The document provides an overview of nanomaterials, covering their significance, properties, and synthesis methods, as well as their applications in various fields. It distinguishes nanomaterials into three categories based on dimensions and explains the impact of nanoscale on physical and chemical properties due to increased surface area and quantum effects. Key synthesis techniques discussed include top-down and bottom-up approaches, while highlighting the influence of size on properties like optical, thermal, magnetic, and chemical behavior.

1. 1
Nano-materials
(Unit-4 Engineering Physics)
Dr. Shyam Sunder Sharma
Department of Physics (H & S)
Women Engineering College, Ajmer- 305002, India
(An Autonomous Institute of Govt. of Rajasthan)
shyam@gweca.ac.in

2.  Nano-materials: Significance of nanoscale
 Properties of nanomaterials
 Basics of Synthesis of nanomaterials: top-down and bottom-up
approach
 Applications of nanomaterials
Topics to be covered:

3.  Nano-science is the study of structures and materials at atomic and
molecular scales, where properties differ significantly from those
at a larger scale.
 Nanotechnology is the design, characterization, production and
application of structures, devices and systems by controlling shape
and size at nanometre scale.
 When the material size of the object is reduced to nanoscale, then
it exhibits different properties than the same material in bulk form.

4.  The word nano technology is relatively new, the existence of
nanostructures and nano-devices is not new. Such structures
existed on the earth as life itself. Although it is not known when
humans began to use nanosized materials, the first known, Roman
glassmakers were fabricated glasses containing nanosized metals.
 Richard Feynman is considered as the Father of modern day
Nanotechnology.
 In 1959, he delivered a lecture in annual meeting of American
Physical Society, with title: “There is a Plenty of Room at the
Bottom”. The focus of his speech was about the field of
miniaturization and how he believed man would create
increasingly smaller and powerful devices.
 After fifteen years, Norio Taniguchi, a Japanese scientist was the
first to use and define the term “nanotechnology” in 1974.
Origin of Nano technology

5.  The prefix ‘nano’ is referred to a Greek prefix meaning ‘dwarf’ or
something very small and depicts one thousand millionth of a meter.
 Nanometer (nm) = one billionth of a meter or one thousand
millionth of a meter (10−9 m).
 Nanomaterials are commonly defined as materials with an average
grain size in the range 1- 100 nm. These have extremely small size
which having at least one dimension 100 nm.
A human hair is 80,000 nm wide
 Atoms are extremely small and the
diameter of a single atom varies from 0.1 to
0.5 nm depending on the type of the
element.
 For example, one carbon atom is
approximately 0.15 nm in diameter and a
water molecule is almost 0.3 nm across. A
red blood cell is approximately 7,000 nm
wide and human hair is 80,000 nm wide.

6. Nanometre scale- DNA
• 2 nm
http://www.gala-instrumente.de/ images/ deben _ CCD_DNA.jpg

7. Nanostructures
• Nanoparticles

8. Nanostructures
• Fullerenes (buckyballs) and carbon nanotubes (CNTs)

9. Nano materials are materials that have at least one of the dimensions in
the range 1- 100 nm. Therefore, Nanomaterials/Nanostructures are
divided into three categories:
 0-dimensional (0D)- If all three dimensions of the material are less
than 100 nm , such materials are called 0-dimensional nanomaterials
such as nanoparticles and quantum dots.
 1-dimensional (1D)-If only two dimensions are less than 100 nm, they
are called 1-dimensional nanomaterials such as nanotubes, nanowires
and nanorods.
 2-dimensional (2D)- If only one dimension is less than 100 nm, it is
called 2-dimensional (thin film) nanomaterials such as nanosheets,
nanoplates, nanowalls and nanodisks.
Nano materials

11. Examples of 0-D Nanomaterials
Examples of 1-D Nanomaterials
Examples of 2-D Nanomaterials

12. Basic principles of nano materials
When the material size of the object is reduced to nanoscale, then it
exhibits different properties than the same material in bulk form. The
factors that differentiates the nanomaterials form bulk material is
a) Increase in surface area to volume ratio and
b) Quantum confinement effect
a) Increase in surface area to volume ratio
The ratio of surface area to volume ratio is large for nano materials.
Surface size is larger so a greater amount of the material comes into
contact with surrounding materials and increases reactivity.
To understand this let us consider a spherical material of radius ‘r’. Then
its surface area to volume ratio is 3/r. Due to decrease of r, the ratio
increases predominantly.

13. a) Surface to volume area ratio
As objects get smaller they have a much greater surface area to volume
ratio. Due to increase of surface of surface area, more number of atoms
will appear at the surface of compared to those inside. For example, a
nano material of size 10 nm has 20% of its atoms on its surface and 4 nm
has 50% of its atoms. This makes the nanomaterials more chemically
reactive and affects the properties of nano materials.
2 cm
2 cm cube has a
surface area of
24 cm2 and a
volume of 8 cm3
(ratio = 3:1)
10 cm cube has
a surface area
of 600 cm2 and
a volume of
1000 cm3
(ratio = 0.6:1)
10 cm

14. b) Quantum confinement effect
In Nano Crystals, the Electronic energy levels are not continuous as in
the bulk but are discrete, because of the confinement of the electronic
Wave function to the physical dimensions of the particles. This
phenomenon is called Quantum confinement and therefore Nanocrystals
are also referred to as quantum dots (QDs).
 2-D or Quantum Wells: The carriers act as free carriers in a plane.
 1-D or Quantum Wires: The carriers are free to move down the
direction of the wire, and
 0-D or Quantum Dots: Systems in which carriers are confined in all
directions (no free carriers).
One of the most direct effects of reducing the size of materials to the
nanometer range is the appearance of quantization effects due to the
confinement of the movement of electrons. This leads to discrete energy
levels depending on the size of the structure. Control over dimensions as
well as composition of structures thus makes it possible to tailor material
properties to specific applications. Hence, quantum confinement effect
affects the optical, electrical and magnetic properties of nanomaterials.

15. Significance of nanoscale
When particles are created with dimensions of about 1–100 nanometers,
the material’s properties change significantly from those at larger scales.
This is the size scale where so-called quantum effects rule the behaviour
and properties of particles. Properties of materials are size-dependent in
this scale range. Thus, when particle size is made to be nanoscale,
properties such as melting point, fluorescence, electrical conductivity,
magnetic permeability, and chemical reactivity change as a function of
the size of the particle.
Thus, the nanoscale has become very significant and important as
 The quantum mechanical properties of the particles at the nanoscale
influence a lot on the physical properties of the particles.
By nanoscale design of the materials it is possible to vary micro and
macroscopic properties such as charge capacity, magnetization,
melting temperature without changing their chemical composition.
 Nanoscale components have high surface area to volume ratio making
them idle for the use in composite materials, drug delivery and
chemical storage.

16. Synthesis of Nanomaterials
The nanomaterials can be synthesized in two ways, namely
 Top-down approach and
 Bottom –up approach
Top-down approach: In this method, the nanomaterials are synthesized by dis-
assembling the solids into finer pieces until the particles are in the order of
nanometers. Examples: Ball milling, plasma arching, Laser Ablation,
Sputtering, Thermal evaporation etc.
Bottom-up approach: In this method, the nanomaterials are synthesized by
assembling the atoms and molecules together. Examples: Sol-gel method,
chemical vapour deposition method, hydrothermal, co-precipitation,
solvothermal, Miniemulsion etc.

17. Top-down approach

18. Ball milling
 Ball milling is a grinding method that grinds nanotubes into extremely
fine powders.
 During the ball milling process, small hard balls are made to continue
moving inside a container to being allowed to fall on a solid to crush it
into nano crystals with large strength.
 When the balls are allowed to rotate with particular rpm inside of a
container, the necessary energy is transferred to the powder which in
turn reduces the powder grain-sized structure to ultrafine or nano
range particles.
 Hard core steel or tungsten carbide balls are placed in a tightly closed
container with a powder.
 At a huge scale, nanoparticles ranging from a
few milligrams to several kilograms may be
manufactured in a short period of time.
 Ball method is to prepare a wide range of
elemental and oxide powders.

19. Plasma arching method
 To produce plasma (an ionized gas), high potential difference is
applied across the electrodes.
 An arc passes from one electrode to another.
 The gas yields up its electrons and positive ions at anode.
 Positively charged ions pass to other electrode (cathode) pick up
electrons and are deposited to form nano particles.
 Using this plasma arching method, very thin films of the order of
atomic dimensions can be deposited on the surface of an electrode.
 This deposition is carried in vacuum or in an inert gas.
 By using carbon electrodes, carbon nanotubes can be formed on the
surface of the cathode.

20. Laser ablation
 The process of removing atom, molecules from solid material by the
influence of irradiated Laser beam.
 It utilizes a thermal or non-thermal process to remove its
components, generally a complex process.
Thermal decomposition
 Compound decomposition due to application of heat, forming two or
more products from one reactant.
 It is a first developing procedure for nanomaterial synthesis.
 Iron oxide formation from iron oxalate complex under heat treatment
is an example of thermal decomposition.
Sputtering
 In this process ionized gas molecules accelerated towards the target.
Atoms eject from the surface of the target.
 Generally a physical process.

21. Bottom-up approach

22. Sol-gel Method
 The sol-gel process is a wet technique i.e., chemical solution deposition technique
used for the production of high purity and homogeneous nanomaterials.
 In solutions ,the molecules of nanometer size are dispersed and move around
randomly and hence the solution are clear.
 In colloids the molecules are suspended in a solvent. When mixed with a liquid is
called as sol. A suspension that keeps its shape is called a gel. Thus the colloids are
suspensions of colloids in liquids that keep their shape. The formation of sol-gels
involves hydrolysis, condensation growth of particles and formation of networks.
 The sol is then evaporated during the production of an inorganic network containing
gel. A drying procedure is followed by calcinations to eliminate the liquid phase
from the gel.
 This is commonly employed in spherical shaped powders, thin film coatings,
ceramic fibers, and very porous aerogels, among other purposes.
 Precursors with high purity, such as metal alkoxides, make it simple to create high-
quality, cost-effective materials.
 The temperature required in the process is low, and no delicate vacuum equipment is
necessary.
 Despite its benefits, the sol-gel technique has certain drawbacks. Due to poor
bonding, low wear resistance, high permeability, and difficulty controlling porosity,
the sol-gel process is not commonly used in industry.

23. Chemical vapour deposition
 In chemical vapour deposition is a well known process in which a
solid is deposited on a cooled surface via chemical reaction from gas
phase.
 The basic steps involved in this process are (i) Generation of vapour
by boiling or subliming a source material (ii) Transformation of the
vapour from the source to the substrate and (iii) Condensation of
vapour on the cool substrate.
 In this method, the atoms/molecules are in gases state allowed to react
homogenously or heterogeneously depending on the applications.
 This method is an excellent method which is used to control the
particle size, shape and chemical compositions.
 This method is used to produce the nano powders of oxides and
carbides of metals.
 Production of pure metal powders is also possible using this method.

24. Co-precipitation
 It is comprised of the following steps: nucleation, growth, coarsening,
and agglomeration.
 Metals, such as nitrates, chlorides, and sulphates, are commonly
utilized as reactants in this process. The pH of the resulting
homogenous solution is adjusted. The procedure of refluxing is used
to convert the solution to precipitate.
 The precipitate is then cleaned and dried. In comparison to other
techniques, co-precipitation is a highly needed after one due to its
simplicity. It is characterized by a large applicability for the
introduction of dopants, cost effectiveness, and suitability for mass
production, in addition to its simplicity.
 The method of co-precipitation has a number of advantages. The
reaction temperature may be reduced due to a homogeneous
combination of reactant precipitates. Directly synthesizing thin metal
oxide nanoparticles is a simple process.
 When sintering at low temperatures, the produced nanomaterials are
extremely reactive.

25. Hydrothermal Method
 Water at higher temperature is used in hydrothermal synthesis, which
is a component of solvothermal synthesis.
 When tiny crystals are exposed to high temperatures and pressures,
they will homogeneously nucleate and develop from solution.
 Water serves as a catalyst as well as a solid-state phase component
during the nucleation and growth process.
 Water becomes supercritical under the harsh conditions of the
synthesis vessel (autoclave or bomb), enhancing the dissolving power,
diffusivity, and mass transport of the liquid by lowering its viscosity.
 Hydrothermal synthesis is environmentally friendly, affordable, and
allows for the lowering of free energy for various equilibriums when
compared to other methods.

26. Properties of Nanomaterials
 Nanomaterials differ from bulk materials in terms of their
characteristics.
 On the other hand, nanoscale materials do not have the same
physical properties as bulk materials because of their small
dimensions.
 Some materials have different and distinct properties when
decreased to nano dimensions compared to their bulk equivalent.
 By changing into a nanoparticle, chemical reactivity can be
increased or decreased.
 The majority of nanostructure materials are crystalline, and they
have unique properties like surface area to volume ratio and
quantum confinement.
 Surface properties including energy levels, electronic structures, and
reactivity can indeed be somewhat unique from within the states,
and lend credence to quite different nanomaterial properties.

27. Optical properties of Nanomaterials are influenced by factors for
example size, shape, surface area to volume ratio, and other factors such
as doping and interaction with the environment. Gold and silver
nanoparticles of different size have different color. The colour changes
because each colour has a specific wavelength.
Different sized nano particles
scatters different of light
incident on it and hence they
appear with different colours.
For example nano gold does
not act as bulk gold. The nano
particles of gold appear as
orange, purple, red or greenish
in colour depending on their
grain size. The bulk copper is
opaque where as nanoparticle
copper is transparent.
1. Optical properties

28. 2. Physical properties
When the material size is reduced to nanoscale, surface area to volume ratio
increases. Due to increase of surface of surface area, more number of atoms
will appear at the surface of compared to those inside. So Interatomic
spacing decreases with size.
3. Thermal properties
Thermal properties of nano materials are different from that of bulk materials.
The Debye Temperature and ferroelectric phase transition temperature are
lower for nano materials. The melting point of nano gold decreases from 1200
K to 800K as the size of particle decreases form 30 nm to 20 nm.
4. Magnetic properties
The magnetic properties of nano materials are different from that of bulk
materials. In explaining the magnetic behavior of nanomaterials, we use single
domains unlike large number of domains in bulk materials. The coercivity
values of single domain is vary large. For example, Fe,Co, and Ni are
ferromagnetic in bulk but they exhibit super par magnetism. Na, K, and Rh are
paramagnetic in bulk but they exhibit ferro-magnetic. Cr is anti ferromagnetic
in bulk but they exhibit super paramagnetic.

29. 5. Mechanical properties
The mechanical properties such as hardness, toughness, elastic modulus,
young’s modulus etc., of nano materials are different from that of bulk
materials. In metals and alloys, the hardness and toughness are increased by
reducing the size of the nano particles. In ceramics, ductility and super
plasticity are increased on reducing grain size. Hardness increases 4 to 6
times as one goes from bulk Cu to nanocrystalline and it is 7 to 8 times for
Ni.
6. Chemical properties
Nanocrystalline materials are strong, hard, erosion and corrosion resistant.
They are chemically active and have the following chemical properties.
1. In electrochemical reactions, the rate of increase in mass transport
increases as the particle size decreases.
2. The equilibrium vapour pressure, chemical potentials and solubilites of
nanoparticles are greater than that for the same bulk material.
3. Most of the metals do not absorb hydrogen. But the hydrogen
absorption increases with the decrease of cluster size in Ni, Pt and Pd
metals.

30. Applications of nanomaterials
Nano materials have unique physical, chemical and mechanical properties, they can be
used for a wide verity of applications.
1. Material technology
 Nanocrystalline aerogel are light weight and porous, so they are used for insulation
in offices homes.
 Cutting tools made of nanocrystalline materials are much harder, much more wear-
resistance and last stranger.
 Nanocrystalline material sensors are used for smoke detectors, ice detectors on air
craft wings, etc,.
 Nanocrystalline materials are used for high energy density storage batteries.
 Nanosized titanium dioxide and zinc dioxide are used in sunscreens to absorb and
reflect ultraviolet rays.
 Nan coating of highly activated titanium dioxide acts as water repellent and
antibacterial.
 The hardness of metals can be predominately enhanced by using nanoparticles.
 Nanoparticles in paints change colour in response to change in temperature or
chemical environment, and reduce the infrared absorption and heat loss.
 Nanocrystalline ceramics are used in automotive industry as high strength springs,
ball bearings and valve lifters.

31. 2. Electronics and Information technology
 Nanotechnology has reduced the size of transistors.
 Nanoparticle copper suspensions is more trustable alternative to lead-based weld and
other toxic substances commonly used in the assembly process to fuse electronics.
 Nanoscale fabricated magnetic materials are used in data storage.
 Nano computer chips reduce the size of the computer.
 Nanocrystalline starting light emitting phosphors are used for flat panel displays.
 Nanoparticles are used for information storage.
 Nanophotonic crystals are used in chemical optical computers.
3. Biomedicals
 Biosensitive nanomaterials are used for ragging of DNA and DNA chips.
 In the medical field, nanomaterials are used for disease diagnosis, drug delivery and
molecular imaging.
 Nanocrystalline silicon carbide is used for artificial heart valves due to its low
weight and high strength.
4. Energy storage
 Nanoparticles are used hydrogen storage.
 Nano particles are used in magnetic refrigeration.
 Metal nanoparticles are useful in fabrication of ionic batteries.
 Nanotechnology is also included into solar panels to increase the efficiency,
resulting in future solar power.