Nanomaterials and chemical sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in
 Syllabus

1.1: An overview of the course

1.2: Physics of nanomaterials

Finite size systems, cluster science, bulk versus nanomaterials, quantum
confinement effects in nano-regime, evolution of electronic structure
from atoms to bulk, density of states, dimensionality and its effect on
electronic structure, surface effects, calculation of surface-to-volume
ratio for different structural arrangements. Size dependent physico-
chemical properties
1.4: Carbon-based nanomaterials
Dimensionality in carbon-based nanomaterials, fullerene, nomenclature
and properties of carbon nanotube, graphene, tuning of the properties of
carbon based nano-materials.

1.5: Common characterization techniques for nanomaterials

Characterization techniques at different length scales, application of and
DLS, Zeta, SAXS, SANS and AFM for characterization of nanomaterials.

1.7: Applications of nanomaterials

Nanomaterials for bio-applications (drug delivery and imaging)
environmental applications (sorbents) and DAE application.

1.8. Sensors
 What is Nano
NANO’ - Greek prefix meaning dwarf and depicts
one billionth (10–9) of a unit.

It’s not just Chemistry, Biology, physics, Material Science,

Electronics, and Engineering. It’s all sciences and technologies
those work with the very small.
Understanding Size
 Understanding Size
How small are nanostructures?

Single Hair

Width = 0.1 mm

= 100 micrometers

= 100,000 nanometers !

1 nanometer = one billionth (10-9) meter

 Understanding Size

6,000 nanometers DNA

Hair

.
Red blood cell

3 nanometer
 Size is relative….just like time

• Polycrystalline materials - grain size is of the

order of 1–100 microns.
• Nano crystalline materials have a grain size of
the order of 1−100 nm, and are therefore 100–
1000 times smaller than conventional grain
dimensions.
• However, size of an atom (0.2–0.4 nm in
diameter), nano crystalline grains are still
significantly big!
 Definition of nanomaterials
• The materials with at least one of its dimension (x/y/z)
in the range of 1 to 100 nano meter.
• Sometimes materials with any external dimension in
the nanoscale or having internal structure or surface
structure in nanoscale are also considered as
nanostructured materials.

• Materials that are in nanoscale rage in one dimension are

layers such as thin films or surface coatings.
• Materials that are in nanoscale rage in two dimension include
Nano wires, Nano tubes and Nano pillar.
• Materials that are in nanoscale rage in three dimension are
particles. Eg. Colloids, Quantum dots, Precipitates
 Nanomaterials are not ‘new’….

• Red colour of some ancient glass

paintings is due to gold and silver
nanoparticles trapped in the glass
matrix.
• The decorative glaze or metallic
film known as ‘luster’, found on
some medieval pottery, contains
metallic spherical nanoparticles
which gives rise to special optical
properties
Lycurgus cup: A piece of ancient
roman nanotechnology
 Colloidal gold was used in ancient roman civilization to
paint the glass intense shade of red, yellow or mauve
based on the concentration of gold.

Lycurgus cup : mystery

• Kept in London museum.

• It appears red when light source is placed inside the cup
and green when light source is kept outside.
• Red : transmitted light
• Green: Reflected light.
• Reason not understood that time.
 Ancient materials with nano-
components
• Steel (an alloy of iron and carbon) is believed
to have been first prepared in India about
1500 years ago and is popularly known as
wootz (India’s Legendary ‘Wootz’ Steel)
• This steel was used to make swords, which
were so strong and sharp that they could
easily cut a helmet into two pieces.
• Very recently, high-resolution electron
microscopy of such a steel showed the
presence of carbon nanotubes in them.
• People now believe that the high strength of
these steels may be due to the presence of
these carbon nanotubes, which are known for
their exceptionally large Young’s modulus.
 Faraday Gold solution
• Faraday prepared that colloidal
gold suspension in 1857.
• Still stable.
• Later found out under TEM (107 x
magnification) it is gold
nanoparticles (2007)

• Carbon black is a nanostructured

material that is used in car tyres to
increase the life of the tyre -
discovered in the 1900s.
Scientific thrust in nanotechnology
Richard Feynman
• Classic lecture on 29th December,
1959 at Caltech, USA in the annual
meeting of American physical
society.
 Norio Taniguchi
15 years later Professor
Taniguchi from Japan coined the
term “ Nanotechnology’ for the
first time in 1974.

He was working on production

technology to get extra high
accuracy and ultra fine dimension
i.e. preciseness and fineness on the
order of 1 nm.

He was cutting gold from bulk to micro to nano.

From micro to nano color changes golden to red.
New branch exist: termed nanoscience.
 Dr. Eric Drexler
1986

Two book
Molecular
manufacturing: 1981

His idea came from ribosome.

Key in producing protein
Structure and function matches to that machine
Think of similar molecular machinery with atoms, nanobots.
Becomes reality in 10 years.
 How Nanoscience and
Nanotechnology improve our lives?
• Materials: Stain-resistant Clothes, Paints, Coating …….
• Health Care: Biological sensors, drugs, drug delivery
devices…………
• Technology: Better data storage, computation, Semiconductor,
Field Effect Transistor, Switch, Optoelectronic, Photovoltaic and
other Nano devices
• Environment: Clean energy, clean air…………

Thin layers of gold are used in Carbon nanotubes can be used Possible entry point for
tiny medical devices for H fuel storage nanomedical device
 Materials: Paint That Doesn’t Chip

Mercedes covered with tougher, shinier nanopaint

• Protective nano paint for cars

– Water and dirt repellent
– Resistant to chipping and scratches
– Brighter colors, enhanced gloss
– In the future, could change color and self-repair?
Automobile industry
Hydrophobic cloths
Some clothing manufacturers are
making water and stain repellent
clothing using nano-sized whiskers in
the fabric that cause water to bead up
on the surface.
Antimicrobial fabrics

Nanohorizons, a company in
Pennsylvania, has started
producing a silver nanoparticle
material as both a dye and use in
polyester and nylon.

The silver nanoparticles are

toxic to microbes, and so colonies
will never form, and clothes using
this material will not
Nanohouse

• Nano house has an efficient

radiative cooling paint on its
outer surface as roofing
material.

• Used in hot and humid areas for

protection from heat.

• New model house for dessert

areas.
 Environment: Paint That Cleans Air
Buildings as air purifiers?

• Nanopaint on buildings could reduce pollution

– When exposed to ultraviolet light, titanium dioxide (TiO2)
nanoparticles in paint break down organic and inorganic
pollutants that wash off in the rain
– Decompose air pollution particles like formaldehyde
 Nanodevice: Nano Solar Cells
• Nano solar cells mixed in plastic could be painted on
buses, roofs, clothing
– Solar becomes a cheap energy alternative!

] 200 nm

Nano solar cell: Inorganic nanorods embedded in

semiconducting polymer, sandwiched between two electrodes
Nanoelectronics

Nanotube Computer
Technology: A DVD That Could Hold a
Million Movies

• Current CD and DVD media have storage scale in

micrometers
• New nanomedia (made when gold self-assembles into
strips on silicon) has a storage scale in nanometers
• That is 1,000 times more storage along each dimension
(length, width)…

…or 1,000,000 times

greater storage
density in total!
Nanomaterials in : the personal care
industry
Nanocosmeceuticals
 Sunscreens

Zinc oxide and Titanium dioxide have been used in

sunscreens because of their powerful UV blocking properties
but they leave a white coating on the skin, which most people
find unpleasant.
Nano TiO2 Large TiO2 particles
Food industry
Environment application
 Water purification

• Made up of carbon nano

tubes with pore size in
nanometer range
– Can remove virus, bacteria,
multivalent toxic metal ions
etc.
– Greater efficacy than micro
and ultra filters
– Operating cost is too low.
 Nanomembrane for H2 and CO2
separation
• Nonporous membrane made up by
researchers in university of
Queensland.
 Based on the pore size they can
separate the H2 and CO2.

 Petroleum industry :
hydrocarbon generation leads to
formation of H2 and CO2.

 H2 can be used as fuel after

separation.
Health Care application
 Nerve Tissue Talking to Computers

• Neuro-electronic networks interface nerve cells with

semiconductors
– Possible applications in brain research, neuro
computation, prosthetics, biosensors

Snail neuron grown on a chip that records the neuron’s activity

 Health Care: Detecting Diseases
Earlier
• Quantum dots glow in UV light
– Injected in mice, collect in tumors
– Could locate as few as 10 to 100 cancer cells

Quantum Dots: Nanometer-sized crystals

that contain free electrons and emit
photons when submitted to UV light
Early tumor detection,
studied in mice
Health Care: Nano robots for body
repairing
Health Care: Novel drug delivery
What is the difference between
Ionization potential and work
function
Ionization energy is the energy required to
remove the outermost shell electrons of an
isolated atom of an element (gaseous phase). We
define ionization energy when we have a single
atom.
The work function is the energy required to
remove the outermost shell electrons of a metal's
surface atoms when they are involved in metallic
bonding. The work function is the energy needed
to take away METALLIC BONDED electrons.
 Work function is generally lower than the
ionization energy for a particular element.

IP: 5.14 eV
Sodium
WF: 2.84 eV
 Average Bond energy

Na dimer bond energy 0.4 eV/atom

Bulk Na metal 1.12 eV/atom
What is so special about ‘Nano’ scale ?
• At the micron (1,000 nm)
and larger scale, classical
physics determines
properties.

• At the Angstrom (0.1 nm)

scale, quantum mechanics
determines properties.

At the nanometer scale,

fundamental properties
depend on exactly how big
the particle is.
 Nanomaterials and chemical
sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in

2nd class
Bulk vs Nano
 Physics of nanomaterials

• Reducing the size of material : Properties changes

dramatically.

• So chemically same material can give rise to different

properties based on the size range. Eg : Au

• That is the reason why nano is so interesting to all of

us.

• Sometimes the same size scale may have different

effect in different materials.

• So we can say the size scale is very much material

dependent property.
 Key factor

Two factors cause the properties of Nano Materials

to differ significantly from other materials

Increase in relative surface area.

 Quantum confinement effect.

These factors can change or enhance properties such as

reactivity strength, optical and electrical characteristics.
 Surface to volume ratio
Dispersion (F) of a sample is the fraction or percentage of atoms
at the surface relative to the total no. of atoms in the sample

Dispersion (F) = Surface area / Volume

For a Sphere
Surface area = 4πr2
Volume = 4πr3/3

Dispersion (F) = 3/r or 6/d

• A spherical particle has a diameter (D) of
100nm. Calculate the volume (V) and
surface area (SA).

4 3 πD3 2 2
V = πr = SA = 4 πr = πD
3 6 -9 2
π(100 × 10 ) -9 3 SA = π(100 × 10 )
V= -14
SA = 3.141× 10 m 2
6
-22 3
V = 5.24 x10 m

Surface area : Volume > 107:1

This gives an approximate surface area to volume
ratio of >107:1 which is significantly larger than a
macro sized particle.
As the surface area to volume ratio increases so
does the percentage of atoms at the surface and
surface forces become more dominant.

• For example, a particle of size 30 nm has 5% of its

atoms on its surface, at 10 nm 20% of its atoms,
and at 3 nm 50% of its atoms.
 Some example calculations for volume and surface
area of nanoparticles. These calculations use nm as
unit of length.

Nanoparticle Nanoparticle Volume Surface Area SA:Vol Ratio

Diameter (nm) Diameter (um) (nm3) (nm2) (nm2/nm3)
1 0.001 0.524 3.14 6
10 0.01 524 314 0.6
100 0.1 523598 31416 0.06
1000 1 5.24E+08 3.14E+06 0.006
10000 10 5.24E+11 3.14E+08 0.0006
100000 100 5.24E+14 3.14E+10 0.00006
1000000 1000 5.24E+17 3.14E+12 0.000006
 Surface Area:Volume Ratio

In this graph:
SA = nm2
Vol = nm3

SA:Vol Ratio = nm2/nm3

The ratio increases dramatically when the nanoparticle diameter drops

below about 100 nm
For a Cubic system

Surface area = 6a2

Volume = a3

Dispersion (F) = 6/a

1.0 m

0.5 m
 Each small cube
Surface area = 6*1 m2 Surface area = 6*0.52 = 1.50 m2
Volume = 1 m3 Volume = 0.53 = 0.125 m3
F=6 F = 12
So on decreasing the side (a) the F value increases
So by decreasing the side to 0.5 m from 1 m, the
surface area increases from 6 to 12 m2.
 Property
fluctuations
 Cluster Surface Analogy: Small Clusters have nearly
all atoms on the surface

Total No. On % Surface

of atom Surface

13 12 92.3
55 42 76.4
147 92 62.6
 Quantum confinement effect

QCE can be observed once the diameter of the particle is of the

magnitude of the wavelength of electron wave function.

In order to understand the QCE, we need to know the basics of

quantum mechanics; namely, the role of a particle in a box.

A particle behaves as if it were free when the confining

dimension is large compared to the wavelength of the
particle.

During this state (bulk solid), the energy levels are closely
spaced, and thus form quasi-continuous bands.
In order to understand the QCE, we need to know the basics of
quantum mechanics; namely, the role of a particle in a box.

• Infinite walls
V(x)=∞ V(x)=∞

Region I Region II Region III

V(x)=∞ V(x)=0 V(x)=∞

0 L x

A simple schematic of a potential well surrounding a local

minimum of potential energy. Energy captured in a potential well
is unable to convert to another type of energy because it is
captured in the local minimum of a potential well.
In order to understand the QCE, we need to know the basics of
quantum mechanics; namely, the role of a particle in a box.

Time Independent Schrödinger Equation

  2 d 2 ( x )
2
 V ( x )  E 
2m dx
KE PE TE

Applying boundary conditions:

Region I and III:

  2 d 2 ( x )
2
  *  E 
2m dx
2
   0
Region II:

d 2 ( x ) 2m E
2
  2
 (x)
dx 
Second derivative of a function equals a
negative constant times the same function.

Functions with this property sin and cos.

2
d s in ( a x )
2
 a 2
s in ( a x )
dx
2
d cos(ax )
 a 2
cos(ax )
dx
Region II:

  2 d 2 ( x )
2
 E
2m dx
b) x=L ψ=0
d 2 ( x ) 2m
  2
 2
E 0  A sin kL
dx 
ButA  0
This is similar to the general
differential equation: kL  n 
d 2 ( x )
  k 2

dx 2
Thus, wave function:
  A sin kx  B cos kx
nx
 II  A sin
Applying boundary conditions: L
a) x=0 ψ=0
But what is ‘A’?
0  A sin 0 k  B cos 0 k
0  0  B *1
 B  0
Normalizing wave function:
L


0
( A sin kx ) 2 dx  1
L
x2 sin 2 kx 
A    1
2 4k 0

 n 
sin 2 L
2  L L 
A    1
n
2 4 
 L 

2 L 
A   1
 2 
2
A 
L
Thus normalized wave function is:

2 nx
 II  sin
L L
Calculating Energy Levels:

2 mE
k 2

2

k 2 2
E 
2m

k 2h 2 h
E  (  )
2 m 4 2
2

n 2 2
h2
E 
L2 2 m 4 2

Thus Energy is:

n 2h 2
E 
8 mL 2
Particle in a 1-Dimensional Box
2
2 nx 2 2  nx 
  sin  II   sin 
II
L L L  L 

+ +
+
-

+ +

E  *
 Difference b/w adjacent energy levels:

 Non-zero zero point energy

 At very high n values, spectrum becomes

continuous convergence with Classical Mechanics
(Bohr’s correspondence principle)
Particle in a 3-D box
 Inference
At nano scale, the energy-level separation increases and discrete
energy levels are observed.
The schematic band diagram shows the change in electron energy
level and band gap between nanomaterials and its bulk state.
 increasing confinement
discrete states

Smaller the dimensions in which electrons are confined, larger

the separation between the energy levels.
 Classification of nanomaterials
Dimension wise

Based on dimensionality the nanomaterials are divided into

four sub class 0, 1, 2, 3 D materials

Composition wise

Based on composition also the nanomaterials are divided into

four sub classes
Dimension wise
 Classification of nanomaterials
schematic

0 D: All dimensions at the nano electron free to move in 0 direction; electron bound in all 3
scale; directions
1 D: Two dimensions at the nano electron free to move in 1 direction; electron bound in 2
scale; One dimension at the directions
macro scale
2 D: One dimensions at the nano electron free to move in 2 direction; electron bound in 1
scale; Two dimension at the directions
macro scale
3 D: No dimensions at the nano scale; electron free to move in 3 direction; electron bound in 0
All dimension at the macro scale directions
 Composition wise

1. Carbon based nanomaterials

2. Metal basd nanomaterials
3. Dendrimers
4. Composite nanomaterials
Carbon based nanomaterials

Rich in carbon content

They can form spherical, hollow, ellipsoidal or cylindrical in shape.
Spherical, hollow are mainly fullerenes, whereas the cylindricals are
carbon
Nanotubes.
This are having very unique features.
Metal based nanomaterials

Quantum dots: tiny semiconductor crystals.

Au, Ag nanoparticles,
Metal oxide NPs
All other metal based NPs. eg; TiO2 used in sunscreen lotion, paints,
toothpaste
Dendrmers

Considered as nano polymers.

The surface of the dendrimers contains several number of chain ends
This chain ends can be functionalized or tailor made.
It can acts as very good catalyst
The interior cavities .
Several substance can be placed inside the cavities.
Useful application in drug delivery
Composite nanomaterials

Mixture of nano materials and bulk materials.

Nanoclay added to bulk material: composite nano materials
The mixing of nanoclay in bulk material enhances the physico-
chemical property of the bulk materials
Based on aspect ratio
Confinement of electrons;
dimensionality
 Density of states (DOS)
The density of states (DOS) refers to the number of energy states per
unit energy.
In other words, the density of states, denoted by , indicates how
densely packed energy states in a particular system.

The number of energy states with energies between E and E+dE,

Integrating the density of states over a range of energy will

produce total number of states.

E

N (E)  E g(E)dE
 Nanomaterials and chemical
sensors

Bijaideep Dutta
Ext. no. 2286
E-mail id: bijaideep@barc.gov.in

3rd class
 Key factor

Two factors cause the properties of Nano Materials

to differ significantly from other materials

Increase in relative surface area.

 Quantum confinement effect.

These factors can change or enhance properties such as

reactivity strength, optical and electrical characteristics.
 Surface to volume ratio
Dispersion (F) of a sample is the fraction or percentage of atoms
at the surface relative to the total no. of atoms in the sample

Dispersion (F) = Surface area / Volume

For a Sphere
Surface area = 4πr2
Volume = 4πr3/3

Dispersion (F) = 3/r or 6/d

This gives an approximate surface area to volume
ratio of >107:1 which is significantly larger than a
macro sized particle.
As the surface area to volume ratio increases so
does the percentage of atoms at the surface and
surface forces become more dominant.

• For example, a particle of size 30 nm has 5% of its

atoms on its surface, at 10 nm 20% of its atoms,
and at 3 nm 50% of its atoms.
 Some example calculations for volume and surface
area of nanoparticles. These calculations use nm as
unit of length.

Nanoparticle Nanoparticle Volume Surface Area SA:Vol Ratio

Diameter (nm) Diameter (um) (nm3) (nm2) (nm2/nm3)
1 0.001 0.524 3.14 6
10 0.01 524 314 0.6
100 0.1 523598 31416 0.06
1000 1 5.24E+08 3.14E+06 0.006
10000 10 5.24E+11 3.14E+08 0.0006
100000 100 5.24E+14 3.14E+10 0.00006
1000000 1000 5.24E+17 3.14E+12 0.000006
 Surface Area:Volume Ratio

In this graph:
SA = nm2
Vol = nm3

SA:Vol Ratio = nm2/nm3

The ratio increases dramatically when the nanoparticle diameter drops

below about 100 nm
For a Cubic system

Surface area = 6a2

Volume = a3

Dispersion (F) = 6/a

1.0 m

0.5 m
 Each small cube
Surface area = 6*1 m2 Surface area = 6*0.52 = 1.50 m2
Volume = 1 m3 Volume = 0.53 = 0.125 m3
F=6 F = 12
So on decreasing the side (a) the F value increases
So by decreasing the side to 0.5 m from 1 m, the
surface area increases from 6 to 12 m2.
 Property
fluctuations
 Cluster Surface Analogy: Small Clusters have nearly
all atoms on the surface

Total No. On % Surface

of atom Surface

13 12 92.3
55 42 76.4
147 92 62.6
 Quantum confinement effect
QCE can be observed once the diameter of the particle is of the
order de Broglie wavelength of electron.
The role of a particle in a box

• Infinite walls
V(x)=∞ V(x)=∞

Region I Region II Region III

V(x)=∞ V(x)=0 V(x)=∞

0 L x

A simple schematic of a potential well surrounding a local

minimum of potential energy. Energy captured in a potential well
is unable to convert to another type of energy because it is
captured in the local minimum of a potential well.
   2 d 2 ( x)
2
 V ( x)  E
2m dx
KE PE TE

Applying boundary conditions:

Region I and III:

  2 d 2 ( x)
2
  *  E
2m dx
2
  0
Region II:

d 2 ( x ) 2mE
2
  2
 ( x)
dx
Second derivative of a function equals a
negative constant times the same function.

Functions with this property sin and cos.

d 2 sin(ax )
2
 a 2 sin(ax )
dx

d 2 cos(ax )
 a 2 cos(ax )
dx
Region II:

  2 d 2 ( x)
2
 E
2m dx
b) x=L ψ=0
d 2 ( x) 2m
  2
 2
E 0  Asin kL
dx 
ButA  0
This is similar to the general
differential equation: kL  n
d 2 ( x)
  k 2
dx 2
Thus, wave function:
  A sin kx  B cos kx
nx
 II  A sin
Applying boundary conditions: L
a) x=0 ψ=0
But what is ‘A’?
0  Asin 0k  B cos 0k
0  0  B *1
 B  0
Normalizing wave function:
L

 dx  1
2
( A sin kx)
0
L
 x sin 2kx 
2
A    1
 2 4 k 0
 n 
sin 2 L
2L L
A    1
2 n
 4 
 L 

2 L 
A   1
2
2
A 
L
Thus normalized wave function is:

2 nx
 II  sin
L L
Calculating Energy Levels:

2mE
k2 
2

k 2 2
E
2m

k 2h2 h
E (  )
2m4 2 2

n 2 2 h2
E
L2 2m4 2

Thus Energy is:

n2h2
E
8mL2
Particle in a 1-Dimensional Box
2
2 nx 2 2 nx 
 II  sin  II   sin 
L L L L 

+ +
+
-

+ +

E  *
 Difference b/w adjacent energy levels:

 Non-zero zero point energy

 At very high n values, spectrum becomes

continuous convergence with Classical Mechanics
(Bohr’s correspondence principle)
Particle in a 3-D box
 Inference
At nano scale, the energy-level separation increases and discrete
energy levels are observed.
The schematic band diagram shows the change in electron energy
level and band gap between nanomaterials and its bulk state.
 increasing confinement
discrete states

Smaller the dimensions in which electrons are confined, larger

the separation between the energy levels.
 Classification of nanomaterials
Dimension wise

Based on dimensionality the nanomaterials are divided into

four sub class 0, 1, 2, 3 D materials

Composition wise

Based on composition also the nanomaterials are divided into

four sub classes
Dimension wise
 Classification of nanomaterials
schematic

0 D: All dimensions at the nano electron free to move in 0 direction; electron bound in all 3
scale; directions
1 D: Two dimensions at the nano electron free to move in 1 direction; electron bound in 2
scale; One dimension at the directions
macro scale
2 D: One dimensions at the nano electron free to move in 2 direction; electron bound in 1
scale; Two dimension at the directions
macro scale
3 D: No dimensions at the nano scale; electron free to move in 3 direction; electron bound in 0
All dimension at the macro scale directions
 Composition wise

1. Carbon based nanomaterials

2. Metal basd nanomaterials
3. Dendrimers
4. Composite nanomaterials
Carbon based nanomaterials

Rich in carbon content

They can form spherical, hollow, ellipsoidal or cylindrical in shape.
Spherical, hollow are mainly fullerenes, whereas the cylindricals are
carbon
Nanotubes.
This are having very unique features.
Metal based nanomaterials

Quantum dots: tiny semiconductor crystals.

Au, Ag nanoparticles,
Metal oxide NPs
All other metal based NPs. eg; TiO2 used in sunscreen lotion, paints,
toothpaste
Dendrmers

Considered as nano polymers.

The surface of the dendrimers contains several number of chain ends
This chain ends can be functionalized or tailor made.
It can acts as very good catalyst
The interior cavities .
Several substance can be placed inside the cavities.
Useful application in drug delivery
Composite nanomaterials

Mixture of nano materials and bulk materials.

Nanoclay added to bulk material: composite nano materials
The mixing of nanoclay in bulk material enhances the physico-
chemical property of the bulk materials
Based on aspect ratio
Confinement of electrons;
dimensionality
 Density of states (DOS)
The density of states (DOS) refers to the number of energy states per
unit energy.
In other words, the density of states, denoted by , indicates how
densely packed energy states in a particular system.

The number of energy states with energies between E and E+dE,

Integrating the density of states over a range of energy will

produce total number of states.

E

N (E)  E g(E)dE
 2 2 2
k p p
E  k 
2m 2m
Nanomaterials and chemical sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in

4th class
 Size and shape dependent properties

At the nanometer scale, properties become size and shape dependent

Thermal Properties
Mechanical properties
Optical properties
Magnetic properties
Chemical reactivity
melting temperature
Increase in mechanical stength
absorption and scattering of light
super paramagnetic effects
surface effects, catalysis
 Effect on melting point

Gaseous state Liquid state solid state

 No interaction they are far apart.

 Relatively closer
 Solid state they are bonded to each other. Thus there is release of energy.

Thus energy state lies like follows

Gaseous state > Liquid state > solid state
 Now for solid state, the situation of atoms in bulk is different than that of the
ones in surface.
 Bulk atoms are bonded in all direction whereas the surface atoms are free from one half
 Thus surface atoms are at relatively higher energy state as compared to the bulk atoms.

This is the origin of surface energy (γ). So it costs energy to put an atom on the surface as
compared to the bulk.
 Surface wants to minimize the surface area to go inside origin of surface tension (σ)

Dimensional analysis

Surface energy (γ) : Energy/ area Surface tension (σ) : Force/length

= Joule/m2 = Newton/m
= Newton. m/m2
= Newton/m

So dimensionally both are similar but their physical significance is different.

In liquid both are equivalent concept ( γ σ)and sometimes used interchangeably.

But for solid they are not equivalent ( γ σ)
An well defined melting point is where the whole crystal lattice breaks and we get the
molten state (Tm)

Tm is basically kind of indicator of bond strength as it is going to solid to liquid.

Though boiling point is better to get an idea of bond strength

 In bulk the S/V ratio is very small. But in NPs the ratio is significant as higher
no of surface atoms are there.
 Higher energy and high degree of freedom associated with surface atoms as
compared to the bulk (unsaturated and dangling unsatisfied valence orbitals
exposed outwards on surface)
 The extra energy possessed by surface atoms compared to the bulk is called
surface free energy ( energy required to create unit area (A) at surface)

 G = H – TS (bulk), (dG=Vdp-Sdt
 G = H-TS + γA (surface) (dG=Vdp-Sdt+ γdA)
Gibbs Thompson equation

 As surface atoms are

at higher energy, they
will easily melts
below the melting
point of bulk.
 It is found that below
100 nm size the
melting points start to
be lowered from
bulk. eg. Au NP (Tm)
is 100 0C lower than
the bulk gold (1064
0C).
Question arises:

How does it melt; what is the mechanism.

Two different picture arises

 Scene 1:

Goes on melting

 Outer surface melts first, followed by the next surface and so on.
 The new surface is still smaller in size and the temp is already above the melting
point of newly arrived surface with reduced r.
 Therefore inward melting
 Scene 2:

Melting in one shot

Inference
 Common intuition will guess the scene 1.
 The experiment carried out by Huang et al. at 1999 on nanorod for melting laser beam showed
no such layer by layer process suggested by scene 1.
 They found the NP melts as whole.
 Still research going on regarding this.
 Special case
For embedded nanoparticles which are not free in nature

 In case of nanoparticles embedded in matrix system the melting point may decrease or increase also depending
upon the relative magnitudes of interfacial energies.

Two different interfacial energy arises

• Particles in matrix
• Interfacial energy between solid particle and
matrix (γPM)

Matrix embedded NPs

• Particles melts in matrix
• Interfacial energy between liquid melt and matrix
(γLM)
 So when,
γPM > γLM; then there will be depression of melting
points.
γPM < γLM; then there will be elevation of melting points
compared to the bulk. eg. Al-In alloy

Summary
 Effect on lattice parameter

 Most solids are crystalline with their atoms arranged in a regular

manner.
 This arrangement of atoms impacts the functionality of the material.
 Some solids have this order presented over a long range as in a crystal.

 Due to high surface to volume ratio more atoms are on surface

 Surface atoms being co-ordinatively unsaturated, they tend to form
stronger bonds with interior as well as nearby surface
atoms.
 Thus the there is decrease in lattice constant which is measure of
distance b/w two atoms.
Altered Lattice Constants

• Compare lattice structure of nano and bulk materials

• Shortening of bonds near the surface
• Surface reconstruction

Original Structure Shortened Surface Bonds Shifted Surface Bonds

 Figure 8.15a shows that the lattice constants of nanoparticles decrease linearly
with an increasing reciprocal particle radius.
 It is further noticed that the CdS nanoparticles with surface modification
demonstrate less reduction in lattice constant than that of bare nanoparticles.
Another observation,
BaTiO3 at grain sizes larger than 1.5μm, a constant ratio of the
lattice parameters, c/a－1＝1.02%, whereas at grain sizes
smaller than 1.5μm, c/a－1＜1%.
 Close-Packed Magic Number Clusters

• Nanoparticles have a “structural magic number”, that is, the optimum

number of atoms that leads to a stable configuration while maintaining a
specific structure.
• Structural magic number = minimum volume and maximum density
configuration
 Possible ways to reduce surface free energy

 Surface relaxation: Due to the inward pull the lattice constant shrunken

 Surface reconstruction: Due to the dangling unsatisfied valence orbitals surface

atoms may form strained bond at surface

 Surface adsorption: Due to the unsaturation at surface chemical adsorption may

occur at surface

 Formation of faceted crystal: Formation of preferred face wit low surface energy
 Effect on defects an mechanical properties
 In general defect creation is thermodynamically favourable from the entropy
point of view (configurational entropy).
 Roughly more than 10% defect leads to higher enthalpy unfavourability than
entropy gain, so not spontaneous in bulk.
 So there is point with max defect density in bulk crystals.

 Now as the size is reduced to nano-scale the configurational entropy value

change disfavours the formation of defects as well due to smaller probable defect
distribution patterns.
 Probability of diffusion of impurities or defects to the surface also increases in
nano sizes ; This is called self purification process (intrinsic thermodynamic
property of nanomaterials)
 With little bit of heat treatment the defect diffusion to the surface increase and
purity increases.

 With decreasing the particle size the probability of finding the imperfections,
vacancies, grain boundaries becomes lesser thus the mechanical strength
enhances significantly

 Hardness, toughness, young modulus (Y) etc increases.

young modulus (Y) = Applied force per unit area/ change of length of object
 Effect on optical properties
Size effect on optical properties

 films of metals may partially transmit, just because there is insufficient material to absorb the radiation.
Au films few 10s of nm thick become partially transparent.
 Apart from ‘insufficient material’ effects, there are important phenomena which come into play in
nanomaterials.
 These include: dominance of quantum confinement effects, surface plasmons etc.
 E.g. in semiconductor quantum dots optical absorption and emission shift to the blue (higher energies) as
the size of the dots decreases.
 The size reduction is more prominent in the case of semiconductors as compared to metals (i.e. quantum
size confinement effects become more important in metals at smaller sizes than semiconductor crystals).
 We have already seen that at very small sizes metal nanoparticles can develop a bandgap (can become a
semiconductor or insulator).
Semiconductor nanoparticles

 On decreasing the size the electron gets confined to the particle (confinement
effects) leading to:
(i) increase in bandgap energy and
(ii)band levels get quantized (discrete).
 Surface states (trap states), which lie in the bandgap become important → alter
the optical properties of nanocrystals.
 The energy level spacing increases with decreasing dimension
→ Qunatum Size Confinement Effect
 In photoluminescence material is excited by EM radiation, followed by
relaxation to ground state by emission of photons.
 When the semiconductor relaxes to the ground state by recombination of
electron and hole, a photon is emitted.
 If the photon energy lies in the range 1.8 - 3.1 eV the radiation will be in
the visible range
→ luminescence.
 By changing the size of the nanoparticles the frequency of emission can
be tailored.
 As the size of the nanoparticles decrease → ‘blue shift’ in frequencies.
 J. Nayak et al., Physica E 24 (2004) 227–233

In spectroscopy, oscillator strength is a dimensionless

quantity that expresses the probability of absorption or
emission of electromagnetic radiation in transitions
between energy levels

oscillator strength per volume is expected to increase with

1/r3

 In nano-GaAs (with size range 7-15 nm) a broad excitonic peak at 526.0 nm (2.36 eV) is
seen → energy gap of the nano-GaAs has been blue shifted by 0.93 eV [bulk band gap
(1.43 eV)] due to the QSE.
 Enhancement of absorbance over the range of wavelengths seen → enhanced
oscillator strength (dimensionless quantity to express the strength of the transition).
 The peak is broad due to the size distribution of crystallites.
One more example
With reducing size of the particle the density of states becomes more quantized
and the band gap shifts to higher energies (shorter wavelengths) → the
absorption spectrum shows a blue shift

Absorption spectra of PbSe nanocryatals

Fluorescence from core-shell quantum dots

ZnS CdSe Fluorescence emission of (CdSe)ZnS core-

shell quantum dots.

Dabbousi et al., J. Phys. Chem. B 1997, 101, 9463-9475

metal nanoparticles
• Surface Plasmons
• Metals can be modeled as an arrangement of positive ions surrounded by a sea
of free electrons.
• Collective oscillation of this free electrons around fixed positive centre is
called Plasmon (plasma oscillation)

In nano sized materials, due to high surface atoms the free surface electrons
oscillate to produce surface Plasmon (SP) but due to confinement they are
localized and called localized surface plasmon (LSP)
 When light falls on the material,
The oscillating electric field of electromagnetic radiation
induce collective oscillation and create a oscillating dipole.
When this frequency of electromagnetic matches with the
inherent frequency of surface plasmon, we see surface
plasmon resonance (SPR) and absorption of light by particles.

-- - -- -- - --- - -- -- - - ---------------------------
- + - + - + - + - -- -- - -- --
------------- -- + - + - + - + --
- - - - ---------------
- + - + -- + - + - - - - -
------------ + + - + +
E-field

The movement of this free electron cloud will form a oscillating dipole
 Formal definition: Plasmons are the coherent excitation of free electrons in a
metal.
 The plasmons resonance frequency (f) depends on particle size, shape, and
material type. It is related to the plasmons energy (E) by Planck’s constant.
E=h*f
 Surface plasmons are confined to the surface of the material.
 The optical properties of metal nanoparticles are dominated by the
interaction of surface plasmons with incident photons.
In contrast to the bulk metal, the electron cloud in nanoparticles is
confined to a finite volume, which is smaller than the wavelength of
light.
Metal nanoparticles like gold and silver have plasmons frequencies in
the visible range.
When white light impinges on metal nanoparticles the wavelength
corresponding to the plasmons frequency is absorbed.
Hence, the frequency of oscillation ( or oscillation wavelength) of
metal nanoparticles is determined mainly by :
 number density of electrons,
 size
 shape ; i.e. distribution of the charge.

In particles with shape anisotropy (e.g. cylinders) more than one type
of plasmons absorption peak may be observed.
Size and shape effect

As the shape of the nanoparticle changes,

the surface electron density and hence the
electric field on the surface varies.
• For the sphere (d~15nm) only the Transverse plasmons peak is observed ( ~ 520nm).
• If the radius of the sphere is doubled (d~30nm), the transverse plasmons absorption
peak will only shift slightly → this is unlike semiconductor nanoparticles where the
absorbance is strongly affected by size in the nanoscale.
• For the cylinder both the surface and longitudinal plasmons peaks are observed.
• For the longer cylinder the longitudinal plasmons peak shifts to longer wavelengths
Size and shape effect
 Very small nanoparticles (<2 nm) of gold
do not show surface Plasmon

Smaller size : Possible transition from metallic to

semiconductor/insulator behavior
 Difference between LSPR and UV-Vis spectra

A peak in UV absorption spectra is obtained when an electron from a HOMO level

absorbs appropriate energy, jumps and goes into higher unfilled shells. Certain selection
rules must be satisfied for this process to occur. Resonance condition must be satisfied
and Transition Dipole Moment (TDM) should be nonzero for such a transition to be
allowed.

A LSPR band is obtained in metal nanoparticles due to collective oscillations of free

electrons. Free electrons have a natural frequency of oscillation and when this matches
the frequency of incident radiation, absorption of incident light occurs leading to a LSPR
band.
Effect on catalytic property

Reaction at surface/interface
 Few Examples
 Platinum or Palladium Based:
 Ex. Pt/Ru/Ni,  Small Size
 Gold Based:
 Ex. Au/TiO2, Au/MgO  More surface area
 Other Metal Nanoparticle Based:  More unsaturated bonds
 Ex. Cu, Rh, V-Mg-O
 Dispersed in Polymers:
 Ex. Pt/polypyrrole, Cu/Polyaniline

Automotive catalytic converter: Pt/Pd nano-

catalysts

Oxidation of carbon monoxide to carbon dioxide:

2CO + O2 → 2CO2
•Platinum based metal nanoparticles: Pt@TiO2 and
Pt@Al2O3
Decomposition of SO3: 2SO3 → 2SO2 + O2 With out
catalyst – 800C
With catalyst – 500C
Catalysis by nano-particles
Influence of temperature on nanoparticle

Sintering
Oswald ripening
The effective bandgap of particle of radius R

 R  Eeffective
g

 Nanomaterials and chemical
sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in

5th class
 Effect on magnetic properties
❖ Magnetic properties of material involve concept based on the
magnetic dipole moment/ magnetic moment.
❖ When the electrons revolves around the nucleus orbital
magnetic moment arises, similarly when the electron spins, spin
magnetic moment arises.
❖ The permanent Magnetic Moments can arise due to the
➢ The orbital magnetic moment of the electrons (due to the “revolution”
of an electron about the nucleus)
➢ The spin magnetic moment of the electrons (due to the “rotation” of
an electron) Electrons produce magnetic moments
magnetic moments
➢ The spin magnetic moment of the nucleus
electron electron

nucleus spin
 Magnetic moment

Magnetic moment, m = p l

Intensity of magnetization (magnetization), M is average dipole

moment per unit volume
 Magnetic Susceptibility
❖ The intensity of magnetization is directly related to the applied
field H.
M H
M = H
M
Magnetic susceptibility  =
H
Magnetic susceptibility, χ is a dimensionless proportionality constant
that indicates the degree of magnetization of a material in response to an
applied magnetic field.
 Origin of Magnetic Moment
(magnetic moment of electrons)
Magnetic moment in a material originates from the orbital motion and
spinning motion of electrons in an atom.

µlm
e

Consider an atom & each electron in that, orbiting around the nucleus
produces a loop current
i=e/t
i=ef
where f is a frequency of electron..

If L is the angular momentum of electron, the Magnetic moment of the electron:

µlm = (Area of loop) x (Current)

 e According to quantum-mechanical theory
 lm = (r )( )
2
of atom:
t
 lm = (r 2 )(ef ) h
L = mvr = l(l + 1)
 lm = (r )(
2 e
 2f )
2
2 e
 lm = .L
e 2m
 lm = (r 2 )(  )
2 e h
 lm = . l(l + 1)
 lm = (r 2 )(
e v
 ) 2m 2
2 r eh
evr  lm = . l(l + 1)
 lm = 4m
2  lm = B . l(l + 1)
e
 lm = .mvr eh
2m B (Bhor magnaton) =
e 4m
 lm = .L = 9.27408  10 −24 A.m2 (SI )
2m
Where L is a Angular Momentum of electron
= 0.927408  10 −20 emu (CGS)
Magnetic moment of single unpaired electron
 Classification of Magnetic Materials
Diamagnetic

In the absence of an external field, no dipoles

opposing
exist; in the presence of a field, dipoles are
none

induced that are aligned opposite to the field

direction
Paramagnetic

Atomic dipole configuration with and without an

random

aligned
external magnetic field for a paramagnetic
material

Ferromagnetic
Schematic illustration of the mutual alignment of
atomic dipoles for a ferromagnetic material,
aligned

aligned

which will exist even in the absence of an

external magnetic field.
 Diamagnetic Materials
Diamagnetic

In the absence of an external field, no dipoles

opposing
none exist; in the presence of a field, dipoles are
induced that are aligned opposite to the field
direction

(Arrows indicate atomic dipole moments)

induced moment opposes applied field
Properties:
❖ It is a very weak form of magnetism that is non-permanent and
persists only while an external field is being applied.
❖ Magnitude of the induced magnetic moment is extremely small, and
in a direction opposite to that of the applied field.
❖ Thus, the relative permeability is less than unity (however, only very
slightly), and the magnetic susceptibility is negative; that is, the
magnitude of the B field within a diamagnetic solid is less than that in
a vacuum.
 Diamagnetic Materials
❖ The value of diamagnetic susceptibility is independent of temperature
and applied magnetic field.
❖ Diamagnetism is found in all materials; but because it is so weak, it can
be observed only when other types of magnetism are totally absent.
❖ This form of magnetism is of no practical importance.
❖ Examples: Organic materials, Alkali earth elements, Bismuth,
superconducting materials
Common for noble gas atoms and alkali halide ions
(i.e., He, Ne, F-, Cl-, Li+, Na+)

No unpaired electrons
 Paramagnetic Materials
Paramagnetic

Atomic dipole configuration with and without an

random

aligned
external magnetic field for a paramagnetic
material (possess permanent dipole)

Common for isolated rare earth ions, iron (group 3d) ions
(i.e., Sm+, Er+, Fe3+, Co2+, Ni2+)

❖ Paramagnetic materials have a net magnetic moment due to

unpaired electrons in partially filled orbitals.
❖ The individual magnetic moments do not interact magnetically, and
like diamagnetism, the magnetization is zero when the field is
removed.
❖ In the presence of a field, there is now a partial alignment of the
atomic magnetic moments in the direction of the field, resulting in a
net positive magnetization and positive susceptibility.

induced moment is favored by applied field (but is

opposed by thermal disorder)
 Paramagnetic Materials
❖ Susceptibility is independent of magnetic field and depends on
temperature

❖ With increase in temperature, the paramagnetic effect decreases

Unpaired electrons
 Non-magnetic vs. magnetic materials
➢ Both diamagnetic and paramagnetic materials are considered to
be nonmagnetic because they exhibit magnetization only when in
the presence of an external field.
➢ Also, for both, the flux density B be in a vacuum.

➢ Certain materials possess a

permanent magnetic moment in
the absence of an external field,
and manifest very large and
permanent magnetizations.
➢ These are the characteristics of
ferro/ferri magnetism.
➢ Magnetic susceptibilities as
high as are possible for
ferromagnetic materials.
Schematic representation of the flux density B versus
the magnetic field strength H for diamagnetic and
paramagnetic materials.
 Ferromagnetic materials
❖ Possess spontaneous magnetization (net magnetization that exists in the
absence of a field) and magnetic ordering temperature.
❖ Materials shows magnetic properties even in absence of magnetic field
❖ Spontaneous magnetization is due to interaction between dipoles called
exchange forces (are very large)

❖ When place in external magnetic field, Ferromagnetic

it strongly attracts magnetic lines of
force
❖ All spins are aligned parallel and in
same direction
❖ Coupling forces align the magnetic
spins
 Domain and domain wall
❖ Ferromagnetic material composed of small-volume
regions in which all magnetic dipole moments are
aligned in one direction is called a domain
❖ Adjacent domains are separated by domain
boundaries or walls, across which the direction of
magnetization gradually changes
❖ Normally, domains are microscopic in size, and for a
polycrystalline specimen, each grain may consist of
more than a single domain. Thus, in a macroscopic
piece of material, there will be a large number of
domains, and all may have different magnetization
Schematic depiction of domains orientations
in a ferro/ferrimagnetic material

❖ In each domain, the magnetic moments were aligned parallel, however, the
direction of alignment varies from domain to domain in a more or less random
manner.
❖ The magnitude of the M field for the entire solid is the vector sum of the
magnetizations of all the domains
 Magnetic domains

Magnetic domains exist in order to reduce the energy of the system.

 Domain wall

The gradual change in magnetic dipole orientation across a domain wall 180o and 90o domain wall

Bloch wall Neel wall

❖ Magnetization in Bloch wall is normal to the plane of film and adds to the wall
energy a demagnetization energy ~ Ms2d per unit length of wall, where  is the
wall thickness and d is the film thickness.
❖ In the Neel wall the magnetization is parallel to the surface; the addition to wall
energy is negligible when d  .
 Ferromagnetic materials
B (M) versus H:

❖ Ferromagnetic/ ferrimagnetic material initially unmagnetized

❖ As the applied field (H) increases: Magnetic moment aligns with H0

Domain configurations during

several stages of magnetization
 Ferromagnetic materials
Saturation Magnetization
M

❑ The maximum possible magnetization, or saturation magnetization of a

ferromagnetic material represents the magnetization that results when all
the magnetic dipoles in a solid piece are mutually aligned with the
external field
❑ The saturation magnetization is equal to the product of the net magnetic
moment for each atom and the number of atoms present.

8
 Magnetic Hysteresis
The striking property of Ferro Magnetic materials is the relation
between Magnetization and the strength of Magnetic field. This
property is called Hysteresis.
M P Saturation
Ms Magnetization
Residual
Q
Magnetization Mr

-Hs R
Hc o Hs
Coercivity
H
S The area of loop indicates the amount of
-Ms energy wasted in one cycle of operation.
Ferro Magnetic Material
 Effect of temperature
❖ Even though electronic exchange forces in ferromagnets are very large,
thermal energy eventually overcomes the exchange and produces a
randomizing effect (magnetic dipoles deviate from parallel arrangement)
❖ At a particular high temperature, ferromagnetism is completely lost and
material becomes paramagnetic and the temperature at which such
transition occur is called as Curie temperature (Tc)
❖ Saturation magnetization goes to zero at the Curie
temperature
❖ On cooling, ferromagnetic/ ferrimagnetic domains
reform

Effect of temperature on
ferromagnetic material

Curie temperature is also an intrinsic property

and is a diagnostic parameter that can be used
for mineral identification. However, different
material in principle, can have the same Tc
 Ferrimagnetic materials
❖ Unlike paramagnetic materials, the atomic moments in these materials
exhibit very strong interactions.
❖ These interactions are produced by electronic exchange forces and
result in a parallel or antiparallel alignment of atomic moments.
❖ Exchange forces are very large, equivalent to a field on the order of 1000
Tesla, or approximately a 100 million times the strength of the earth's
field.
Ferrimagnetic

Ferrimagnetism is therefore similar to ferromagnetism. However, ferro- and

ferrimagnets have very different magnetic ordering.
 Ferrimagnetic materials
❖ In ionic compounds, such as oxides, more complex forms of magnetic
ordering can occur as a result of the crystal structure.
❖ The magnetic structure is composed of two magnetic sublattices (called A
and B) separated by oxygens.
❖ The exchange interactions are mediated by the oxygen anions. When this
happens, the interactions are called indirect or superexchange
interactions. The strongest superexchange interactions result in an
antiparallel alignment of spins between the A and B sublattice.
❖ The magnetic moments of the A and B sublattices are not equal and result
in a net magnetic moment.

❖ Fe3O4 crystallizes with the inverse

spinel structure. Its structural formula
is [Fe3+]A [Fe3+,Fe2+]B O4
❖ The large oxygen ions are close packed
in a cubic arrangement and the smaller
Fe ions fill in the gaps.
With negative AB exchange interactions, the net
magnetic moment of magnetite is due to the B-site Fe2+.
 Ferrites: Magnetic moment
Common formula: M 2+Fe23+O4 (MO.Fe2O3) M = Fe, Mn, Co, Ni, Zn
Soft magnetic materials are used in devices that are
subjected to alternating magnetic fields and in which
Hard vs. Soft Magnetic Materials
energy losses must be low

❖ Both ferromagnetic and ferrimagnetic materials are classified as either soft

or hard on the basis of their hysteresis characteristics.
Hard vs. Soft Magnetic Materials
 Antiferromagnetic materials
➢ The alignment of the spin moments of neighboring atoms or ions in
exactly opposite directions. The opposing magnetic moments cancel one
another, and, as a consequence, the solid as a whole possesses no net
magnetic moment.

Sublattices magnetization of an antiferromgnet

Antiparallel alignment of spin
magnetic moments (AB interaction but no AA and BB interaction)

Lattice of magnetic ions divided into two identical sublattices, A and B such that A
ion has only B ions as nearest neighbor and vice versa. If the A and B sublattice
moments are exactly equal but opposite, the net moment is zero.

➢ Examples: FeO, MnO, NiO, Cr2O3 and salts of transition elements

Summary on classification of magnetic materials
 Comparison between diamagnetic,
paramagnetic and ferromagnetic materials
 Magnetic Energy
❖ System achieved most stable structure:- when overall potential energy is
minimum
❖ Total magnetic energy of a ferromagnetic material is the sum of the
following energies:

➢ Exchange energy – potential energy within a domain is minimized

when all atomic dipoles are aligned in single direction. The alignment
is associated with a positive exchange energy
➢ Magnetostatic energy – potential magnetic energy produced by its
external field. The formation of multiple domain reduces magnetostatic
energy
➢ Magnetocrystalline anisotropy energy – the work done to rotate all
domains to reach Saturation. Magnetization with applied field for a
single crystal varies with crystal orientation
➢ Domain wall energy – domain changes orientation gradually with a
boundary
➢ Magnetostrictive energy – the energy due to mechanical stress created
by magnetostriction
 Exchange energy
❖ Exchange energy – potential energy within a domain is minimized when all
atomic dipoles are aligned in single direction. The alignment is associated
with a positive exchange energy
❖ If two atoms i and j have spin angular momentum Sih/2 and Sjh/2
respectively, then the exchange energy between them is given by

where Jex is a particular integral, called the exchange integral, which occurs in the
calculation of the exchange effect, and  is the angle between the spins.

❖ If Jex is positive, Eex is a minimum when the

spins are parallel (cos  = 1) and a
maximum when they are antiparallel (cos 
= -1).
❖ If Jex is negative, the lowest energy state
results from antiparallel spins.
❖ A positive value of the exchange integral is
therefore a necessary condition for
ferromagnetism to occur.
Exchange Interaction
 Magnetostatic energy
❖ Magnetostatic energy – magnetic energy produced by its external field.
❖ The formation of multiple domain reduces magnetostatic energy

Formation of multidomain Closure domain

The break up of the magnetisation into two domains reduces the magnetostatic
energy by half (Magnet breaks down into N domains then the magnetostatic
energy is reduced by a factor of 1/N)
In closure domain structure where the magnetostatic energy is zero, however,
this is only possible for materials that do not have a strong uniaxial anisotropy,
and the neighboring domains do not have to be at 180º to each other.
 Domain wall energy
➢ Domain wall energy – domain changes orientation gradually with a
boundary
➢ Domain walls have a finite width that is determined principally by
exchange and magnetocrystalline energy.
➢ Equilibrium wall width is width at which sum of two energies are minimum
➢ A strong magnetocrystalline anisotropy will favor a narrow wall, whereas a
strong exchange interaction will favor a wider wall.
 Domain wall width
Let's consider a domain wall in which the magnetization changes by 180°.
The change in magnetization within the wall can be gradual as in (a) or
abrupt as in (b).

The exchange energy acts to keep spins parallel and can be kept small if the
180°rotation takes place gradually, over many atomic units. Therefore, the
exchange energy is small in (a) but large in (b).

This number of domains will depend on the size and shape of the
sample (which will affect the magnetostatic energy) and the intrinsic
magnetic properties of the material (which will affect the
magnetostatic energy and the domain wall energy).
 Magnetocrystalline anisotropy energy
❖ Are magnetic properties same in all direction ?

❖ Its depends on crystallographic direction in which magnetic dipole are

aligned (varies with crystal orientation)

❖ Magnetic axis of a domain lie along some fixed direction(s) in a sample

known as the easy axis is the phenomenon of magnetic anisotropy.

❖ Magnetocrystalline anisotropy (crystal anisotropy) energy – the work done

to rotate all domains to reach saturation.
 Magnetocrystalline anisotropy energy
(BCC and FCC structure)

BCC Fe saturation magnetization occurs most easily for the <100> direction
saturation magnetization occurs with highest applied field for <111> direction

FCC Ni and FCC Fe3O4 the easy directions of magnetization are <111> and
<100> the hard direction grains at different orientations will reach saturation
magnetization at different field strength
Superparamagnetism (SPM)

Properties and applications

 Superparamagnetism (Nanomagnetism)

❖ Surface effect
❖ Volume effect

❖ Small size and larger magnetic moment for each particle like
Ferromagnetism --Large M S
❖ Response to external field like paramagnetic response---No open loop
 The superparamagnetic behavior, below a
critical size

The coercivity for the nanocrystalline materials is small when they are in their multidomain
state and will be maximum at the critical single domain size and decreases further with
grain size reduction as it approaches superparamagnetism, due to increase in the thermal
energy compared to the anisotropy energy.
Crbon based nanomaterials

❑ Graphene
❑ Carbon nano tubes
❑ Fullerene
 Graphene

Graphene is an atomic-scale honeycomb lattice

made of carbon atoms.
❑Graphene can be described as a one-atom thick layer of graphite.
❑It is the basic structural element of other allotropes, including graphite,
charcoal, carbon nano tubes and fullerenes.
❑Graphene is the strongest, thinnest material known to exist.
Graphene is a 2D
crystal of carbon
atoms, arranged in a
honeycomb lattice

Each carbon atom is

sp2 hybridized and it
is bound to its three
neighbors.
 History
• One of the very first patents pertaining to the
production of graphene was filed in October, 2002
entitled, "Nano-scaled Graphene Plates“.

• Two years later, in 2004 Andre Geim and Kostya

Novoselov at University of Manchester extracted
single-atom-thick crystallites from bulk graphite

• Geim and Novoselov received several awards for

their pioneering research on graphene, notably the
2010 Nobel Prize in Physics.
 Structure
• Graphene is a 2-dimensional network of carbon atoms.
• These carbon atoms are bound within the plane by strong
bonds into a honeycomb array comprised of six-membered
rings.
• By stacking of these layers on top of each other, the well
known 3-dimensional graphite crystal is formed.
• It is a basic building block for graphitic materials of all other
dimensionalities.
• It can be wrapped up into 0D fullerenes, rolled into 1D
nanotubes or stacked into 3D graphite.
• Thus, graphene is nothing else than a single graphite layer.
 Chemical Properties
• Graphene is chemically the most reactive form of
carbon.
• Only form of carbon (and generally all solid
materials) in which each single atom is in exposure
for chemical reaction from two sides (due to the
2D structure).
• Carbon atoms at the edge of graphene sheets
have special chemical reactivity.
• graphene burns at very low temperature (e.g.,
350 °C).
• Graphene has the highest ratio of edgy carbons (in
comparison with similar materials such as carbon
nanotubes).
• Graphene is commonly modified with oxygen- and
nitrogen-containing functional groups
 Electronic Properties
• It is a zero-overlap semimetal (with both holes and
electrons as charge carriers) with very high electrical
conductivity.
• Electrons are able to flow through graphene more easily
than through even copper.
• The electrons travel through the graphene sheet as if they
carry no mass, as fast as just one hundredth that of the
speed of light.
• High charge carrier mobility, for which values of 10,000
cm2/Vs, in some cases even 200,000 cm2/Vs were
reported.
In an insulator or semiconductor, an electron bound to an atom can
break free only if it gets enough energy from heat or passing photon
to jump the ‘band gap’.
But in graphene the gap is infinitesimal. This is the main reason why
graphene’s electron can move easily and very fast.
 Mechanical Properties

• To calculate the strength of

graphene, scientists used a
technique called Atomic Force
Microscopy.
• It was found that graphene is
harder than diamond and about
300 times harder than steel.
• The tensile strength of graphene
exceeds 1 TPa.
• It is stretchable up to 20% of its
initial length.
It is expected that
graphene’s mechanical
properties will find
applications into making
a new generation of
super strong composite
materials and along
combined with its optical
properties, making
flexible displays.
 Thermal Properties
• Graphene is a perfect thermal conductor
• Its thermal conductivity is much higher than all the other
carbon structures as carbon nanotubes, graphite and
diamond (> 5000 W/m/K) at room temperature
• Graphite, the 3 D version of graphene, shows a thermal
conductivity about 5 times smaller (1000 W/m/K)
• The ballistic thermal conductance of graphene is isotropic,
i.e. same in all directions
The material's high electron
mobility and high thermal
conductivity could lead to
chips that are not only faster
but also better at dissipating
heat.

This schematic shows a

three-dimensional stacked
chip with layers of graphene
acting as heat spreaders.
 Optical Properties

• Graphene, despite it is only

1 atom thick, is still visible
to the naked eye.
• Due to its unique electronic
properties, it absorbs a high
2.3% of light that passes
through it.

Photograph of graphene in transmitted light.

This one-atom-thick crystal can be seen with the
naked eye.
 Applications
While as of 2014, graphene is not used in commercial
applications, many have been proposed and/or are under active
development, in areas including electronics, biological
engineering, filtration, lightweight/strong composite materials,
photovoltaics and energy storage.
Biomedical
Graphene could soon be used to
analyze DNA at a record-breaking
pace.
That’s the claim of a physicist in
the US who has proposed a new
way of reading the sequence of
chemical bases in a DNA strand by
sending the molecule through a
tiny slit in a graphene sheet.
Integrated
circuits
o Graphene has a high carrier
mobility, as well as low noise,
allowing it to be used as the
channel in a field-effect transistor.
o Processors using 100 GHz
transistors on 2-inch (51 mm)
graphene sheets.
o Graphene-based integrated circuit
handled frequencies up to 10 GHz.
o Transistors printed on flexible
plastic that operate at 25 gigahertz
o Terahertz-speed transistor
Optical
Electronics

✓ Graphene's high electrical conductivity and high optical transparency

make it a candidate for transparent conducting electrodes.
✓ Graphene's mechanical strength and flexibility are advantageous
compared to indium tin oxide, which is brittle.
✓ So it would work very well in optoelectronic applications:
touchscreens, liquid crystal displays, organic photovoltaic cells, and
organic light-emitting diodes.
Filters

Desalination: By very precise

control over the size of the
holes in the graphene sheet,
graphene oxide filters could
outperform other techniques of
desalination by a significant
margin.
Ethanol distillation: Graphene
oxide membranes allow water
vapor to pass through, but are
impermeable to other liquids
and gases.
Solar cells

• Graphene turned to be a
promising material for
photoelectrochemical energy
conversion in dye sensitized
solar cells.
• The transparent, conductive,
and ultrathin graphene films are
fabricated from exfoliated
graphite oxide, followed by
thermal reduction.
• The obtained films exhibit a
high conductivity of 550 S/cm
Energy
Storage
Devices

✓ Due to the extremely

high surface area to
mass ratio of graphene,
one potential
application is in the
conductive plates of
Supercapacitors.

✓ It is believed that
graphene could be
used to produce
Supercapacitors with a
Anti-
Bacterial

• In 2010, the Chinese

Academy of Sciences
has found that sheets
of graphene oxide are
highly effective at
killing bacteria such as
Escherichia coli.
• This means graphene
could be useful in
applications such as
hygiene products or
packaging that will
 Other Applications
• Composite Materials
• Liquid Cells for Electron
• Graphene nanoribbons
Microscopy
• IR detectors
• Thermal management
• Single-molecule gas materials
detection
• Optical Modulators
• Piezoelectric materials
• Chemical sensors
• Energy Harvesting
Nanomaterials and chemical
sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in

6th class
Allotropes of
carbon

a) diamond
b) graphite
c) lonsdaleite
d) - f)
fullerenes
(C60,
C540,
C70);
g) amorphou
s carbon
h) carbon
nanotube
 Graphite
•Layered structure with strong
bonding within the planar layers and
weak, van der Waals bonding between
layers
•Easy interplanar cleavage, applications
as a lubricant and for writing (pencils)
• Good electrical conductor
•Chemically stable even at high
temperatures
•excellent thermal shock
resistance

Applications:

Commonly used as heating elements (in non- oxidizing

atmospheres), metallurgical crucibles, casting molds, electrical
contacts, brushes and resistors, high temperature refractories,
welding electrodes, air purification systems, etc.
3D stalking of ABAB structure
 Graphite

Graphite is a layered compound. In

each layer, the carbon atoms are
arranged in a hexagonal lattice with
separation of 0.142 nm, and the
distance between planes is 0.335 nm
The acoustic and thermal properties of
graphite are highly anisotropic, since
phonons propagate very quickly along the
tightly-bound planes, but are slower to travel
from one plane to another.
11
 Diamond
- chemical bonding is purely covalent
- highly symmetrical unit cell
- extremely hard
- low electrical conductivity
- high thermal conductivity (superior)
- optically transparent
-used as gemstones and industrial grinding, machining and
cutting

12
 Introduction on Carbon Nanomaterials

• Carbon is one of the very interesting elements which

constitutes a major part of the living as well as non-living
world.
• Clusters and Nanomaterials that we know today provide a
rich variety of Carbon forms.
• Crystalline carbon can exist in diamond, graphite,
fullerene, carbon nanotubes, graphene etc.

7
Types of Carbon nanomaterials

0-D • Small Clusters, Fullerenes

Nanodiamonds.

1-D
• Carbon Nanotubes

2-D
• Graphene
 Fullerenes
• Fullerene was discovered around 1985.
• Diameter of C60 fullerene is just 0.7 nm; that is
why we can consider fullerenes as 0-D
material
• Fullerene crystal is a molecular crystal
having Face Centered Cubic (FCC) structure.
• At the corners and faces of a cube there are
ball shaped carbon molecules which
themselves belong to fullerene family.

9
In geometry, an icosahedron is a polyhedron with 20 faces.

Vertices= 12 (corners)
Edges = 30
Face= 20 Equilateral triangle

So all edges are equal,

all vertices are identical (where 5 equilateral triangle meet)
Now we need to truncate the vertices or to chop of the vertices

Now we have a pentagonal face

Now the chopping off of the original triangular face in all 12 vertices are done in
such way that it becomes a regular hexagon

So now we have 12 pentagonal face as well as 5 hexagon

surrounding the pentagonal face. In total 20 hexagonal faces. It
is thus called truncated icosahedron.

So now we have 60 total vertices and if we put each C atom on each vertices,
It becomes C60 molecule.
12
• Each fullerene molecule has a cage-like
structure.
• All the carbon atoms are located on the
surface of a nearly spherical figure.
• Fullerenes can have 60, 70, 78 or more number
of carbon atoms on the surface, out of which
60-atom molecule (or cluster) is the most
stable and spherical in shape.

13
 Fullerene – Why the
name?
• Kroto, Smalley and Curl were
working on simulating interstellar
molecules in their laboratory.
• They were trying to laser ablate a
graphite rod and study its mass
spectrum using a mass spectrometer.
• Evaporation from graphite was carried
out in ultra high vacuum chamber in
helium atmosphere.
14
• To their great surprise they repeatedly got a
mass signal due to 60 carbon atom cluster.
• They tried to model it nearly for a week
and suddenly Kroto remembered of an
industrial exhibition he had once visited.
• There he had seen a domelike steel
structure constructed by a very famous
architect Buckminster Fuller.
• This dome had some pentagons and
some hexagons distributed on its
surface.

15
• Kroto, Smalley and Curl succeeded in
constructing 60 atoms cluster model with 12
pentagons and 20 hexagons with a restriction
that no two pentagons touched each other and
each pentagon shared an edge with hexagon.
• It was in the honour of Buckminster Fuller that
the name Fullerene was given to the family of this
newly found cage-like carbon cluster.
• Kroto, Smalley and Curl received the Nobel
Prize in 1996 for their discovery.

16
 Properties of fullerenes
• Arranged in pentagons and hexagons

• Also has20 the highest packing density of all

known structures (including diamonds)
• Impenetrable to all elements under normal
circumstances, even a helium atom with an energy
of 5eV (electron Volt)
Variations of buckyballs
dodecahedral
graph

The
26-fullerene 70-fullerene
smallest
graph graph
fullerene C
 Carbon Nanotubes
• This 1-D form of carbon was accidentally
observed in 1991 by S. Iijima under a
transmission electron microscope. He
was actually examining some sample of
carbon clusters viz. ‘fullerenes’
synthesized using electric arc discharge
method.
• Further it was found that not only carbon but
many other materials like ZnO, TiO2, and
MoS2 can have shape of nanotube.

18
• Carbon nanotubes can be considered as
cylinders made of graphite sheets, mostly
closed at the ends, with carbon atoms on the
apexes of the hexagons, just like on a graphite
sheet.
• One can consider carbon nanotube as folding of
a graphite sheet (it is only an imaginary sheet,
actual growth can be different), just like one rolls
a piece of paper into a cylindrical form.

19
20
• The difference however is that, a paper is a
two dimensional solid material (area much
larger, a few cm2, as compared to thickness
of few micrometres) and the graphite sheet
we are talking about has an area of few μm2
and thickness just the atomic size of a
Carbon Atom.

21
• If we consider the rolling of graphite sheet,
we can imagine carbon atoms being spread
in hexagonal arrangement with some lattice
strain.
• Besides, during their formation,
nanotubes get capped with hemispheres
of fullerenes.

Fullerene Cap on CNT’s

22
 Types of CNTs

• D – 1-
SWCNT 2nm

• D – 2-25 nm
MWCNT
• More
common 23
• MWCNTs can be turned into
SWCNTs using some etching
methods.

A) Russian doll
B) Parchment type

24
• As the carbon nanotubes can be imagined
as folding of a graphite sheet, two things
are observed,
• (1) Carbon atoms on nanotubes are
bonded like in graphite, although some
strain would be expected due to curvature
.
• (2) There should be more than one way
of folding the graphite sheet.

25
• The tubes whose mirror image is identical
with its own image is known as ‘achiral’ tube
and ‘chiral’ otherwise.
• The tubes are normally terminated with
the hemispheres of fullerenes as was
predicted by Smalley.
• These are simply called as ‘caps’ or ‘end
caps’. Caps contain six pentagons (half the
number in C60 fullerene) and different
number of hexagons so that they can fit on
the tubes properly.

26
Classification Based upon Chirality

Zigzag CNT

Armchair

CNT Helical

CNT
27
Zigzag CNT

28
Armchair CNT

29
Helical CNT

30
Zig zag
Arm chair

(3,3)
 Chiral

(1,4)
Geometry of NT
 Synthesis of Carbon Nanotubes
• Iijima had detected carbon nanotubes in
an electric arc discharge set up for
synthesizing fullerenes. His nanotubes
were chiefly of the multiwall type.
• The yield of nanotubes was very low
compared to the fullerene content.
• Soon Electric arc discharge and other
methods like laser ablation and chemical
vapour deposition were optimized to
increase the yield and even to get
SWCNTs.
35
• MWCNT – Electric Arc
discharge Method

• SWCNT – Laser Ablation

• Mixture - CVD

36
 1. Electric Arc Discharge Method
• Electrodes: Graphite
• Diameter of electrodes: 5–20 mm
• Gap between the electrodes: 1 mm
• Helium gas pressure: 100–500 Torr (no
CNT formed if p<100 Torr)
• Current: 50–120 A
• Voltage: 20–25 V
• Cooling of the chamber is preferred.
• Yield of MWCNT: 30–50 %

37
38
• Nanotubes are found to be deposited in the
central region of cathode.
• For MWCNT it is not necessary to use any
catalyst.
• The central region of cathode is surrounded by a
region in which nanoparticles, fullerenes and
amorphous carbon are formed.
• It, therefore, becomes necessary to purify the
MWCNTs to get rid of these other particles.
• No tubes are found to be deposited on the walls of
the experimental chamber as is the case with
fullerenes.

39
 2. Chemical Vapour Deposition (CVD)

• Here a hydrocarbon gas is cracked

for large scale production of the
nanotubes.
• As there are no graphitic hexagons
present in some of the precursors used
to deposit carbon nanotubes, catalysts
play a very important role in carbon
nanotubes formation.

40
41
42
• Advantage of this method is that aligned
nanotubes can be deposited on some solid
substrates so that they can be used for some
electronics or other application.
• Both MWCNT and SWCNT are possible to
obtain by this method. No nanoparticles or
amorphous carbon formation takes place,
making high purity nanotubes.

43
 3. Laser Ablation
• Advantage of using laser in the
synthesis of carbon nanotubes is
that the nanotubes are invariable
SWCNTs.
• Ropes of 10–20 nm diameter and
lengths 100μm also are observed.
• Narrow size distribution of
diameters of SWCNTs is an
attractive feature of this
technique. 44
45
 Nanotube key properties
 A broad range of electrical, thermal, and structural
properties depending on the tube diameter, length, and
chirality, or twist.

 Diameter : 1−30 nm
Length : < 1 mm

 1000 times better electrical conductors than copper.

 Transport heat twice as good as diamond. Tensile

strength 20 times that of steel and still flexible.

 Highly chemically reactive in nature.

 Graphene

Graphene is an atomic-scale honeycomb lattice made of

carbon atoms.
Graphene can be described as a one-atom thick layer of graphite.
It is the basic structural element of other allotropes, including graphite,
charcoal, carbon nano tubes and fullerenes.
Graphene is the strongest, thinnest material known to exist.
The nearest neighbors are not equivalent in nature in graphene.
Graphene is a 2D crystal
of carbon atoms,
arranged in a
honeycomb lattice

Each carbon atom is sp2

hybridized and it is
bound to its three
neighbors.
 History
• One of the very first patents pertaining to the
production of graphene was filed in October, 2002
entitled, "Nano-scaled Graphene Plates“.

• Two years later, in 2004 Andre Geim and Kostya

Novoselov at University of Manchester extracted
single-atom-thick crystallites from bulk graphite

• Geim and Novoselov received several awards for

their pioneering research on graphene, notably the
2010 Nobel Prize in Physics.
 Structure
• Graphene is a 2-dimensional network of carbon atoms.
• These carbon atoms are bound within the plane by strong
bonds into a honeycomb array comprised of six-membered
rings.
• By stacking of these layers on top of each other, the well
known 3-dimensional graphite crystal is formed.
• It is a basic building block for graphitic materials of all other
dimensionalities.
• It can be wrapped up into 0D fullerenes, rolled into 1D
nanotubes or stacked into 3D graphite.
• Thus, graphene is nothing else than a single graphite layer.
 Chemical Properties
• Graphene is chemically the most reactive form of
carbon.
• Only form of carbon (and generally all solid materials)
in which each single atom is in exposure for chemical
reaction from two sides (due to the 2D structure).
• Carbon atoms at the edge of graphene sheets have
special chemical reactivity.
• graphene burns at very low temperature (e.g., 350 °C).
• Graphene has the highest ratio of edgy carbons (in
comparison with similar materials such as carbon
nanotubes).
• Graphene is commonly modified with oxygen- and
nitrogen-containing functional groups
 Electronic Properties
• Electrons are able to flow through graphene more easily
than through even copper.
• The electrons travel through the graphene sheet as if they
carry no mass, as fast as just one hundredth that of the
speed of light.
• High charge carrier mobility, for which values of 10,000
cm2/Vs, in some cases even 200,000 cm2/Vs were
reported.
 Mechanical Properties

• To calculate the strength of graphene,

scientists used a technique called
Atomic Force Microscopy.
• It was found that graphene is harder
than diamond and about 300 times
harder than steel.
• The tensile strength of graphene
exceeds 1 TPa.
• It is stretchable up to 20% of its initial
length.
It is expected that
graphene’s mechanical
properties will find
applications into making
a new generation of
super strong composite
materials and along
combined with its
optical properties,
making flexible displays.
 Thermal Properties
• Graphene is a perfect thermal conductor
• Its thermal conductivity is much higher than all the other
carbon structures as carbon nanotubes, graphite and
diamond (> 5000 W/m/K) at room temperature
• Graphite, the 3 D version of graphene, shows a thermal
conductivity about 5 times smaller (1000 W/m/K)
• The ballistic thermal conductance of graphene is isotropic,
i.e. same in all directions
The material's high electron
mobility and high thermal
conductivity could lead to chips
that are not only faster but also
better at dissipating heat.

This schematic shows a three-

dimensional stacked chip with
layers of graphene acting as
heat spreaders.
 Optical Properties

• Graphene, despite it is only

1 atom thick, is still visible
to the naked eye.
• Due to its unique electronic
properties, it absorbs a high
2.3% of light that passes
through it.

Photograph of graphene in transmitted light.

This one-atom-thick crystal can be seen with the
naked eye.
 Applications
While as of 2014, graphene is not used in commercial
applications, many have been proposed and/or are under active
development, in areas including electronics, biological
engineering, filtration, lightweight/strong composite materials,
photovoltaics and energy storage.
Biomedical
Graphene could soon be used to
analyze DNA at a record-breaking
pace.
That’s the claim of a physicist in
the US who has proposed a new
way of reading the sequence of
chemical bases in a DNA strand by
sending the molecule through a
tiny slit in a graphene sheet.
Integrated
circuits
o Graphene has a high carrier
mobility, as well as low noise,
allowing it to be used as the
channel in a field-effect transistor.
o Processors using 100 GHz
transistors on 2-inch (51 mm)
graphene sheets.
o Graphene-based integrated circuit
handled frequencies up to 10 GHz.
o Transistors printed on flexible
plastic that operate at 25 gigahertz
o Terahertz-speed transistor
Filters
Desalination: By very precise control over the
size of the holes in the graphene sheet,
graphene oxide filters could outperform other
techniques of desalination by a significant
margin.
Ethanol distillation: Graphene oxide
membranes allow water vapor to pass through,
but are impermeable to other liquids and
gases.
Such membranes could revolutionize the
economics of biofuel production and the
alcoholic beverage industry
Solar cells
• Graphene turned to be a promising
material for photoelectrochemical
energy conversion in dye sensitized
solar cells.
• The transparent, conductive, and
ultrathin graphene films are
fabricated from exfoliated graphite
oxide, followed by thermal
reduction.
• The obtained films exhibit a high
conductivity of 550 S/cm and a
transparency of more than 70% over
1000-3000 nm.
Energy Storage
Devices

 Due to the extremely high surface area to mass ratio of

graphene, one potential application is in the conductive plates
of Supercapacitors.

 It is believed that graphene could be used to produce

Supercapacitors with a greater energy storage density than is
currently available.
 Anti-
Bacterial
• In 2010, the Chinese Academy of
Sciences has found that sheets of
graphene oxide are highly
effective at killing bacteria such
as Escherichia coli.
• This means graphene could be
useful in applications such as
hygiene products or packaging
that will help keep food fresh for
longer periods of time.
 Other Applications
• Composite Materials
• Liquid Cells for Electron
• Graphene nano ribbons
Microscopy
• IR detectors
• Thermal management
• Single-molecule gas materials
detection
• Optical Modulators
• Piezoelectric materials
• Chemical sensors
• Energy Harvesting
Nanomaterials and chemical
sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in

7th class
Experimental Techniques
Books:
(1) Introduction to nanotechnology ( Authors : C. P.
Poole and F. J. Owens)

(2) The chemistry of nano materials ( Authors; C. N. R.

Rao, A. Muller and A. K. Cheetham )

(3) Nanotechnology : An introduction to nano

structuring techniques ( Authors : M. Kohler and W.
Fritzsche)
Materials Characterization

Particulate Materials

Composition Geometry
(size, shape, charge, polydispersity ..)

Physical properties can be tuned by geometry

➢ Flow behavior of suspensions, Formulation stability

(colloids, pharmaceutical, pesticide etc),
Microstructure evaluation

How to characterize them?

➢ Size, shape, polydispersity etc

Direct counting: Seeing is believing

❖ Electron/optical microscopy

➢It is important to count a large number of particles from the

images in order to get a good statistical average.

➢For self assemblies, certain polymers and biological materials-

Solvent sensitive: Cryo-TEM is required.
Microstructure evaluation

Option –

Indirect analysis using scattering of radiation

❖ Scattering methods (Light, neutrons, X-rays)

What is scattering ???

➢ The interaction of radiation with matter results in scattering events in

addition to other processes such as absorption, reflections etc.

➢When energy waves (such as light, and various electromagnetic waves) are
caused to depart from a straight path due to inhomogeneity in the medium, it
is called scattering.

➢ Different from reflection, where radiation is deflected in one direction, the

particles and molecules have the ability to scatter electromagnetic radiation
in all directions.

The particles/molecules which

scatter light are called scatterers
How to use Scattering techniques
for particle characterization
Theory of Scattering

sample

 2
detector

Fig. Schematic representation of a scattering experiment

ki Elastic scattering experiment

kf Q │ki│=│kf│=2/

Q = |ki-kf| = 4sin/
➢ This leads to the use of different radiations for scattering such as
light, neutron, X-rays.

➢Light Scattering
Static Light Scattering
Dynamic Light Scattering
➢Small-Angle Scattering (SAS) Techniques
Small Angle Neutron Scattering (SANS)
Small Angle X-ray Scattering (SAXS)

➢ The scattering arises from

❖ refractive index of scatterers for light

❖ Electron density for x-rays
❖ Scattering length density for neutrons.

➢ The interpretation of data from scattering of different radiation is similar

with a difference that they probe at different length scales depending
upon the wavelength of the radiation.
 Techniques for the Measurement of Different Structures

MICROSCOPIC
MACROSCOPIC
length scale
length scale

MESOSCOPIC (NANO) length scale

Scattering – comparison of length scale

Light, neutron and X-ray scattering

Size range of different scattering methods

1 10 100 1000 10000 Dimension (nm)

SANS, SAXS USANS

Comparison (Static scattering)
SLS - Different length scales
RGD MIE light (refractive index)
x-rays (electron density)
DLS neutrons (scattering length density)
Light Scattering

➢Light Scattering
Static Light Scattering
Dynamic Light Scattering
 Light Scattering Techniques

➢ The intensity of scattered light from a colloid suspension depends upon the
scattering angle and the observation time.

I()
Static Light Scattering
(Time averaged scattering)
LASER  2

I(,t)
Dynamic Light Scattering
(Time dependent scattering)
Static Light Scattering (SLS)

❖ Time averaged, angular dependence

❖ The dimension of the colloids should be in the same range as wavelength
of the light.

Dynamic Light Scattering (DLS)

❖Time resolved
❖DLS can measure particles that are much smaller than the wavelength of
light.
 Overview
Introduction to Light Scattering

Basis of Dynamic Light

Scattering

How does DLS works

Instrumentation

Plan of an Experiment

Advantages/Disadvantages
Length Scales Covered By Different Techniques

Dynamic Light Scattering

 Elastic and Inelastic Scattering

Ki Inelastic
scattering
Incident  Kf
Q Ki
direction 2
Incident
Kf directio Ki  K f
n
Q/2 Scattered Lose in energy
Sin  = direction
K
uur uuur
Ki = K f = K
Kf
Q
Q = 2 KSin Ki
2
4 n Gain in energy Ki  K f
= Sin

 Particles are not stationary: Brownian Motion

Brownian motion is the random motion of particles suspended in a

fluid resulting from their collision with the quick atoms or molecules of
surrounding medium.

A suspended particle is constantly and randomly

bombarded from all sides by molecules of the liquid. If the
particle is very small, the number of hits it takes from one
side at a given time will be stronger than the bumps from
other side. This make the particle jump. These small
random jumps are what make up Brownian motion.

Brownian motion of the particles is related to the size and describes the
way in which very small particles moves in a fluid suspension
 What will Happen if The particles undergoing
Brownion Motion?

Since particles are moving randomly in space, the distance traveled by the
scattered waves from the particle to the detector varies with time.
Due to the interference of scattered
waves from particles, the net intensity
fluctuates randomly in time as the
relative positions of the particles
change.

This produces random “speckles ” in

space, which appear as randomly
fluctuating dark or bright spots in a
detector.
 Brownian motion is related to size

Smaller particle Larger particle

Moves faster Moves slower

Quick fluctuations in Intensity Slow fluctuations in Intensity

The larger the particle, the slower the Brownian motion will be. Smaller
particles are “kicked” further by the solvent molecules and move more rapidly.

This characteristics of colloids, related to Brownian motion is utilized in

dynamic light scattering to extract the size of the particles.
 Making Sense of Brownian Motion
Dynamic Light Scattering
Dynamic light scattering (DLS) has evolved as a fast, convenient tool for particle size
analysis of non-interacting spherical colloids.

Unlike static light scattering (SLS) in which the time averaged scattering intensity
is measured at various scattering angles and the DLS in which the time dependence
of the intensity is measured.

DLS can measure particles that are much

smaller than the wavelength of light.

The time dependence of

scattering intensity arises from
the fact that, at ambient
conditions, colloidal particles
are no longer stationary in the
suspension medium, rather
they move in a random walk
fashion by the Brownian motion
process.
 Time range of DLS

DLS
QENS
NMR
Raman
Brillouin
Dielectric

-14 -10 -6 -2 2
LOG(TIME (s))

DLS covers a very large time range!

Typically: 10-7 - 103 s! => 10 decades in time!
 How does DLS Work?
In dynamic light scattering, the speed at which the particles are diffusing due to
Brownian motion is measured. This is done by measuring the rate at which the
intensity of the scattered light fluctuates when detected using a suitable optical
arrangement.
Quantitative information regarding the time scale of these fluctuations in the scattered intensity is obtained
by a signal processing technique known as autocorrelation. Because of this reason, this technique is known
also under the name photon correlation spectroscopy (PCS).

The velocity of the Brownian

motion is defined by a property
known as the translational
diffusion coefficient .

A correlator is basically a signal comparator. It is designed to

measure the degree of similarity between two signals, or one
signal with itself at varying time intervals
 Auto Correlation Function
To understand the autocorrelation of scattered intensity, consider a time varying signal, I(t)
monitored at different intervals of time. If we represent the scattered intensity at an arbitrary
time as I(t) and those after a delay time τ as I( t + τ), the normalized auto correlation function of
the scattered intensity, K(τ)can be written as:

K ( ) = I ( t ) I (t +  )
Experimentally, the average designated by the brackets in above equation is a time
average over the data collection interval T:
T
1
K ( ) =  I ( t ) I (t +  )dt
T0

I ( t ) I (t +  ) 1
T

g (2) ( ) = 2
I (t ) =  I ( t ) dt
I (t ) T 0

The normalized intensity autocorrelation function

 I ( t ) I (t +  )
g ( ) =
(2)
2
I (t )
When the delay time τ is zero, the signal is perfectly correlated and the
unnormalized correlation function) in above expression yields a value of ⟨I2⟩.

When τ is infinity, it is perfectly uncorrelated yielding a value of ⟨I⟩2.

From statistics, one can see that ⟨I2⟩ is greater than or equal to ⟨I⟩2.

The decay of this function follows a characteristic time scale depending on the
diffusion coefficient of the scatterers.

Electric field autocorrelation function of

scattered light from polystyrene
particles of size 54 nm and the
corresponding fit to the data using single
exponential decay.
For photo counts obeying Gaussian statistics, g2(τ) is related to the first-order
correlation function of the electric field g1( τ)by the relationship
2
g ( ) = g ( ) + 1
(2) (1)

Where, function g1(τ) is Electric field correlation function.

Es ( t ) Es (t +  )
g ( ) =
(1)

I (t )

N
Es (t ) =  bi ( q )eiq.ri ( t )
where i =1

bi (q) =  d 3r[ni (r ) − n0 ]eiq. R

v

n is the refractive index

 g (1)
( ) = e − Dq2

Where D is the translational diffusion coefficient related to particle size.

kT
D=
3 Dh

Dh= hydrodynamic diameter

D = translational diffusion coefficient
k = Boltzmann’s constant
T = absolute temperature
η = viscosity

Note that the size measure in DLS is not actual size rather is hydrodynamic size.
Experimental determination of Correlogram
K ( ) =  I ( ti ) I (ti +  k )
i =0
 Size dependence in Correlogram

1
 D 
Dh
If the particles are large the signal will be changing slowly and the correlation
will persist for a long time. If the particles are small and moving rapidly then
correlation will reduce more quickly.
Dynamic Light Scattering: Instrumentation

Main components
A light Source
Sample
Detector
Correlator
 Essentials of Light Source
Practical requirements for a sufficiently intense light source demand a narrow-
band, polarized, monochro-matic which are fulfilled CW laser.

Light Source
• Monochromatic, polarized and continuous (laser)
• Static light scattering goes as 1/λ4, suggests shorter
wavelengths give more signal (typical Ar+ ion laser at 488 nm)
• Dynamic light scattering S/N goes as λ, while detector
• Sensitivity goes as 1/λ, so wavelength is not too critical.
(HeNe lasers are cheap and compact, but weaker λ = 633 nm)
• Power needed depends on sample (but there can be heating!)
• Calculation of G(") depends on two photons, and so on the
• Power/area in the cell. Typically focus the beam to about
200 µm

DPSS have become widely available within the last few years. Their wavelength is
typically 532 nm (frequency doubled from powerful 1064 nm diode lasers) and
their other properties match well with the requirements of DLS instruments.
 Detectors
Photo Multipler Tubes (PMT) are almost universally used as detectors in DLS
instruments.

Basic Requirements are:

▪ Low dark count
▪ High gain

A comparatively new development is the single photon counting mode (SPCM)

which incorporates an avalanche photo diode (APD), active reset and quenching
electronics and a Peltier-type temperature controller in a small package.
These are successfully implemented into small fiber-optic-based DLS devices.
New SPCMs can replace PMTs in many applications, par-ticularly for
wavelengths of more than 680 nm (near infrared).

However, some of the reports suggests that these are not well suited for DLS
applications owing to the lack of active quenching and the lack of an integrated
temperature control for the semiconductor junction.
Zeta potential
 Content
❖ Introduction.
❖ Definition.
❖ Factor Affecting.
❖ Measurement.
❖ DLVO Theory.
❖ Applications.
❖ Conclusion.
❖ References.
 Introduction
• Zeta potential is a scientific term for electrokinetic potential in
colloidal dispersions.

• It is usually denoted using the Greek letter zeta (ζ), hence

ζ - potential.

• The electric potential at the boundary of the double layer is

known as the Zeta potential of the this particles and has values
that typically range from +100 mV to -100 mV.
 Definition
• Zeta potential: It is the potential
observed at the shear plane.

• Zeta potential or electro-kinetic

potential is defined as the difference
in the potential between shear plane
and electro-neutral region of motion
the solution.
 Conti...
• Zeta potential is more important than Nernst potential because the
electrical double layer also moves, when the particle is under motion.

• Nernst potential: It is the potential of the solid surface itself owing to

the presence of potential determining ions.
• Nernst potential or electro thermodynamic potential is defined as the
difference in potential between the actual surface and the
electroneutral region of the solution.
5
 Factors affecting zeta potential
1. pH : In aqueous media, the pH of the
sample is one of the most important
factors that affects its zeta potential.
zeta potential versus pH curve will be
positive at low pH and negative at high
pH. There may be a point where the
plot passes through zero zeta potential.
This point is called isoelectric point and
is very important from a practical
consideration.
 Conti...

2. Thickness of double layer: The thickness of the double layer

depends upon the concentration of ions in solution and can be
calculated from the ionic strength of the medium.

• The higher the ionic strength, the more compressed the double layer
becomes. The valency of the ions will also influence double layer
thickness.
 Zeta Potential
Measurement
• Zeta potential is not directly measurable, it can be calculated using
theoretical models like electrokinetic phenomena and electroacoustic
phenomena.
1. Electrokinetic Phenomena:
a. Electrophoresis:
The movement of charged particle relative to the liquid it is suspended
in under the influence of an electric field.
Conti...

• Zeta potential of dispersion is measured by applying an electric field

across the dispersion. Particles within the dispersion with a zeta
potential will migrate towards the electrode of opposite charge with a
velocity proportional to the magnitude of the zeta potential.

• The velocity of a particle in a unit electric field is referred to as its

electrophoretic mobility. Zeta potential is related to the
electrophoretic mobility by the Henry equation
 Henry
equation
UE = 2 ε z f(κa)/3η

Where:
UE = electrophoretic mobility,
z = zeta potential,
ε = dielectric constant,
η = viscosity
f(κa) = Henry’s function.
 Instrumentation
1. LASER

2. Cell

3. Detector

4. Digital signal Processor

5. Attenuator
1. Light Amplification by Stimulated Emission Radiation ( LASER ):

a. 632.8 nm Blue colour sample

b. 532 nm Red colour sample
 Zeta potential
Cell
• a) Folded Capillary cell: (DTS1060)

• solvent : water / alcohol

• sample volume : 0.75 mL.

Body of cell : Polycarbonate

Electrodes : Gold plated copper
b) Universal Dip cell (ZEN1002):

Solvent: : Water / Alcohol

Sample Volume : approximately 0.7mL

3. Detector :
Avalanche Photodiode
 DLVO
Theory
• The scientists Derjaguin, Landau, Verwey and Overbeek developed a theory in
the 1940s which dealt with the stability of colloidal systems.

• DVLO theory suggests that, the stability of a colloidal system is determined by

the sum of the Vander Waals attractive (VA) and electrical double layer repulsive
(VR) forces that exist between particles as they approach each other due to the
Brownian motion they are undergoing.

• The Vander waal forces depend on chemical nature and size of particle. The
electrostatic repulsive forces depend on density, surface charge and thickness of
double layer.
 Methods for stabilizing
colloids
Physical Stability can be achieved by maintaining the particle in
Brownian motion
a) Provide Electric charge on surface of dispersed particle:
The like charge on the particles will prevent these coming closer
together and thus maintaining a Brownian motion
Conti...
b) Maintain solvent sheath around the particle:
The solvent layer prevent the particle coming closer and also
maintain Brownian motion
 Applications

• Flocculate ( stick together )

• Suspension

• Emulsion

• Ceramics

• Waste water
 Conclusion
• Zeta potential has long been recognized as excellent tool for
characterizing colloidal system.
• In recent years the concept of zeta potential has been applied to are
as beyond classical colloidal sciences and industrial process.
• The expanding role of zeta potential in pharmaceutical sciences is
attributable to the advance in modern instrument of zeta potential
measurement, the rapid development of colloidal drug delivery
system and emphasis on interdisciplinary basic research.
Small-Angle Scattering
Different Scattering Techniques

Light Scattering  ~ 5000 Å

Small-Angle Neutron Scattering ~5Å

Small-Angle X-Ray Scattering ~1Å

The type of samples that can be studied, the sample environment that
can be applied, the actual length scales that can be probed and the
information that can be ultimately obtained, all depend on the
Scattering Technique used.
Comparison of Scattering Techniques

➢ SAXS can’t be employed to study thick samples or samples requiring

complex containers.

➢ SANS and SAXS probe different length scales to Light scattering.

➢ For hydrogenous samples SANS is a very good technique.

➢ Neuron with a wavelength of 1.5 Å has an energy of ~ 36meV, while

Energy of 1.5 Å X-rays is ~ 8.2 KeV.

➢ Neutrons have a particular advantage over X-rays in the study of

sensitive samples such as biological samples.
➢ These are complementary techniques and share several similarities.
➢ The same basic equations and laws can be used to analyse the data.

Q Important Factors

Q - Range

Neutron or X-Ray
Flux

Sample
Environment
 Small angle neutron scattering (SANS)

➢ Neutron is certainly particulate, it also has a wave nature and can display the
wave behaviours including reflection, refraction and diffraction.

➢ During a SANS experiment a beam of neutrons is directed at a sample, which can

be an aqueous solution, a solid, a powder, or a crystal.

➢ The neutrons are elastically scattered by nuclear interaction with the nuclei.
 Small-Angle Neutron Scattering
Time averaged, angular dependence of scattered intensity

sample

 2

To characterize size ‘D’ one needs

detector to do a scattering experiment
Q= scattering wave vector in which Q spans in a range
around the value of Q ~ /D.
ki

kf Q

D ~ 1 nm – 1000 nm
Q = |ki-kf| = 4sin/ Q range ~ 0.001 – 0.1 Å-1
Why is it called Small-Angle Scattering

D ~ 1 nm – 1000 nm
Q range ~ 0.001 – 0.1 Å-1 Q = 4sin/

low Q values

large wavelength small angles

() (☺)

………..Small-angle scattering (SAS)

Introduction to Small-Angle Scattering
2
Real Space 1 Scattering Data
I (Q) =   (r ) exp( iQ.r )dV
VV
I(Q)

Fourier Transform
Q

I(Q)

value of Q ~ /D
Q

Larger Length Scale Q~/D

I(Q)
D Q
Low Q Techniques Q
 Small-Angle Scattering Instrumentation

Source Monochromator Collimator Sample Detector

I-D & 2-D

X-ray:
Gas Detectors
Lab or Synchrotron
CCD
Neutron:
Reactor or Spallation

Wavelength Selection Different Environments

X-ray: 1.54 Å
Neutron: 4-10 Å
Tight Collimation
(long instruments)
 Small angle neutron scattering (SANS)

Neutron 
source

sample
Filter (BeO) Detector
slits

Dhruva reactor
For  = 5.2 Å, Q range ~ 0.018 – 0.32 Å-1.
Typical SANS Instrument
Information those can be obtained using SAS

Scattering intensity

I (Q) = n V2 ( p - s)2 P(Q) S(Q)

Number Density

}
n = number density of particles
&
V = volume of the particle Volume Fraction

 = scattering length density (p → particle, s → solvent) } contrast

}
P(Q) = |F(Q)|2 =Intraparticle structure factor Shape, Size
&
depends on the shape and size of the particles Size Distribution

S(Q) = Interparticle structure factor

decided by the interaction between the particles } Interaction

&
Ordering
Contrast – A Key Parameter

I (Q) = n V2 ( p - s)2 P(Q) S(Q)

(p-s)2 = contrast factor b i

= i

where ‘b’ is the nuclear scattering length of the nucleus,  is the scattering
length density and V is the volume containing n atoms

➢ The scattering length is a measure of the strength of the interaction of a

neutron wave with a given nucleus.

➢ Scattering intensity is proportional to “the square of the scattering length

density difference between studied materials and medium”.
S(q), Concentration dependence

1.4

1.2

1.0 =0.01

0.8
Vol. Fraction
S(q)

0.6
Charge
=0.1
Ionic strength
0.4

0.2

0.0
1E-3 0.01 0.1
-1
q (Å )

As concentration increases, peak develops at ~ 2/d

d is the average interparticle distance
 Scattering for X-rays vs. Neutrons
➢ Scattering is different for X-rays and neutrons as the X-rays are
scattered by the electron clouds and neutrons by the nuclei.
Atomic number
1 6 8 22 26 28 82

X-rays

H C O Ti Fe Ni Pb
Neutrons
1 46 54 58 Mass
2 Number
47 56 60
48 57 61

50 62

➢ SANS & SAXS provide different information on the structure of

micelles.
 Hydrogenous sample in salt solutions

Hydrogenous sample
counterion (micelles)
distribution
e.g. Cs+

D2O

neutrons x-rays
Nanomaterials and chemical
sensors

Bijaideep Dutta
Ext. no. 20286
E-mail id: bijaideep@barc.gov.in

9th class
Zeta potential
 Introduction
• Zeta potential is a scientific term for electrokinetic potential in
colloidal dispersions.

• It is usually denoted using the Greek letter zeta (ζ),

hence
ζ - potential.

• The electric potential at the boundary of the double layer is

known as the Zeta potential of the this particles and has values
that typically range from +100 mV to -100 mV.
 Definition
• Zeta potential: It is the potential
observed at the shear plane.

• Zeta potential or electro-kinetic

potential is defined as the difference
in the potential between shear plane
and electro-neutral region of motion
the solution.
 Conti...
• Zeta potential is more important than Nernst potential because the
electrical double layer also moves, when the particle is under motion.

• Nernst potential: It is the potential of the solid surface itself owing to

the presence of potential determining ions.
• Nernst potential or electro thermodynamic potential is defined as the
difference in potential between the actual surface and the
electroneutral region of the solution.
5
 Factors affecting zeta potential
1. pH : In aqueous media, the pH of the
sample is one of the most important
factors that affects its zeta potential.
zeta potential versus pH curve will be
positive at low pH and negative at high
pH. There may be a point where the
plot passes through zero zeta potential.
This point is called isoelectric point and
is very important from a practical
consideration.
 Conti...

2. Thickness of double layer: The thickness of the double layer

depends upon the concentration of ions in solution and can be
calculated from the ionic strength of the medium.

• The higher the ionic strength, the more compressed the double layer
becomes. The valency of the ions will also influence double layer
thickness.
 Zeta Potential
Measurement
• Zeta potential is not directly measurable, it can be calculated using
theoretical models like electrokinetic phenomena and electroacoustic
phenomena.
1. Electrokinetic Phenomena:
a. Electrophoresis:
The movement of charged particle relative to the liquid it is suspended
in under the influence of an electric field.
Conti...

• Zeta potential of dispersion is measured by applying an electric field

across the dispersion. Particles within the dispersion with a zeta
potential will migrate towards the electrode of opposite charge with a
velocity proportional to the magnitude of the zeta potential.

• The velocity of a particle in a unit electric field is referred to as its

electrophoretic mobility. Zeta potential is related to the
electrophoretic mobility by the Henry equation
 Henry
equation
UE = 2 ε z f(κa)/3η

Where:
UE = electrophoretic mobility,
z = zeta potential,
ε = dielectric constant, η =
viscosity
f(κa) = Henry’s function.
 Instrumentation
1. LASER

2. Cell

3. Detector

4. Digital signal Processor

5. Attenuator
1. Light Amplification by Stimulated Emission Radiation ( LASER ):

a. 632.8 nm Blue colour sample

b. 532 nm Red colour sample
 Zeta potential
Cell
• a) Folded Capillary cell: (DTS1060)

• solvent : water / alcohol

• sample volume : 0.75 mL.

Body of cell : Polycarbonate

Electrodes : Gold plated copper
b) Universal Dip cell (ZEN1002):

Solvent: : Water / Alcohol

Sample Volume : approximately 0.7mL

3. Detector :
Avalanche Photodiode
 DLVO
Theory
• The scientists Derjaguin, Landau, Verwey and Overbeek developed a theory in
the 1940s which dealt with the stability of colloidal systems.

• DVLO theory suggests that, the stability of a colloidal system is determined by

the sum of the Vander Waals attractive (VA) and electrical double layer repulsive
(VR) forces that exist between particles as they approach each other due to the
Brownian motion they are undergoing.

• The Vander waal forces depend on chemical nature and size of particle. The
electrostatic repulsive forces depend on density, surface charge and thickness of
double layer.
 Methods for stabilizing
colloids
Physical Stability can be achieved by maintaining the particle in
Brownian motion
a) Provide Electric charge on surface of dispersed particle:
The like charge on the particles will prevent these coming closer
together and thus maintaining a Brownian motion
Conti...
b) Maintain solvent sheath around the particle:
The solvent layer prevent the particle coming closer and also
maintain Brownian motion
 Applications

• Flocculate ( stick together )

• Suspension

• Emulsion

• Ceramics

• Waste water
 Conclusion
• Zeta potential has long been recognized as excellent tool for
characterizing colloidal system.
• In recent years the concept of zeta potential has been applied to are
as beyond classical colloidal sciences and industrial process.
• The expanding role of zeta potential in pharmaceutical sciences is
attributable to the advance in modern instrument of zeta potential
measurement, the rapid development of colloidal drug delivery
system and emphasis on interdisciplinary basic research.
Heater
 Detectable Phenomenon
Stimulus Quantity
Acoustic Wave (amplitude, phase, polarization), Spectrum, Wave
Velocity
Biological & Chemical Fluid Concentrations (Gas or Liquid)

Electric Charge, Voltage, Current, Electric Field (amplitude,

phase,
polarization), Conductivity, Permittivity

Magnetic Magnetic Field (amplitude, phase, polarization), Flux,

Permeability

Optical Refractive Index, Reflectivity, Absorption

Thermal Temperature, Flux, Specific Heat, Thermal Conductivity

Mechanical Position, Velocity, Acceleration, Force, Strain, Stress,

Pressure, Torque
 Important specifications for sensors

• Sensitivity, • Linearity

• Range, • Interchangeability, long-term

• Accuracy, stability,

• Precision/Repeatability • Response and recovery time,

• Offset, • Resistance to chemical and

physical contaminants,
• Resolution,
• Size, packaging and cost
effectiveness.
The sensitivity of the sensor is defined as the slope of
the output characteristic curve or, more generally, the
minimum input of physical parameter that will create
a detectable output change.
In some sensors, the sensitivity is defined as the
input parameter change required to produce a
standardized output change. In others, it is defined as
an output voltage change for a given change in input
parameter. For example, a typical blood pressure
transducer may have a sensitivity rating of 10
mV/V/mm Hg; that is, there will be a 10-mV output
voltage for each volt of excitation potential and each
mm Hg of applied pressure
•The range of the sensor is the maximum and minimum
values of applied parameter that can be measured.

•The accuracy of the sensor is the maximum difference

that will exist between the actual value (which must be
measured by a primary or good secondary standard) and
the indicated value at the output of the sensor. Again,
the accuracy can be expressed either as a percentage of
full scale or in absolute terms.

•The concept of precision refers to the degree of

reproducibility of a measurement.
•The offset error of a transducer is defined as the
output that will exist when it should be zero or,
alternatively, the difference between the actual output
value and the specified output value under some
particular set of conditions.

•The resolution specification is the smallest detectable

incremental change of input parameter that can be
detected in the output signal
The linearity of the transducer is an expression of the
extent to which the actual measured curve of a
sensor departs from the ideal curve. Linearity is often
specified in terms of percentage of nonlinearity,
which is defined as:
Nonliearity (%) =(Din(max)/INfs) x 100
where
Nonlinearity (%) is the percentage of nonlinearity
Din(max) is the maximum input deviation
INf.s. is the maximum, full-scale input
 Natural sensor
• Flowers open when the sun shines.
• Seeds react to warm weather.
• Plants grow in the opposite direction of gravity.
• Sniffer dog
 MAN Made SENSORS
• Solar cells and photographic film detect light.
• Microphones detect sound.
• Thermometers sense the change in heat or
temperature.
• Pressure gauges detect touch.
 Sensors and detectors
Sensor: Device to measure a particular substance quantitatively and
translate it into an output signal.

Detector: It detects the presence of a particular substance above a

threshold level.

• Measure quantity, send information

– Two types
• Some detect presence of a stimulus (Detector)
• Some detect quantity/value of a stimulus (Sensor)
• Can you give an example of a touch detector
and touch sensor?
– Answer: Detector tells you if it got pressed or not,
sensors tells you how hard it got pressed.
Temperature sensor
 Electrochemical sensor
Either a chemical reaction takes place or the charge transport is
modulated by the reaction

Oxidation - Reduction
Blood glucose monitors measure the amount of sugar in a sample
of blood using a complex chemical process. Within the test
strip the blood is mixed with glucose oxidase, which reacts with
the glucose in the blood sample to create gluconic acid.
Another chemical within the test strip, called ferricyanide,
then reacts with the gluconic acid to create ferrocyanide. The
electrode within the test strip then runs a current through the
blood sample and the ferrocyanide influences this current in
such a way that the concentration of blood glucose within the
sample can be accurately measured within a fair margin of
error.
 Direct Potentiometric pH Sensors
• The glass bulb creates an
electric ‘boundary’
potential across the • All modern pH meters
membrane w.r.t. the
internal Ag/AgCl record potential (mV) and
reference electrode. transform the voltage
RT  2.303RT caused by H+ into pH units
E cell  constant + ln a H  constant - pH unknown
F F • Standard buffers (4.0, 7.0,
10.0) are used for calibration
Where a H+ = activity of H+ • Automatically recognize
(= concentration in very standard buffers and adjust
dilute solutions). Slope for temperature
factor (2.303RT/F) is
temperature dependent,
pH meter must be
adjusted for changes in
temperature
 Example of other sensors
• Light Sensor
– photoconductor
• light  R

– photodiode
• light  I

– membrane pressure sensor

• resistive (pressure   R)
• capacitive (pressure  C)
 Ultrasonic Sensor
• Ultrasonic sensors are used
for position measurements
• Sound waves emitted are in
the range of 2-13 MHz
• Sound Navigation And
Ranging (SONAR)
• Radio Dection And Ranging
(RADAR) –
ELECTROMAGNETIC WAVES
!!
Choosing a Sensor
 Sensors: Some typical examples

Material Type Sensing Probing

action for mechanism

SnO2 Semiconductor Gases Resistivity

(NH3, H2S)
Yttria-doped Insulator Water ingress Ionic
thoria (YDT) in Na (FBR) conductivity
Calixarene Organic Cs-137 in Electro-
nuclear waste chemical
Ag@R6G Hybrid material Pb2+ in potable Optical
water
Conducting Organic Progesterone Conductivity
polymers (PANI) antibodies
 CO2 Gas Sensor
• CO2 sensor measures
gaseous CO2 levels in an
environment

• Measures CO2 levels in the

range of 0-5000 ppm

• Monitors how much

Infrared Source IR Detector
infrared radiation is
absorbed by CO2 molecules