UNIT-6 MODERN ENGINEERING MATERIALS

Introduction and basic properties of Nanomaterials and Superconductors.

Nanomaterials

 Nanomaterials: Nanomaterials can be defined as materials possessing, at minimum, one

external dimension measuring 1-100 nm.
 Nanotechnology: Nanotechnology is the science, engineering, and technology related to
the understanding and control of matter at the length scale of approximately 1 to 100
nanometers.
 A nanometer is one billionth of a meter (10-9 m). This is roughly ten times the size of an
individual atom.

TYPES OF NANOMATERIALS

 Materials that are Nano scale in zero dimension including carbon quantum dots (CQDs),
fullerenes, inorganic quantum dots (QDs), magnetic nanoparticles (MNPs), noble metal
nanoparticles.
 Materials that are Nano scale in one dimension are layers, such as a Thin films or
Surface coatings for example Graphene.
 Materials that are Nano Scale in two dimensions include Nano wires and Nano tubes,
for example carbon nano tubes.
 Materials that are Nano scale in three dimensions are particles for example precipitates,
colloids and quantum dots (Small particles of Semiconductor Materials)
Why the materials properties differ as size is reduced?

 The properties of Nano Materials are very much different from those at a larger scale.
 Two principal factors cause the properties of Nano Materials to differ significantly from
other materials.
1. Increased relative surface area.
2. Quantum confinement effect.
 These factors can change or enhance properties such as reactivity, strength and electrical
characteristics.

1. Increase in a Surface Area to Volume ratio

 Nano Materials have a relatively larger Surface area when compared to the same volume
or mass of the material produced in a larger form.
Let us consider a Sphere of radius “r”.
Its Surface Area =4πr2 and its volume= 4/3πr3
Surface Area to Volume Ratio= 3/r.
 Thus when the radius of the Sphere decreases, its Surface to Volume ratio increases.
 Now this approximation gives us an idea that as the size of the particle decreases the
number of atoms on the surface is in greater proportion of the total number of atoms.
 Hence, as the particle size becomes smaller and smaller the surface atoms start
dominating the properties of the whole material.
 This is what gives rise to the difference in the properties of nanoparticles and their so
varied applications.

2. Quantum Confinement

 In Nano Crystals, the Electronic energy levels are not continuous as in the bulk but are
discrete, because of the confinement of the electronic Wave function to the physical
dimensions of the particles. This phenomenon is called Quantum confinement.
 The quantum confinement effect is observed when the size of the particle is too small to
be comparable to the wavelength of the electron.
 To understand this effect, we break the words like quantum and confinement
 The word confinement means to confine the motion of randomly moving electron and to
restrict its motion in specific energy levels (discreteness)
 Quantum reflects the atomic realm of particles. (i.e quantum effects dominate the
behaviour of matter at this size)
 The decrease in confining dimension makes the energy levels discrete. This increases or
widens up the band gap and ultimately the band gap energy also increases.
PROPERTIES OF NANOMATERIALS

 Nano Materials have properties that are different from those of bulk materials.
 Most Nano structure materials are Crystalline in nature and possess unique properties.
 Production Techniques

Two main techniques are used in

nanotechnology

i) Bottom-up technique,

ii) Top-down technique,

i) Bottom –up technique ii) Top- Down technique

 The technique in which the materials and  Technique in which devices are fabricated by
devices are built up atom by atom. removing existing material from larger
entities.
 Bottom-up manufacturing would provide
components made of single molecules,  The current top down method for manufacturing
which are held together by covalent forces involves the construction of parts through
that are far stronger than the forces that methods such as cutting, carving and molding.
hold together macro-scale components.
 Using these techniques, a variety of machinery
 The amount of information that can be stored and electronic devices are being fabricated.
in devices build from the bottom-up
 But the limitation of this technique is that the
approach would be enormous.
size at which the devices can be made is
 Nanomaterial can be synthesized using limited by the ability to cut, carve and mold.
Bottom up technique in mainly two ways:
 Three different techniques are used to make
a) Molecular self-assembly Nanostructures using Top – down approach:

b) Positional Assembly
a) Lithography
b) Nano imprint lithography
c) Dip pen Lithography
CHARACTERIZATION TECHNIQUES

 In order to characterize different nanoparticles various tools are used. (Working

principles only?)
1) Transmission Electron Microscopes [TEM]
The TEM operates on the same basic principles as the light microscope but uses electrons
instead of light. When an electron beam passes through a thin section specimen of a
material, electrons are scattered. A sophisticated system of electromagnetic lenses
focuses the scattered electrons into an image or a diffraction pattern or a nano-analytical
spectrum, depending on the mode of operation.
2) Scanning Electron Microscope [SEM]
A scanning electron microscope (SEM) is a type of electron microscope that produces
images of a sample by scanning the surface with a focused beam of electrons. The
electrons interact with atoms in the sample, producing various signals that contain
information about the surface topography and composition of the sample. The electron
beam is scanned in a raster scan pattern, and the position of the beam is combined with
the intensity of the detected signal to produce an image. In the most common SEM mode,
secondary electrons emitted by atoms excited by the electron beam are detected using a
secondary electron detector (Everhart-Thornley detector). The number of secondary
electrons that can be detected, and thus the signal intensity, depends, among other things,
on specimen topography. Some SEMs can achieve resolutions better than 1 nanometer.
3) Scanning Tunnelling Microscope [STM]
The scanning tunnelling microscope (STM) works by scanning a very sharp metal wire
tip over a surface. By bringing the tip very close to the surface, and by applying an
electrical voltage to the tip or sample, we can image the surface at an extremely small
scale – down to resolving individual atoms. The STM is based on several principles. One
is the quantum mechanical effect of tunnelling. It is this effect that allows us to “see” the
surface. Another principle is the piezoelectric effect. It is this effect that allows us to
precisely scan the tip with angstrom-level control. Lastly, a feedback loop is required,
which monitors the tunnelling current and coordinates the current and the positioning of
the tip. This is shown schematically below where the tunnelling is from tip to surface
with the tip rastering with piezoelectric positioning, with the feedback loop maintaining
a current set point to generate a 3D image of the electronic topography:
4) Atomic Force Microscope [AFM]
AFM microscopes operate on the principle of surface sensing using an extremely sharp
tip on a micro machined silicon probe. This tip is used to image a sample by raster
scanning across the surface line by line, although the method varies dramatically between
distinct operating modes. The two primary groups of operating modes are widely defined
as contact mode and dynamic, or tapping, mode.
APPLICATIONS OF NANOTECHNOLOGY

 Since nanomaterials possess unique chemical, physical and mechanical properties, they
can be used for a wide variety of applications.
 Nanotechnology is finding applications in virtually all fields ranging from science to
engineering, influencing our lifestyle in many ways.
 Nanomaterials are finding application in cosmetics, textiles, healthcare, tissue
engineering, catalysis, functional coatings, medical diagnosis and therapeutics, sensors
and communication engineering, water and air pollution treatment.
 Some of these applications are discussed below.

SCRATCH RESISTANCE COATINGS

 Scratch resistance coatings are common on everything, from cars to eyeglass lenses.
 Adding aluminium silicate nanoparticles to scratch resistant polymer coatings made the
coatings more effective and also increased the resistance to chipping and scratching.
CLOTHING
 Scientist are using nanoparticles to enhance clothing.
 By coating fabrics with a thin layer of zinc oxide nanoparticles, manufacturers can create
clothes that give better protection form UV radiation.
 Some clothes have nanoparticles in the form of little hairs or whiskers that help repel
water and other materials, making the clothing water resistant and stain resistant.
ANTIMICROBIAL BANDAGES
 Antibacterial bandages are manufactured using nanoparticles of silver.
 Silver ions block microbes’ cellular respiration.
 Hence, silver smothers harmful cells by killing them.
DRUG DELIVERY
 In medicine, nanomaterials have been used for drug delivery.
 Nanotechnology creates the so called mechanical surgeons that could travel to trouble
spots inside the body.
 Biocompatible nanoparticles can be loaded with an optical imaging agent and a drug
using a polymer.
 The entire entity migrates to the trouble spot in human body and releases the drug.
 Simultaneous release of the drugs allows real-time monitoring of the drug delivery by
optical imaging.
IC TECHNOLOGY
 A Nano chip, fabricated using nanomaterials, is an integrated circuit (IC) that is so
small, in physical terms, that individual particles of matter play major roles.
 The smaller an electronic system can be made, the more processing power can fit into
a given physical volume, the less energy is required to run it, and the faster it can work.
 Silicon Nano photonics components can be integrated into CMOS integrated circuits.
This optical technique provides higher speed data transmission between integrated
circuits than is possible with electrical signals.
 Transistors built in single atom thick graphene film enable very high speed transistors.
ENERGY
 The most advanced nanotechnology projects related to energy are: storage, conversion,
manufacturing improvements by reducing materials and process rates, energy saving
and enhanced renewable energy sources.
 Previously used incandescent lamp and CFL lamp convert only 20% and 55-70%
respectively. But CFL contains hazardous mercury vapour.
 Nano technological approaches like LED convert almost 100% electrical energy into
light.
SUPERCONDUCTORS

Contents:
Introduction, Properties and types of Superconductors, BCS Theory, Applications
Introduction

 Superconductors are materials which show zero electrical resistance and expel magnetic
flux fields when cooled below a characteristic critical temperature.
 This phenomenon known as superconductivity was discovered by the Danish physicist H.
Kamerlingh Onnes (1853–1926; Nobel Prize in Physics, 1913), who found a way to liquefy
helium, which boils at 4.2 K and 1 atm pressure.
 He discovered that at about 4.15 K, the resistivity of metallic mercury decreased suddenly
to essentially zero, rather than continuing to decrease only slowly with decreasing
temperature as expected.
The electrical resistance of a metallic conductor decreases gradually as temperature is lowered.
In ordinary conductors, such as copper or silver, this decrease is limited by impurities and
crystal defects. Even near absolute zero, a real sample of a normal conductor shows some
residual resistance due to scattering of electrons by these impurities and defects (fig.1). In a
superconductor, the resistance drops abruptly to zero when the material is cooled below its
critical temperature (Tc).
Examples of superconductors are Nb, Pb, Tc,
MgB2, Nb3Al, Nb3Ge, etc.

Element Critical T. (K) (˚C) (˚F)

Aluminum 1.75 -271 -457
Mercury 4.15 -269 -452
Lead 7.2 -266 -447
Tin 3.72 -269 -453
Niobium 9.25 -264 -443

Fig: Electrical resistance of anormal metal and a superconductor.

Properties of superconductors

1. Zero electrical dc resistance

The resistance of a superconducting material to direct current flow below the
superconducting transition temperature Tc is zero.
2. Persistent Current
Superconductors are able to maintain a steady current termed as persistent current with no
applied voltage or external power to maintain it due to the absence of I2R losses.
Experiments have demonstrated that currents in superconducting coils can persist for years
without any measurable degradation. Experimental evidence points to a current lifetime of at
least 100,000 years, and theoretical estimates for the lifetime of a persistent current exceed the
estimated lifetime of the universe.
Superconductor coils with persistent current flowing through them produce magnetic fields and
can therefore act as magnets. This property is exploited in superconducting electromagnets
such as those found in MRI machines.
3. Perfect Diamagnetism – Meissner effect
In 1933, Walter Meissner and Robert Ochsenfeld discovered a
magnetic phenomenon that showed that superconductors are not just
perfect conductors.
Imagine that both the ideal conductor and superconductor are above
their critical temperature, Tc. i.e, they both are in a normal
conducting state and have electrical resistance (fig.2). A magnetic
field, Ba, is then applied. This results in the field penetrating both
materials.

Ab Bel
Fig: Illustration of Meissner effect.
Both samples are then cooled below their critical temperature, Tc, so that the ideal conductor
now has zero resistance. Now, the magnetic field is switched off.
In case of ideal conductor, switching off the field induces currents in the ideal conductor that
prevent changes in the magnetic field inside it – by Lenz’s law. Thus, the ideal conductor
𝑑𝐵
maintains its interior field. In an ideal conductor, = 0.
𝑑𝑡

The superconductor, on the other hand, expels the magnetic field from inside it. For a
superconductor, at T <Tc, B = 0 and 𝜇0 (𝐻 + 𝑀) = 0.
Hence, M = -H (M represents the magnetization of the sample and H is the applied magnetic
field). The susceptibility,  of the material is
 = M/H = -1. (exhibited by a diamagnetic material).
Thus, a superconducting specimen becomes a perfect diamagnet when the magnetization
completely cancels the external magnetic field. The Meissner effect is a reversible effect. In a
superconductor, both B and dB/dt are 0.
How is the magnetic field expelled from the interior of a superconductor?
Superconductor expels magnetic field from the interior by setting up electric current at the
surface. The surface current creates magnetic field that exactly cancels the external magnetic
field. The energy to set up this electric current comes from the exothermic superconducting
transition.
A common demonstration of the Meissner effect is to cool a high Tc superconductor
(YBa2Cu3O7), then place a small and strong permanent magnet on top of it to demonstrate the
repulsion of the magnetic field by the superconductor. This repulsion results in the levitation
(floating) of the magnet (fig.3).
 Figure 3: Demonstration of Meissner effect.

4. Critical Temperature
When a superconducting material is cooled below a
certain temperature, it goes into the superconducting
state from normal state (fig. 4). The temperature at
which a material in normal state goes into
superconducting state is known as the critical
temperature Tc. Different materials have different
critical temperatures. The transition is thermodynamic
phase transition and is reversible.

Figure 4: Resistivity curve of mercury as a function of temperature.

5. Critical Magnetic Field

Superconducting state depends on the strength of the magnetic field in which the material is
placed. Superconductivity vanishes if a sufficiently strong magnetic field is applied (fig. 5).
The minimum magnetic field, which is necessary to regain the normal resistivity, is called the
critical magnetic field, Hc. The superconducting state is destroyed when the applied magnetic
field exceeds the critical value Hc. The value of Hc varies with temperature.
The dependence of critical field on temperature is given by the relation

𝑇 2
𝐻𝑐 (𝑇) = 𝐻𝑐 (0) [1 − ( ) ]
𝑇𝑐
where 𝐻𝑐 (0) is the critical field at 0 K.

Figure 5: Variation of magnetic field with temperature.

6. Critical Current Density

An electric current flowing through a superconducting material itself can produce magnetic
field of requisite strength to destroy superconductivity. The maximum current density at which
superconductivity disappears is called critical current density, Jc. This effect was observed in
1916 by Silsbee and is known as Silsbee effect. A superconducting ring of radius R ceases to
be a superconductor when the current is Ic = 2RHc.
The existence of a critical current sets a definite limit to the size of the current that can flow
through a superconducting coil without disturbing its superconducting state.

Figure 6. Phase diagram of a superconductor.

7. London Penetration Depth

When a magnetic field is applied to a superconductor, the applied field does not suddenly drop
to zero but decays exponentially according to the formula

𝐻(𝑥) = 𝐻(0)𝑒 −𝑥/

H(0) is the field applied at the surface x = 0 and x is the distance from the surface.
The length  called the London penetration depth defines the effective depth to which a
magnetic field penetrates a superconductor. The penetration depth ranges from 300 to 5000Å
depending on the material. It is independent of frequency of magnetic field but strongly
depends on temperature.
(0)
The temperature dependence of  is given by (T) = 4
√1−( 𝑇 )
𝑇𝑐

T) and (0) are the penetration depths at T K and 0 K.

8. Flux Quantization
A.A. Abrikosov predicted the existence of magnetic flux quanta in 1957. A closed
superconducting loop can enclose magnetic flux Φ only in integral multiples of flux quantum
called a fluxon (Φ0).
ℎ
Φ = n2𝑒 = n Φ0 where n is an integer.

The value of fluxon is Φ0 = 2.07 x 10-15 weber.

9. Specific Heat
The transition from normal to superconducting state is a second order thermodynamic phase
transition in the absence of magnetic field. The specific heat changes discontinuously at the
transition temperature Tc (fig. 7). The specific heat (Cn) of a metal is contributed from the lattice
and conduction electrons
C = Clatt + Cel
The properties of the lattice do not change at the phase transition.
For a normal metal the electronic part of specific heat is (Cel)n =  T ( = constant).

For a superconductor the electronic part of specific heat is (Cel)s  exp(-/kT) (k = Boltzmann’s
constant = 1.38 x 10-23 J/K ) (for T<Tc).
The variation of specific heat implies presence of forbidden energy gap in the electronic
spectrum of the superconductor.

Figure 7: Variation of specific heat for a normal conductor and a superconductor with
temperature.
10. Isotope Effect
C. A. Reynolds and E. Maxwell found the isotope effect in 1950. The phenomenon of decrease
of critical temperature with increasing atomic mass is called isotope effect.
It is given by the relation
Tc  M   M  Tc  cons tan t

where M is the isotopic mass and  is a constant which is approximately equal to ½.

(ln Tc )
 
(ln M )

Significance of isotope effect:

 Change in isotopic mass does not change the electronic structure.
 However, mean square of amplitude of lattice vibrations  M1/2 (at low temperatures).
 Isotope effect suggests that electron-lattice interactions are involved in
superconductivity.

Type I and Type II Superconductors

The interior of a bulk superconductor cannot be penetrated by a weak magnetic field (Meissner
effect). When the applied magnetic field becomes too large, superconductivity breaks down.
Superconductors can be divided into two types (Type I and Type II) according to how this
breakdown occurs.
Type I Superconductor
 In type-I superconductors, superconductivity is abruptly destroyed via a first order
phase transition when the strength of the applied magnetic field rises above a critical
value Hc (fig.8).
 The maximum value of Hc is of the order of 0.1 W/m2.
 Perfectly diamagnetic and exhibit complete Meissner effect.
 Exhibit zero electrical resistivity below a critical temperature.
 The transition at Hc is reversible.
 Normally exhibited by pure metals, e.g. aluminium, lead, and mercury. The only alloy
known up to now which exhibits type I superconductivity is TaSi2.
 Superconductivity in Type I superconductors is modeled well by the BCS theory.
 Type I superconductors are sometimes called "soft" superconductors.
Disadvantages:
 Cannot carry large currents and hence are of not much use in producing high magnetic
fields.
Fig: Variation of magnetization as a function of applied magnetic field and magnetic field as
a function of temperature for Type I superconductor.
Type II Superconductors
 Type II superconductivity was discovered by Schubnikov in 1930’s and explained by
Abrikosov in 1957.
 They have two values of critical magnetic fields Hc1 and Hc2.
 The material is perfectly diamagnetic and exhibits complete Meissner effect below the
lower critical field Hc1. Above the upper critical field, Hc2, superconductivity is
destroyed.
 Type-II superconductors exist in a mixed state of normal and superconducting regions
between the critical fields Hc1 and Hc2. This is sometimes called a vortex state, because
vortices of superconducting currents surround filaments or cores of normal material
(fig.9).

Fig: Variation of magnetization as a function of applied magnetic field and magnetic field as
a function of temperature for Type II superconductor.

 Type II superconductors do not exhibit complete Meissner effect between the critical
fields Hc1 and Hc2.
 Normally exhibited by alloys.
 Exhibit much higher critical magnetic fields and critical temperatures. Hence, type II
superconductors are called hard superconductors.
  Upper value of critical magnetic field HC2 is of the order of 30 Wb/m2.
 Type II superconductors such as niobium-titanium (NbTi) are used in the construction
of high field superconducting magnets.

Vortex state of superconductors

 Magnetic fields can penetrate through cores of normal material surrounded by
superconducting current vortices. As long as these vortices are stationary (pinned), the
magnetic fields can penetrate while still maintaining zero electric resistivity paths
through the material.
 As the temperature or the external magnetic field is increased, the normal regions are
packed closer together. The vortices feel a force when current flows, and if they move,
the superconducting state is lost (fig. 10).

Fig: Vortex state of superconductors.

Applications of superconductors

1. Magnetic levitation is an application where superconductors perform extremely well.

Transport vehicles such as trains can be made to "float" on strong superconducting
magnets, virtually eliminating friction between the train and its tracks. This is termed
as Maglev technology.

2. An area where superconductors can perform a life-saving function is in the field of

biomagnetism. Doctors need a non-invasive means of determining what's going on
inside the human body. By impinging a strong superconductor-derived magnetic field
into the body, hydrogen atoms that exist in the body's water and fat molecules are forced
to accept energy from the magnetic field. They then release this energy at a frequency
that can be detected and displayed graphically by a computer. This is known as
magnetic resonance imaging (MRI).

3. High-energy particle research hinges on being able to accelerate sub-atomic particles

to nearly the speed of light. Superconductor magnets make this possible. CERN, a
 consortium of several European nations, is doing something similar with its Large
Hadron Collider (LHC) recently inaugurated along the Franco-Swiss border.

4. Electric generators made with superconducting wire are far more efficient than
conventional generators wound with copper wire. In fact, their efficiency is above 99%
and their size about half that of conventional generators.

5. Josephson Effects: Some of the most important applications of superconductivity are

connected with Josephson effects, e.g. extremely fast switches. Another application is
the measurement of magnetic flux (to the precision of a fraction of a flux quantum) with
two Josephson contacts (also called Josephson junctions) embedded into a ring
structure. They are of two types dc and ac josephson effect.

SQUIDS
A SQUID (for superconducting quantum interference device) is a very
sensitive magnetometer used to measure extremely subtle magnetic fields, based on
superconducting loops containing Josephson junctions. SQUIDs are sensitive enough to
measure fields as low as 5 aT (5×10−18 T) within a few days of averaged measurements. There
are two main types of SQUID: direct current (DC) and radio frequency (RF). RF SQUIDs can
work with only one Josephson junction (superconducting tunnel junction), which might make
them cheaper to produce, but are less sensitive.
DC SQUID
SQUIDs convert magnetic flux, which is hard to measure, into voltage, which is easy to
measure. A dc SQUID has two Josephson junctions in parallel in a superconducting loop (fig.
13). In the absence of any external magnetic field, the input current I splits into the two
branches equally. If a small external magnetic field is applied to the superconducting loop, a
screening current, Is , begins circulating in the loop that generates a magnetic field canceling
the applied external flux. The induced current is in the same direction as I in one of the branches
of the superconducting loop, and is opposite to I in the other branch; the total current
becomes I/2 + Is in one branch and I/2 - Is in the other. As soon as the current in either branch
exceeds the critical current, IC , of the Josephson junction, a voltage appears across the junction.
Now suppose the external flux is further increased until it exceeds Φ0/2, half the magnetic flux
quantum. Since the flux enclosed by the superconducting loop must be an integer number of
flux quanta, instead of screening the flux the SQUID now energetically prefers to increase it to
Φ0. The screening current now flows in the opposite direction. Thus the screening current
changes direction every time the flux increases by half integer multiples of Φ0. Thus the
critical current oscillates as a function of the applied flux. If the input current is more than IC,
then the SQUID always operates in the resistive mode. The voltage in this case is thus a
function of the applied magnetic field and the period equal to Φ0. Thus, measuring the voltage,
the changes in magnetic flux can be detected.
Fig: Diagram of a DC SQUID.