Electrical materials

contents
Ohm’s law, resistivity,
classification –
metals
semiconductors (intrinsic & extrinsic-Si)
insulators
superconductors
Ohm’s Law and resistivity

One of the most important electrical characteristics of a solid material is the ease with which it transmits
an electric current. Ohm’s law relates the potential difference, V (in volts ), with the electrical resistance,
R (in ohms and the electrical current, I (in amp ). as follows:
1

This law is applicable to most but not all materials. The resistance R is the resistance of the material
through which the current is passing. The value of R is influenced by specimen configuration (size,
shape); materials properties; and for many materials is independent of current.

where l is the length (cm) of the resistor, A is the cross-sectional area (cm2) of the resistor. The ρ is the
resistivity or Electrical resistivity ([Link] or Ω.cm). From the expression for Ohm’s law and Eq. (2)
Factors affecting resistivity:
(a)Temperature
(b)Alloying
(c)Mechanical stress
(d)Age Hardening
(e)Cold Working
Classification
Energy Band
Theory:-
In a single isolated atom, the electrons in each orbit have definite energy associated
with it. But in case of solids all the atoms are close to each other, so the energy levels of
outermost orbit electrons are affected by the neighboring atoms. When two single or
isolated atoms are brought close to each other then the outermost orbit electrons of
two atoms interact or shared with each other. i.e., the electrons in the outermost orbit
of one atom experience a attractive force from the nearest or neighboring atomic
nucleus. Due to this the energies of the electrons will not be in same level, the
energy levels of electrons are changed to a value which is higher or lower than that of
the original energy level of the electron.
The electrons in same orbit exhibits different energy levels. The grouping of this
different energy levels is called energy band.
However, the energy levels of inner orbit electrons are not much affected by the
presence of neighboring atoms.
Important Energy Bands in Solids:
• There are number of energy bands in solids but three of them are very
important. These three energy bands are important to
understand the behavior of solids. These energy bands are
• Valence band
• Conduction band
• Forbidden band or forbidden gap
• Valence band
The energy band which is formed by grouping the range of energy levels of the valence
electrons or outermost orbit electrons is called as valence band. Valence band is present below the
conduction band as shown in figure below. Electrons in the valence band have lower energy than the
electrons in conduction band. The electrons present in the valence band are loosely bound to the
nucleus of atom.
• Conduction band
The energy band which is formed by grouping the range of energy levels of the free
electrons is called as conduction band. Generally, the conduction band is empty but when external
energy is applied the electrons in the valence band jumps in to the conduction band and becomes free
electrons. Electrons in the conduction band have higher energy than the electrons in valence band. The
conduction band electrons are not bound to the nucleus of atom.
• Forbidden gap
The energy gap which is present between the valence band and conduction band by
separating these two energy bands is called as forbidden band or forbidden gap.
Classification of Conductors, Semiconductors and Insulators
on the basis of Energy Band Diagram:-

15eV
[Link]:-
In conductors , conduction band is overlapped with valence band. So , large number
of electrons can jump from valence band to conduction band with the application of
small potential difference. The energy band diagram is shown in the figure above.
2. Semiconductors:-
In these materials , valence band is full of electrons while conduction band is empty.
In this case, energy gap is very small (1 eV).With the application of small potential
difference, electrons can jump from valence band to conduction band. The
semiconductor behaves as an insulator at room temperature or low temperature. As
the temperature increases, more electrons pass through valence band to conduction
band resulting conductivity increases. Energy band diagram for semiconductor shown
above.
Insulators:-
In insulators , conduction band remain is empty, while valence band has
many electrons. The forbidden energy gap between valence band and
conduction band is quite large (15 eV). So it is not easy to conduct electric
current through them. The electrons of the valance band require very high
electric field in order to cross it and move in the conduction band.
The electrons of the valence band do not have enough energy to cross and
move towards conduction band therefore the conductivity of the insulator
is almost zero.
comparison between conductors, insulators, and semi-conductors
[Link] Conductor Insulator Semi-conductor
1 The materials which allow electrical The materials which does not allow The materials which allow electrical
current through them very easily are electrical current through them are known current partially through them are known
known as Conductors. as Insulators. as Semi-conductors.
2 There are more free electrons to jump There are no free electrons to jump from There are few free electrons to jump from
from one atom to another. one atom to another. one atom to another.
3 Good conductors of electricity. Bad conductors of electricity. Partial conductors of electricity.
4 The resistivity lies between 10-8 to 10-6 The resistivity lies between 1012 to 1018 The resistivity lies between 100 to 102
ohm-m. ohm-m. ohm-m.
5 Electrical conductivity is very high. Electrical conductivity is negligible. Electrical conductivity is very less.
6 Number of valence electrons are less than Number of valence electrons are more Number of valence electrons are equal to
four. than four. four.
7 No forbidden gap between valence band Wider forbidden gap between valence Narrow forbidden gap between valence
and conduction band band and conduction band band and conduction band
(i.e., EG = 0 ev) (i.e., EG >5 ev) (i.e., EG >5 ev)
8 Very less energy is required for electrons Very high energy is required for electrons High energy is required for electrons to
to pass from valence band to conduction to pass from valence band to conduction pass from valence band to conduction
band. band. band.
9 They have positive temperature co- They have negative temperature co- They have negative temperature co-
efficient of resistance efficient of resistance efficient of resistance
10 Examples are Copper, Aluminium, Examples are Paper, Wood, Glass, Plastics, Examples are Germanium, Silicon,
Tungsten, Silver, etc. etc. Selenium, Carbon, etc.
Conducting materials – metals – low resistivity materials :
Material having low resistivity or high conductivity are very useful for manufacturing
electrical engineering machines or equipment’s. These material used as conductors for
all kind of winding required in electrical machines, apparatus and devices. These material
are also used as conductor in transmission and distribution of electrical energy.

Required Properties in Low Resistivity or High Conductivity Conducting Material

Highest possible conductivity (ideally zero).

Least possible temperature coefficient of resistance (ideally zero).
High melting point.
High mechanical strength.
High ductility, so that can be drawn in the form of wire easily.
High corrosion resistance (free from oxidation).
Solder ability, so that can be soldered easily to join the conductors.
Low cost.
Long life or durable.
High flexibility.
The above required properties varies with the purpose for which material is being used. Any
impurity whether metallic or non metallic increase the resistivity of metals. Even an impurity of
low resistivity will increase the resistivity of metal. The reason behind this is that the addition of
slight impurity creates imperfections in the crystal lattice which disturb the flow of electrons
through metals.

Some of low resistivity or high conductivity materials and their resistivity with temperature
coefficient of resistance are given in table below:-

Temperature
Sl No. Metals Resistivity (µΩ -cm) Coefficients of Resistance (/ 0C)

1
Silver 1.58 0.0038
2
Copper 1.68 0.00386
3
Gold 2.21 0.0034
4
Aluminium 2.65 0.00429
Copper (Cu)
The extensively used, high conductivity material as conductor for electrical machines or equipment, is
copper. Malleability, weld ability and solder ability are most important properties of copper. Copper in
pure form is having good conductivity. But the conductivity of standard grade copper is reduced due
presence of impurities.
Properties:
1. Resistivity : 1.68 µΩ -cm
2. Temperature coefficient of resistance at 20oC: 0.00386 /oC
3. Melting point: 1085oC
4. Specific gravity: 8.96gm /cm3
Application
(1) Hard Drawn Copper:- It is used for high voltage underground cable, bus bars and conductors
because of its high mechanical strength.
(2) Annealed Copper:- It is soft Copper. It is used for insulated conductor in low voltage cables,
winding wires for electrical machines and transformers, flexible wires and in making coils for any
purpose.
Aluminium is an element which is a silver-white, light weight, soft, non-magnetic and ductile metal. Aluminium is the third most
abundant element (after oxygen and silicon) and most abundant metal found in earth’s crust. The main ore of aluminium is
bauxite. Aluminium is having low density, high ductility, good corrosion resistance and good conductivity, which makes it
suitable to use as electric conductor for transmission and distribution of electricity.
Properties:
1. Resistivity: 2.65 µΩ -cm
2. Temperature coefficient of resistance at 20oC: 0.00429 /oC
3. Melting point: 660oC
4. Specific gravity: 2.70 gm /cm3

Aluminium Conductor Steel Reinforced - It consists of a central core of steel wires surrounded by layers of
aluminum wires
 Semiconductors

▪ A semiconductor is a substance, usually a solid chemical element or compound that

can conduct electricity under some conditions but not others, making it a good medium
for the control of electrical current.
▪ It has almost filled valence band, empty conduction band and very narrow energy gap i.e.,
of the order of 1 eV. Energy gap of Silicon (Si) and Germanium (Ge) are 1.0 and 0.7 eV
respectively. Consequently Si and Ge are semiconductors.

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 Effect of temperature on conductivity of semiconductors:
▪ At 0 K electrons freeze at valence band and hence all semiconductors are insulators.
▪ Electrical conductivity of a semiconductor material increases with increasing temperature
as resistivity decreases.
▪ At higher temperature transition from the valence band to the conduction band gets
facilitated ⇒ higher conductivity or lower resistivity.

Temperatur
15
e
Types of semiconductors:

16
 Intrinsic Semiconductor
▪ Intrinsic semiconductor material is chemically very pure and possesses poor conductivity.
▪ It has equal numbers of negative carriers (electrons) and positive carriers (holes)

Absence of Presence of
electrical field electrical field

17
 Extrinsic Semiconductor.
▪ Extrinsic semiconductor is an improved intrinsic semiconductor with a small amount
of impurities added by a process, known as doping, which alters the electrical
properties of the semiconductor and improves its conductivity.
▪ Introducing impurities into the semiconductor materials (doping process) can control
their conductivity.
▪ Doping process produces two groups of semiconductors:
• The negative charge conductor (n-type)
• the positive charge conductor (p-type)
▪ Semiconductors are available as either elements or compounds.
▪ Silicon and Germanium are the most common elemental semiconductors.
▪ Compound Semiconductors include InSb, InAs, GaP, GaSb, GaAs, SiC, and GaN.

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 n-type Semiconductor
▪ An n-type semiconductor is an intrinsic semiconductor doped with pentavalent
impurity, such as, P, As, Sb, etc.
▪ If a small amount of phosphorus is added to a pure silicon crystal, one of the
valence electrons of phosphorus becomes free to move around (free electron) as
a surplus electron.

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 p-type Semiconductor
▪ An p-type semiconductor is an intrinsic semiconductor doped with trivalent
impurity, such as, B, Al, In, etc.
▪ If a small amount of boron is doped to a single crystal of silicon, valence
electrons will be insufficient at one position to bond silicon and boron, resulting
in holes that lack electrons.

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comparisons between N and P type semiconductors

[Link] N-Type Semiconductor P-Type Semiconductor

1 Pentavalent impurity is added to pure Trivalent impurity is added to pure
semiconductor to form N-Type semiconductor. semiconductor to form P-Type semiconductor.
2 The impurity atom has one extra electron i.e., The impurity atom has one short fall electron
five. i.e., three.
3 The doping agent is called donor. The doping agent is called acceptor.
4 Large number electrons are produced by doping. Large number holes are produced by doping.
5 In this electrons are the majority carriers and In this holes are the majority carriers and
holes are minority carriers. electrons are minority carriers.
6 Current conduction is predominantly by elctrons. Current conduction is predominantly by holes.
7 The impurity atom becomes positively ionized The impurity atom becomes negatively ionized
by donating an electron. by accepting an electron.
8 Examples of donors: Arsenic, Antimony, Examples of acceptors; Boron, Gallium, Indium,
Bismuth, Phosphorous, etc. Aluminium, etc.

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∙ Applications
∙ Temperature sensors are made with semiconductor devices.
∙ They are used in 3D printing machines
∙ Used in microchips and self-driving cars
∙ Used in calculators, solar plates, computers and other electronic devices.

∙ Transistor and MOSFET(metal-oxide-semiconductor field-effect transistor) used as a

switch in Electrical Circuits are manufactured using the semiconductors.

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 Insulators
In insulators , conduction band remain is empty, while valence band has many
electrons. The forbidden energy gap between valence band and conduction band is
quite large (15 eV). So it is not easy to conduct electric current through them. The
electrons of the valance band require very high electric field in order to cross it and
move in the conduction band. The electrons of the valance band do not have enough
energy to cross and move towards conduction band therefore the conductivity of the
insulator is almost zero.

These materials which have very high resistivity i.e. offers a very high resistance to the
flow of electric current. Insulating materials play
an important part in various electrical and electronic circuits. In
domestic wiring insulating material protect us from shock and prevent leakage current
 Examples
Asbestos and asbestos products

Glass

Insulating resins and their products

Laminates, adhesives, enamels

superconductors
Superconductivity was discovered by Dutch Physicist Heike Kamerlingh Onnes
in 1911 in Leiden. He was awarded the Nobel Prize in Physics in 1913 for his
low-temperature research. Some materials when they are cooled, below
certain temperature their resistivity get abolished means they exhibit the
infinite conductivity.
The temperature at which the metals change from normal conducting state to
superconducting state, is called critical temperature/transition temperature.
An example of superconductors, is Mercury. It becomes superconductor at 4k.
In superconducting state the materials expel the magnetic field.
Meissner effect

Walther Meissner and

Robert Ochsenfeld in
1933 by measuring the
magnetic field distribution
outside superconducting tin and
lead samples.

A superconductor with little

or no magnetic field within it is
said to be in the Meissner state.
Application

Transportation:
• Maglev Trains: Superconducting magnets enable magnetic levitation, allowing
trains to float above the tracks and travel at high speeds with minimal friction and
energy loss.
Medical Imaging:
• Superconducting magnets in MRI (Magnetic Resonance Imaging) machines
create strong, stable magnetic fields for high-resolution medical imaging.
Power Transmission and Energy Storage:
• Superconducting cables can transmit electricity over long distances with
minimal energy loss, offering significant efficiency gains.
Computing:
• Superconducting circuits are used in the development of quantum computers,
offering potential for faster and more powerful computation
 Magnetic Materials

, Magnetic: para, dia, ferro & anti ferro magnetism, applications in storage devices
MAGNETIC DIPOLE:

The ends of a magnet are where the magnetic effect is the strongest.
These are called “poles.” Each magnet has 2 poles – 1 north, 1 south.

Any two opposite poles separated by a finite distance constitute a

magnetic dipole.
 Response of materails to a magnetic field can be
different and studied in magnetism.

Magnetic field:
The space surrounding the magnet upto which
its influence felt is known as magnetic field.

Michael Faraday
 • The magnetic behavior of materials can be traced to the
structure of atoms.
• Bohr magneton - The strength of a magnetic moment of an
electron (μB) due to electron spin.

Origin of magnetic dipoles: (a) The spin of the electron produces

a magnetic field with a direction dependent on the quantum
number ms. (b) Electrons orbiting around the nucleus create a
magnetic field around the atom.
Origin of magnetic moment
1. Orbital Motion - Orbital magnetic moment
2. Spin motion – Spin magnetic moment
• Magnetic moment (µBM)
• μ eff = μs.o = 2√S(S+1) = √n(n+2) BM
• n number of un paired electrons
• s.o- Spin only value

• If there is a possibility for contribution from the orbital angular

momentum,then
• μ = √L(L+1) + 4S(S+1)
 Magnetization,
Permeability, and the Magnetic Field

□ Magnetic permeability - The ratio between inductance and

magnetic field. It is a measure of the ease with which
magnetic flux lines can ‘‘flow’’ through a material.
□ Magnetization (M) - The total magnetic moment per unit
volume.
□ Magnetic susceptibility (𝝌,)- The ratio between magnetization
and the applied field. 𝝌 = M /H

□ H is magnetic field
 Permeability: ( µ )
The Magnetic induction B is proportional to the applied Magnetic
field intensity H.

Where µ permeability of a medium

 Relative permeability µr
The ratio of permeability of medium to the permeability of free
space is called relative permeability µr of the solid.
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

A current passing through a coil sets up a magnetic field H with

a flux density B. The flux density is higher when a magnetic
core is placed within the coil.
 Magnetization
• Magnetization refers to the process of converting a non-magnetic
material into a Magnetic material.
• The intensity of Magnetization is directly related to the applied
field H.
✔ Every substance is formed from an assembly of atoms which can be
either non-magnetic or magnetic.

The magnetic materials are classified into five groups depending on

their response to the magnetic field.

1. Diamagnetic Materials
2. Paramagnetic Materials
3. Ferromagnetic Materials
4. Antiferromagnetic Materials
5. Ferrimagnetic Materials
 DIAMAGNETISM

✔ Diamagnetism characterizes the substances that have only non-

magnetic atoms. These don’t have unpaired electrons.

✔ Origin:
• Diamagnetism is associated with orbital motion of filled (
paired) electrons .

• Due to different orientations of various orbits of an atom, the

net magnetic moment is zero in diamagnetic materials.

• When an external field is applied the motion of electrons in

their orbits changes resulting in induced magnetic moment in a
direction opposite to the direction of applied field.
✔ The magnetization induced by the applied magnetic field is very
weak and the magnetic lines of force are repelled.

✔ This magnetism also exists in substances with magnetic atoms, but

very weak and completely masked by the contribution of magnetic
atoms.

✔ Relative permeability is slightly less than unity.

✔ The magnetic susceptibility is independent of applied magnetic

field strength.
 Magnitude of Temperature dependence Examples
susceptibility

Small & negative Independent Organic materials,

light elements
Intermediate & Below 20K varies with field and Alkali earhs,
negative temperature Bismuth

Large & Negative Exists only below critical Superconducting

temperature (Meissner effect) materials
 PARAMAGNETISM

✔ Paramagnetic materials consists of magnetic atoms that posses

unpaired electrons oriented at random on different atoms.

✔ Origin
These unpaired spins may interact with each other leading to
cooperartive phenomenon like ferromagnetism
▪ When the shells are unfilled there is net magnetic moment.
▪ In the absence of the external field the net moments of the
atoms are arranged in random directions because of thermal
fluctuations. Hence there is no magnetization.
▪ When external magnetic field is applied, there is tendency for the
dipoles to align with the field giving rise to an induced positive
dipole moment.
▪ The induced magnetism is the source for paramagnetic behaviour.
✔ Paramagnetic susceptibility is small and positive and is
independent of applied field strength.
✔ Spin alignment is random.

Magnitude of Temperature dependence Examples

susceptibility

Small & positive Dependence Alkali metals,

transition
Curie law C- Curie
metals, rare
earths
constant
 FERROMAGNETISM

⮚ Even in the absence of external applied field, some substances

exhibit strong magnetization due to unpaired electrons interacting
cooperatively.

⮚ This is due to a special form of interaction called exchange coupling

between adjacent atoms that results in spontaneous magnetization
of the substance.

⮚ When placed inside a magnetic field, it attracts the magnetic lines

of force very strongly.

⮚ Each ferromagnetic material has a characteristic temperature

called the ferromagnetic Curie temperature θf. Below this
temperature the spontaneous magnetization exists.
✔ Spin alignment is parallel.

✔ Ferromagnetic materials exhibit Hysteresis.

✔ They Consists of a number of small regions which are called domains.

Magnitude of Temperature dependence Examples

susceptibility

Very large & Fe, Co, Ni, Gd

positive
For T>θf paramagnetic behavior
For T<θf ferromagnetic behavior
 ANTI-FERROMAGNETISM

✔ Antiferromagnetism macroscopically similar to paramagnetism, is

a weak form of magnetism.

✔ In certain materials when the distance between the interacting

atoms is small the exchange forces produce a tendency for
antiparallel alignment of electron spins of neighboring atoms.

✔ The magnetic susceptibility increase with the increase of

temperature and reaches maximum at a certain temperature.
This temperature is known as Neel temperature (TN). Above this
temperature the susceptibility again decreases.
Spins are aligned antiparallel

Magnitude of Temperature dependence Examples

susceptibility

small & positive when T>TN NiO, MnO

when T<TN
 FERRIMAGNETISM

✔ This is a special case of antiferromagnetism.

✔ The net magnetization of magnetic sublattices is not zero, since

antiparallel moments are of different magnitudes.

✔ Hence ferrimagnetic materials possesses a net magnetic moment.

✔ This moment disappears above a Curie temperature analogous to the

Neel temperature.

✔ Above TC, thermal energy randomizes the individual magnetic

moments and the material becomes paramagnetic.
✔ Ferrimagnetic domains become magnetic bubbles to act as memory
elements.
✔ Spin alignment is antiparallel of different magnitudes.

Magnitude of Temperature dependence Examples

susceptibility

Very large & when T>TN Ferrites

positive
when T<TN behaves as paramagnetic
material
TC and TN values of some elements
Magnetic susceptibility vs T plots
Inverse susceptibility vs T for different behaviour
Ferromagnetism (FM)

❑ Ferromagnetism, Antiferromagnetism and Ferrimagnetism involve no new

types of magnetic moments; but involve the way the magnetic moments are
coupled (arranged).

❑ Two important ways of understanding ferromagnetism in metals are:

(i) assuming that moments are localized to atoms,
(ii) using the band structure of metals (giving rise to itinerant electrons).
The former is conceptually easier and has been assumed in the 'molecular
field theory' and the Heisenberg's approach. It should be noted right at the
outset that even in metals (e.g. Fe), most of the electrons behave as if they
are 'localized' and the number of itinerant electrons could be a small number.
⮚ In Fe there are 8 valence electrons which occupy the (3d + 4s) bands. Out
of these 8 electrons only ~0.95 in the 4s band are 'truly' free/itinerant and
remaining ~7.05 are occupy the 'localized' 3d band.
 Mechanism of ferro and antiferro magntic ordering – super exchange

• In paramagnetic state individual moments of ions with unpaired electrons( magnetic dipoles)
are oriented at random. On application of magnetic field partial alignment occurs.

• In ferro and anti ferro state magnetic diploes ( unpaired electrons) align spontaneously due
to the positive energy of interaction between the spins. The origin of this cooperative
interaction is quantum mechanical.
• One mechanism that leads to antiferromagnetism in NiO is through super exchange ( refer
fig next slide)
• The singly occupied electrons in dz2 and dx2-y2 orbitals of a Ni2+ ion couples
antiferromagnetically with that on neighbouring Ni2+ through
• the p orbital of the oxide ion. This is the superexchange
 Hysteresis

The striking property of Ferro Magnetic materials is the relation

between Magnetization and the strength of Magnetic field. This
property is called Hysteresis.

Ferromagnets have a domain structure and within each domain the spins are
Parallel . In the saturation magnetization conditions different domains have
Same orientation.
 Saturation
P Magnetiza
Ms tion
Residual
Magnetiza Mr Q
tion

-Hs R
Hc o Hs
Coerci
vity
Hard magnetic materials –
Large hysteresis loop ex
Alnico alloy
S
-Ms Soft magnetic materials – small
Ferro Magnetic hysterisis loop ex ferrous nickel
Material Alloy
• If we start with no Magnetized specimen
(M= 0) with the increasing values of magnetizing field H.

• The Magnetization of the specimen increases from zero to higher

values and attains its maximum value at a point P, at this point the
Magnetization referred as Saturation Magnetization.

• When we increase Magnetic field H there is no further increment in

Magnetic moment.

• When we decrease Magnetic field H to Zero, the Magnetization M

attains point Q.

• At this point Magnetization referred as residual Magnetization Mr.

• Further if we increase the Magnetic field from zero to negative values, the
Magnetization of material becomes zero at a point R, at that point the Magnetic field
Hc is referred as Coercivity of the specimen.

• If we increase Magnetic field H in reverse direction Magnetization of material reaches

its peak value at a points S.

• On reversing the polarities of Magnetic field and increasing its strength the
Magnetization slowly decreases first to residual value then to zero and finally
increases to saturation state and touches the original saturation curve.

• The area of loop indicates the amount of energy wasted in one cycle of operation.
 Applications of Magnetic Materials

□ Soft Magnetic Materials - Ferromagnetic materials are often

used to enhance the magnetic flux density (B) produced when
an electric current is passed through the material.
Applications include cores for electromagnets, electric
motors, transformers, generators, and other electrical
equipment.
□ Data Storage Materials - Magnetic materials are used for
data storage.
□ Permanent Magnets - Magnetic materials are used to make
strong permanent magnets
Soft magnetic materials have low coercivity.
Magnetic oxides have significant applications in memory storage, particularly in non-volatile
memory technologies like hard disk drives (HDDs) and magnetic random access memory
(MRAM). Their ability to retain magnetization even when power is removed makes them suitable
for persistent data storage.

MgFe2O4 ferrites are used in transformer core, magnetic recording and

Information storage devices.

For cassettes, tapes and floppy disks, sound data are recorded as variations in the amount of
magnetisation on the surface of a recording medium, which is usually either a composite consisting of a
polymer film embedded with tiny particles of magnetic CrO2 or γ-Fe2O3, or a thin film of magnetic
material deposited on a substrate. Each particle or domain can be magnetised in either of two
directions, representing 0 or 1. The read–write recording head is a tiny electromagnet of a soft
material, such as MnZn ferrite,
Schematic- next slide

FeCr multilayers which exhibit Giant magneto resistance is used in high density Hard drives. Mgneto
resistance is change in resistance when there is an applied Magnetic field.
For high density hard disk, the material used is SmCo5 alloy.
 Functional Materials

Nanomaterials: introduction, top-down and

bottom-up approaches for synthesis -
bulk vs nano (gold), quantum dots

70
 Nanomaterials: Introduction
❖ Nanomaterials are cornerstones of nanoscience and nanotechnology.

❖ Nanostructure science and technology is a broad and interdisciplinary area of research

and development activity that has been growing explosively worldwide in the past few
years.

❖ It has the potential for revolutionizing the ways in which materials and products are
created and the range and nature of functionalities that can be accessed.

❖ It is already having a significant commercial impact, which will assuredly increase in the
future.

71
 What are nanomaterials?
❖ Nanoscale materials are defined as a set of substances where at least one dimension is
less than approximately 100 nanometers.

❖ A nanometer is one millionth of a millimeter - approximately 100,000 times smaller than

the diameter of a human hair.

❖ Nanomaterials are of interest because at this scale unique optical, magnetic, electrical,
and other properties emerge.

❖ These emergent properties have the potential for great impacts in electronics, medicine,
and other fields.

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 Nano is a millionth of a millimeter or a billionth of a meter, i.e. 1 nm = 10-9 m.

Atom is about 0.1 nanometer - 10 atoms side by side make up 1 nm.

Human hair:
50,000–100,000 nm in diameter.

73
 Where are nanomaterials found?
• Some nanomaterials occur naturally, but of particular interest are engineered
nanomaterials (EN), which are designed for, and already being used in many commercial
products and processes.
• They can be found in such things as sunscreens, cosmetics, sporting goods, stain
resistant clothing, tires, electronics, as well as many other everyday items, and are used
in medicine for purposes of diagnosis, imaging and drug delivery.
• Nanocoatings and nanocomposites are finding uses in diverse consumer products, such
as windows, sports equipment, bicycles and automobiles
• There are novel UV-blocking coatings on glass bottles which protect beverages from
damage by sunlight, and longer-lasting tennis balls using butyl-rubber/nano-clay
composites.
• Nanoscale titanium dioxide, for instance, is finding applications in cosmetics, sun-block
creams and self-cleaning windows, and nanoscale silica is being used as filler in a range
of products, including cosmetics and dental fillings
74
 Where do we use?
Mechanical Biotechnology
Engineering
/ Robotics

Transportatio
Advance n
Materials
NANOMATERIALS OR
& Textiles
NANOTECHNOLOGY

Energy & National

Environment Security
&
Defense
Aerospace Medicine
Food and
/ Health
Agriculture

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Classification: based on the number of free dimensions
0D nanomaterial: all three dimensions are in the nanoscale.
(Nanoparticles, Colloids, Quantum dots)
1D nanomaterial: one dimension beyond the nanoscale and two other dimensions in the nanoscale.
(Nanowires, Nanorods, Nanotubes & Biopolymers).
2D nanomaterial: any two dimensions can be outside of the nanoscale and one dimension in the
nanoscale. (Plate-like shapes - nanolayers, surface coatings and thin films).
3D nanomaterial: all three dimensions can be outside of the nanoscale. Made of a nanomaterials.
(nanoparticle dispersions, nanowire/ nanotube bundles & multiple nanolayers).

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Categories of Nanomaterials

77
Why so much interest in nanomaterials?

These materials have created a high interest in recent years by virtue of their
unusual mechanical, electrical, optical and magnetic properties. Some examples
are given below:

Nanophase ceramics are of particular interest because they are more ductile at
elevated temperatures as compared to the coarse-grained ceramics.

Nanostructured metal-oxide (MnO2) finds application for rechargeable batteries for

cars or consumer goods

Very small particles have special atomic structures with discrete electronic states,
which give rise to special properties in addition to the superparamagnetism
behaviour

Bulk gold Vs Nano gold (In detail)

78
Bulk vs Nano (gold)

79
 Size and shape dependent colors of Au and Ag nanoparticles
Gold NPs in Glass Silver NPs in Glass
25 nm
100 nm
Sphere
Sphere
reflected
reflected

50 nm 40 nm
Sphere Sphere
reflected reflected

100 nm
100 nm prism
Sphere reflected
reflected

80
80
 Size and shape dependent colors of Au and Ag nanoparticles

Note: nanomaterials scatter visible light rather than

absorb
⮚ Distance between particles also effects colour

81
81
 Gold : Bulk vs. Nano
Bulk Gold Nano Gold
1 Lustrous–they have a shiny surface Are never gold in colour but found in a
when polished range of colours
2 Malleable–they can be hammered, bent Size & Shape of the nanoparticles
or rolled into any desired shape determines the colour
3 Ductile–they can be drawn out into wires For example, Gold particles in glass
25 nm > red reflected
50 nm > green reflected
100 nm > orange reflected
4 Is metallic, with a yellow colour when in Are not “metals” but are semiconductors
a mass (Band gap energy = 3.4 eV)
5 Good conductors of heat and electricity Are very good catalysts
6 Generally have high densities
7 Have high melting point (~1080oC) Melts at relatively low temp (~940º C)
8 Are often hard and tough with high
tensile strength
9 Having high resistance to the stresses
of being stretched or drawn out
10 Not easily breakable
11 Inert-unaffected by air & most reagents
82
 Why Nanomaterials are different
The two main reasons why materials at the nano scale can have different properties are
increased relative surface area and new quantum effects.

• Increase of Surface area/Volume

ratio

Area = 6 x 1cm2 = 6 cm2 Area= 6 x (1/2cm)2 x 8 =12 cm2

Better
catalytic
efficiency
Area= 6 x (1/3cm)2 x 27 =18 cm2

83
• Small size effect (Quantum size effect)
✔ The particles are so small that electrons are not free to move about as in bulk gold. As the
movement is restricted, the particles react differently with light
Tunable fluorescent
emission
✔ Electronic states are quite different from bulk. Discrete energy levels; Quantum confinement
effect occurs, increases the energy gap between energy levels leading to metal to
semiconductor to insulator transition.
Quantum confinement refers to the spatial
confinement of electrons in a nanomaterial
rather than the free existence within the bulk
materials

Electron hole pairs become spatially confined

when the diameter of the particle approaches
the de Broglie wavelength of electrons in the
conduction band

The quantum confinement occurs when the

size of the particle is too small o be
comparable to the de Broglie wavelength of
the electron 84
• Decreased imperfections and defects: reason for changing electrical conductivity
than bulk matter. etc.

• This more structural perfection in the nanomaterials improves their mechanical

properties (increases mechanical strength e.g. hardness, toughness etc.).

• Increased paramagnetism and supermagnetism behaviour Magnetic Property

changes

• Due to smaller size, permeability through the biological membrane Increases

Biological
Property

85
 Top-down and bottom-up approaches
for synthesis
• Top-down
• Involves breaking down larger pieces of material to create nanostructures. This approach
is good for producing structures with long-range order and for making macroscopic
connections.

• Bottom-up
• Involves assembling single atoms and molecules into larger nanostructures. This approach
is best suited for assembly and establishing short-range order at nanoscale dimensions

• For example, in the top-down approach to produce nanosilver, a bulk piece of material is
mechanically ground. In the bottom-up approach, chemical and biological methods are
used to make nanostructures and nanoparticles.

86
 Bulk

Powder

(Clusters
)

87
Mechanical Milling
method
Mechanical milling is a cost-effective method for producing materials at the nanoscale level
from bulk materials.

Mechanical milling is an effective method for producing blends of different phases, and it is
helpful in the production of nanocomposites.

Mechanical milling is used to produce oxide- and carbide-strengthened aluminum alloys,

aluminum/nickel/magnesium/copper-based nanoalloys, and many other nanocomposite
materials

Ball-milled carbon nanomaterials are considered a novel class of nanomaterial, providing the
opportunity to satisfy environmental remediation, energy storage, and energy conversion
demands

88
Mechanical milling, also known as mechanical alloying or mechanochemical synthesis, is a
"top-down" method for producing nanomaterials by physically reducing the size of bulk
materials through grinding and impacting.

This technique involves using high-energy mills to repeatedly impact and deform powder
materials, leading to size reduction and the creation of new phases

To produce nonequilibrium structures including nanocrystalline, amorphous and

quasicrystalline materials

Powders diameters of about 50 µm with a number of hardened steel or tungsten carbide

(WC) coated balls in a sealed container which is shaken or violently agitated. The most
effective ratio for the ball to powder mass is 5 : 10.

Different millers are tumbler mills, attrition mills, shaker mills, vibratory mills, planetary mills
etc

Shaker mills (e.g. SPEX model 8000) uses small batches of powder (approximately 10 cm3
is sufficient 89
❖ Advantage: High production rates
❖ Disadvantages
⮚ Severe plastic deformation associated with mechanical attrition due to generation of
high temp in the interphase, 100 to 200 oC.
⮚ Difficulty in broken down to the required particle size
⮚ Contamination by the milling tools (Fe) and atmosphere (trace elements of O2, N2 in
rare gases) can be a problem (inert condition necessary like Glove Box)(Fe <1-2%
and Trace elements<300 ppm)
⮚ Protective coating to reduce milling tools contamination (MTC) increases cost of the
process
⮚ Working duration (>30 h) increases MTC (>10%)

90
91
 Schematic representation of the principle of mechanical milling
High-energy_ball_milling

WC coated
50 µm powder ball

Ball_mill

220px-8000M_Mixer_Mill_%28open%29_incl_accessories

92
 Sol-gel method (Bottom up approach)

❖ This method is used for the development of various kinds of high-quality metal-oxide-based
nanomaterials.

❖ This method is called a sol–gel method as during the synthesis of the metal-oxide
nanoparticles, the liquid precursor is transformed to a sol, and the sol is ultimately converted
into a network structure that is called a gel.

❖ Conventional precursors for the generation of nanomaterials using the sol–gel method are
metal alkoxides.

❖ The synthesis process of nanoparticles via the sol–gel method can be completed in several
steps.

❖ In the first step, the hydrolysis of the metal oxide takes place in water or with the assistance of
alcohol to form a sol.

93
In the next step, condensation takes place, resulting in an increase in the solvent viscosity to
form porous structures that are left to age.

During the condensation or polycondensation process, hydroxo- (M–OH–M) or oxo- (M–O–M)

bridges form, resulting in metal–hydroxo- or metal–oxo-polymer formation in solution.

During the aging process, polycondensation continues, with changes to the structure,
properties, and porosity. During aging, the porosity decreases, and the distance between the
colloidal particles increases.

After the aging process, drying takes place, in which water and organic solvents are removed
from the gel.

Lastly, calcination is performed to achieve nanoparticles.

94
95
96
❖ Advantages
• Synthesizing nonmetallic inorganic materials like glasses, glass ceramics or
ceramic materials at very low temperatures compared to melting glass or firing
ceramics
• Monosized nanoparticles possible by this bottom up approach.
❖ Disadvantages
• Controlling the growth of the particles and then stopping the newly formed
particles from agglomerating.
• Difficult to ensure complete reaction so that no
unwanted reactant is left on the product
• Completely removal of any growth aids
• Also production rates of nanopowders are very slow by this process

97
 Quantum Dots
• Quantum dots are semiconductor particles with typical diameter of 2–10 nm. They are so
named because, due to their nanoscale size, quantum effects play a significant part in
their light emitting properties.

• Quantum dots emit light via this mechanism: under external stimulus, some of the
electrons of the dot material absorb sufficient energy to escape their atomic orbit. This
creates a conductance region in which the electrons can move through the material,
effectively conducting electricity.

• As these electrons drop back into atomic orbit, energy is released in the form of light, the
color of which depends on the amount of energy released.

• Examples: cadmium selenide (CdSe), cadmium sulfide (CdS), and indium

phosphide (InP)

98
99
 QDs contain 100 to 1000 electrons and are 2 to 10 nanometers in diameter, or 10 to 50
atoms.

Changing the band gap of semiconductors is the most attractive due to fundamental and
technological importance.

Widely tunable bandgap semiconductor are considered materials for new generation flat
panel display photovoltaic, optoelectronic devices, lasers, sensors, photon bandgap
devices, etc.
Properties of QDs
• High extinction coefficient
• High electron mobility
• Bandwidth and position adjustment
• Solution Process capabilities 100
 The release of confinement energy is a key property of a
quantum dot, which explains the positive relationship between
the QD size and the frequency of the light it emits.

Unlike bulk semiconductors, which have continuous energy

levels within the bands, the quantum confinement effect
Schrödinger: creates a large band gap with observed discrete energy levels.
electrons in confined systems And because of this quantized band gap, a quantum dot can
occupy quantized energy levels emit light at a very constant wavelength, which can be fine-
tuned by changing the size of the quantum dots (or in other
words, changing the energy levels).
101
• Because of the dots’ small size, the amount of energy released is relatively consistent
from electron to electron, yielding emissions of a single color.
• The color is entirely dependent upon the size of the dot, with larger dots (e.g., 5-6 nm)
providing lower energy emissions (i.e., reds and oranges) and smaller dots (e.g., 2-3 nm)
providing higher energy emissions (i.e., blues and violets).
• This property is sometimes referred to as “quantum confinement,” indicating that
constraints at the atomic level are predominant.

Quantum dot emissions from violet to deep red

102
 Emission properties of Quantum Dots

1. Band gap decreases as the QDs size increases

2. Emission wavelength becomes red shifted with increase in size of QDs

103
 Synthetic Procedures of Quantum Dots
1. High temperature synthesis

2. Hydrothermal synthesis 4. Ultrasonication synthesis

3. Microwave synthesis
 Applications:
Displays:
Quantum dots are used in displays to create brighter, more vibrant colors, particularly in QD-
OLED TVs
Solar Cells:
Quantum dots can enhance the efficiency of solar cells by absorbing a wider range of light
wavelengths
Biomedical Imaging:
Their tunable emission makes them useful for imaging tissues and cells, aiding in
diagnostics and drug delivery.
Solid-State Lighting:
Quantum dots can be used to create more energy-efficient and colorful lighting solutions
Other applications
Quantum dots are also being explored for use in sensors, lasers, quantum computing, and
other areas of research.

105
 Quantum Dots and applications
Quantum dots (QDs) are semiconductor particles of few nanometers (<10
nm) in size, having optical and electronic properties that differ from larger
particles.

5 nm

Cancer cell imaging Metal ions sensing Light emitting diode

Liquid Coolants
 Liquid Coolants
• Types of coolants
• Thermal Conductivity
• Applications
 What are Coolants?
• Coolants are fluids that run across an engine to absorb the
heat and carry it to the radiator where it can be cooled and
recycled. Coolants, cool machinery that produces heat during
operation.
• Electronics, especially miniature electronics, require cooling
because the chips are highly power-dense, and they can
generate heat flux of up to 1000 W/cm2.
• High power density leads to an increase in heat generation,
which can bring down the performance of the engine/device.
 Coolants are Everywhere
• Automobiles
• HVAC systems
• Home air-conditioners
• Computers
• Supercomputers
• Data centers
• Miniature electronics
• Military devices
• Mobile devices
Examples of Cooling Systems

[Link]
used-liquid-cold-plates-electronics-cooling/
Thermal Conductivity
 Requirements for Coolants
• Thermophysical properties
– Thermal conductivity, specific heat, latent heat of vaporization, surface
tension, and viscosity
• Electrical conductivity
– Water and glycol-water are highly conductive and spills may damage the
electronics
– Non-aqueous coolants are preferred when electronics are involved
• Flammability
– Coolants for electronics must be non-flammable
– Any liquid that has a flash point of <93 °C is considered flammable
– Ethanol, methanol, and benzene are all flammable
– PFC and HFE are inflammable and suitable for cooling applications
 Requirements for Coolants
• Toxicity
– Coolant should be non-toxic as leakages may happen and
harm biological organisms
– Fluorocarbons and hydrofluoroether-based coolants have low
toxicity compared to ethylene glycol-based coolants
• Material Compatibility
– Wetted surface and the coolant must be compatible to minimize
corrosion
– Copper and aluminum are preferred materials to build devices
as they have high thermal conductivity and are compatible with
most coolants
 Requirements for Coolants
• Environmental Impact
– Coolant should how low global warming potential (GWP) and
ozone layer depletion potential (ODP)
– Perflouoro carbon based coolants have high GWP but zero
ODP
– Hydrofluoroether based coolants have low GWP and zero ODP
• Cost
– Coolants based on water are usually low-cost, but addition of
antifreee, glycols and anti-corrosion materials may increase the
cost
 Classification of Coolants
• Aqueous coolants
– Water has a good thermal conductivity, high specific heat, high
latent heat of vaporization, and low viscosity
– It is a low-risk coolant
– Water is compatible with most materials
– Freezing temperature of water makes it unsuitable in certain
conditions
– In such cases, additives such as glycol help lower the freezing
point
– Water – NaCl or water-CaCl2 have low FP
– Salt solutions are highly corrosive
 Classification of Coolants
• Deionized water
– Tap water contains minerals and pathogens
– Deionized water is less corrosive than tap water
– One should add corrosion inhibitors even to deionized water
because exposure to air can make it corrosive
– Common corrosion inhibitors are: phosphates, tolytriazole, and
2-ethyl hexanoic acid.
• Water-glycol solutions
– Water-ethylene glycol and water-propylene glycol have low
freezing point compared to water
 Classification of Coolants
• Water potassium formate/acetate solutions
– Less corrosive compared to water-NaCl or water-CaCl2
– Their low freezing point (-70 C) is ideal for many applications
– Food, beverage, chemical and pharmaceutical industries use
these solutions.
 Classification of Coolants
• Dielectric Coolants
– High electrical conductivity of water restricts direct usage in
contact with chips and circuits.
– Data centers use these coolants in immersion cooling or direct-
to-chip cooling
 Thermal Conductivity Measurements
The current methods developed for thermal conductivity
measurements are static methods and can be divided in
Steady State Methods and Transient State Methods to
avoid convective heat transfer in liquid.
Steady State Methods:
the parallel plane and coaxial cylinders methods
Transient State Methods: the transient hot wire, the
transient plane source theory, the temperature oscillation
method, the laser flash method and the 3ω method
 Thermal Conductivity Measurements

[Link]
• [Link]
systems/
• [Link]
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