheres
~100nm ~100nm ~50nm ~100nm ~80nm ~40nm billionths of a meter were used.
Instead of scattering light, the
particles cause light to bounce
off their surface at different
Silver and Gold nano quantum dots were used in wavelengths, giving metallic or
making stained glass windows iridescent effects.

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 Introduction to Nanomaterials and its properties
EMERGENCE OF NANOTECHNOLOGY

First electron microscope Richard Feynman gave a lecture:

Einstein estimated the size of
sugar compound to 1nm
was constructed by Ernest “There’s plenty of Room at the
Ruska and Max Knoll Bottom”

Scanning tunnelling microscopy (STM) was Norio Taniguchi first time used the
developed by Gerd Binning and Henrich Rohrer term “Nanotechnology”

Eric Drexler seems popularization of Sumio Jijima invented the carbon

nanotechnology “Engines of Cration” nanoparticles

Royal Society report on the The National Nanotechnology initiative

implication of Nanotechnology (NNI) was created in the US

Nanoparticles are used for drug delivery Studying the effects of nanoparticles
to cure cancer on the environment and organisms

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 Introduction to Nanomaterials and its properties
SURFACE AREA TO VOLUME RATIO
The surface area to volume ratio is the amount of surface area per unit volume of an object. Chemical
reactions which involve solid materials, the surface area to volume ratio is an important factor for the
reactivity.

 Nanoscale materials have a larger surface areas than the macroscopic materials

 A greater amount of material come into contact with surrounding materials thus affecting
reactivity

SURFACE AREA TO VOLUME RATIO - CUBE

As the volume of cube increases, the surface area decreases and vice versa. It can be observed that on
decreasing the volume of the cube, the surface area increases which results in greater amount of material
contact with the external environment.

SURFACE AREA TO VOLUME RATIO - SPHERE

𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 4π𝑟 2

=
𝑉𝑜𝑙𝑢𝑚𝑒 4π𝑟 3
𝟏 3
𝑺𝒖𝒓𝒇𝒂𝒄𝒆 𝒂𝒓𝒆𝒂 ∝
𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 3𝒓
=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑟
Volume ∝ 𝒓

It can be seen that as the volume decreases the surface area increases in both cases (cube and sphere).
This is applicable for all kinds of geometrical shapes. This is why when the size of the particle is
reduced its surface area increases, this property enhances a greater amount of material to contact with
the external stimuli due to larger surface area and result in high reactivity.
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 Introduction to Nanomaterials and its properties
SURFACE ENERGY

 Surface free energy is a measure of the excess energy present at the surface of a material, in
comparison to at its bulk.

 Surface energy is a relative measurement of the energy at the surface

(which is a result of this incomplete bonding)

 It can be used to describe wetting and adhesion between materials

The molecular force of attraction between unlike materials determines their adhesion. The
strength of attraction is depends on the surface energy of the substrate. Higher surface energy means
a strong molecular attraction, while lower surface energy means weaker attractive forces. For a
liquid adhesive to effectively wet out a surface, the surface energy of the adhesive must be lower
than the surface energy of the substrate to be bonded. When surface energy of the substrate is more,
the liquid dropped on the surface completely wets it. Wetting can also be measured based on the
contact angle (θ) of the liquid on the surface. As surface energy of the substrate increases, the liquid
contact angle decreases and results in more wetting. At lower surface energy, the contact angle is
very high and wetting of liquid over the surface is very low.

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 Introduction to Nanomaterials and its properties
SURFACE STRESS
The amount of the reversible work per unit area needed to elastically stretch a
pre-existing surface.

Surface stress components

Positive
Tensile stress
Negative Compressive stress
TENSILE STRESS COMPRESSIVE STRESS

SURFACE DEFECTS
Surface defects are the boundaries, or planes, that separate a material into regions, each
region having the same crystal structure but different orientations. Surface defects for a
substrate should be minimum inorder to achieve uniform coating. The various kinds of
surface defects are
Grain boundaries Groove
Surface crack Blister
Artificial cracks Cavity
Internal crack Wrinkle
Scratch Grooves

Grain boundary Blisters

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 Introduction to Nanomaterials and its properties
PROPERTIES AT NANOSCALE
• The properties of nanomaterials depend on size, crystal structure, surface characteristics and particle size.
 Two primary factors that cause nanomaterials to behave different from bulk,
 Surface effects
 Quantum confinement effects
When a material size is reduced from bulk to nano form various properties like
 Physical
 Chemical
 Mechanical
 Optical properties gets altered
MECHANICAL PROPERTIES
 As an object gets smaller its relative strength increases. Nanomaterials have a higher strength when
compared with bulk materials of larger volume.
 The number of imperfections in an object decreases as its size decreases which results in increase of
strength at nanoscale.
 The enhancement in mechanical strength is due to the reduced probability of defects.

OPTICAL PROPERTIES

 When the size of a material is reduced to nanoscale, confinement of electron takes place.
 Electrons cannot move about as freely at nanoscale and becomes restricted.
 The confinement of electrons causes them to react to light differently.
 At nanolevel, there is a shift in band gap, the band gap of a material increases which alters the optical
properties at nanoscale level.

Bulk Gold Nano Gold

Nanosized gold microstructure

Example: Bulk gold appears yellow in colour, whereas nanosized gold appears red in colour
Nanosized zinc oxide particles will not scatter visible light and block UV light, thus it is
used in sun screens.
The bandgap of nanomaterials varies based on the particle size, which results in emission of different
colours for different particle sizes.

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 Introduction to Nanomaterials and its properties
MELTING POINT

 Nanomaterials have significantly lower melting point.

 Lower phase transition temperature.
 Since the size of nanomaterials are small, spacing between atoms decreases which reduce the lattice
constant.
 Due to huge fraction of surface atoms in total number of atoms, the material can be easily melted
 Melting point of a nanomaterial depends on its
particle size. As the particle size decreases,
the melting point also decreases
 Since at nanoscale level, more surface atoms
are present than the bulk. For a small
temperature itself surface atoms gets
disturbed and reaches into the bulk which
results in lower melting point.

ELECTRICAL CONDUCTIVITY
The movement of electrons and holes decide the electrical property of a material. These properties are
based on the chemical and physics structure of the material. Materials at nanoscale exhibit interesting
electrical properties.
 The electrical conductivity decreases due to the reduced dimensions and confinement of electrons.
 The electrons gets confined and no space is available for the electrons to move freely

CHEMICAL PROPERTIES

Since nanoparticles have a larger surface area than the bulk material. It can have contact with the
external stimuli at a larger scale and result in high reactivity.