MM254:

Electronic and Magnetic

Materials

Dr. S. Uma Maheswara Rao

Office: MM206

5/4/2019 NIT Warangal

 Superconductivity

• History
• Introduction
• Applications
• Processing
• Structure
• Properties
• Challenges

2
 Temperature Dependence of Resistance

Electrical
Resistivity
ρ = ρo + ρ(T)
•Impurities
•Phonons

High Temperature Low Temperature

Impure Metals Pure Metals Impure Metals In some Pure Metals

ρ = ρo + ρ(T) ρ = ρ(T) ρ = ρo If ρ = 0,
Superconductor

All good electrical conductors are not superconductors Eg.: Cu, Ag, Au
How This All Began ?
Three different hypotheses existed on how
resistance would respond as temperature
approaches 0 K :

1. Resistance would increase (Kelvin)

2. Resistance would plateau (Matthiessen)

3. Resistance would gradually drop to 0 

at 0 K (Dewar).

Unpredicted Result
None of the three hypotheses predicted
the real data –
The resistance of mercury SUDDENLY
drops to ZERO near 4.2 K, &
Superconductivity is discovered.
 What is a superconductor ?

• Above critical temperature (TC), the material may have

conventional metallic conductivity.

• As temperature drops below Tc (Very low), resistivity

rapidly drops to zero and current can flow freely without
any resistance.

 Resistivity : m ~ 1x10-13  cm for a normal metal

 Resistivity : s ~ 4x10-23  cm for a superconductor
 Superconductivity - The phenomenon of resistivity
reaching zero value when sufficiently cooled to a very
low temperature (below a certain critical temperature).
H. Kamerlingh Onnes first discovered zero resistance in 1911
while doing experiments on mercury cooled with liquid helium.

For this discovery he won NOBEL

PRIZE in PHYSICS in 1913.

Zero Resistance

Resistance measurement of pure mercury.

At 4.2 K the resistance suddenly dropped to zero.
Comparison of Temperature of Various
Physical Phenomena
Temperatures F C K
water boils 212.0 100.0 373.2
body temp 98.6 37.0 310.2
room temp 77.0 25.0 298.2
water freezes 32.0 0.0 273.2
mercury freezes -37.8 -38.8 234.4
dry ice -108.4 -78.0 195.2
liquid Oxygen -297.4 -183.0 90.2
liquid Nitrogen -320.8 -196.0 77.2
liquid Helium -452.1 -269.0 4.2
absolute zero -459.7 -273.2 0.0
Superconducting Elements TC (K)
Sn (Tin) 3.72
Hg (Mercury) 4.15
Pb (Lead) 7.19
Superconducting Compounds
NbTi (Niobium Titanium) 10
Nb3Sn (Niobium Tin) 18.1
High Temperature Superconductors

Characteristics
• High Critical Transition (TC)
• Perovskite crystal structure
• Direction dependent (Anisotropy)
• Reactive, brittle
• Oxides of Cu + other elements
Transition temperatures in Inorganic superconductors

Compound Tc (K)
PbMo6S8 12.6
Ba0.6K0.4BiO3 30
Lal.85Sr0.l5CuO4 40
Ndl.85Ce0.l5CuO4 22
YBa2Cu3O7 90
Tl2Ba2Ca2Cu3O10 125
HgBa2Ca2Cu3O8+d 133
 Three Hallmarks of Superconductivity
Complete Diamagnetism
Only in a weak magnetic field Macroscopic Quantum Effects
Zero Resistance
I Flux F

V
DC Resistance

Magnetic Induction
T>Tc T<Tc

0 Flux quantization F = nF0

Tc 0
Tc Josephson Effects
Temperature
Temperature
Magnetic Flux Quantization
Magnetic flux enclosed in a superconducting ring = integral multiples of fluxon
Φ = nh/2e = n Φ0 (Value of a fluxon, Φ0 = 2x10-15 Wb)
 Effect of Magnetic Field

In type-II, even below

TC, the field penetrates

Above TC Below TC
In Type-I, superconductivity exists
only below TC and below a critical
magnetic field strength.
Type – I is Soft Superconductor
Type – II is Hard Superconductor
Type-II are found to have higher critical
fields and carry higher current densities in
their superconducting state.
 Type-I Superconductors

Mat. Tc (K) Mat. Tc (K)

Be 0 Gd* 1.1
Rh 0 Al 1.2
W 0.015 Pa 1.4
Ir 0.1 Th 1.4
Lu 0.1 Re 1.4
Hf 0.1 Tl 2.39
Ru 0.5 In 3.408
Os 0.7 Sn 3.722
Mo 0.92 Hg 4.153
Zr 0.546 Ta 4.47
Cd 0.56 V 5.38
U 0.2 La 6.00
Ti 0.39 Pb 7.193
Zn 0.85 Tc 7.77
Ga 1.083 Nb 9.46
 Type II Superconductors

Almost All alloys and oxide Superconductors are Type-II

 Meissner Effect
The idea that a superconductor can pin a magnet in free
space was first conceived by Meissner & Ochsenfeld in
1933. This phenomenon is known as “Meissner effect.”

• When a transition from normal to superconducting state occurs, it actively

excludes magnetic fields from its interior, this is called Meissner effect.

• This constraint to zero magnetic field inside a superconductor is distinct from

the perfect diamagnetism which would arise from its zero electrical resistance.

• Zero resistance imply that if we tried to magnetize a superconductor, current

loops would be generated to exactly cancel the imposed field (Lenz’s Law).
BCS Theory - Superconductivity explained

John Bardeen Leon Cooper Bob Schrieffer

“Cooper Pairs”

e- e-
Two coupled e-s with opposite momenta & spins
Does not scatter - resistanceless
Energetically favorable below TC
 Model for electrons in a metal -
Non-interacting, scattering is higher

Cooper pairs are spin up and

down electrons paired.

Superconductivity decays very

rapidly when comes contact
with a Ferromagnet.
 S + +
+ +
v v +
+ + +
S

Second electron is attracted to the

First electron polarizes the lattice concentration of positive charges
left behind by the first electron
 Pairs are related by momentum ±
p, and NOT position.

Through Phonons !

 Electron–lattice interaction
 Cooper pairs

Two coupled e-s with opposite momenta & spins

Does not scatter - Resistanceless
Energetically favorable below TC
- When a metal is cooled below the critical temperature, electrons form Cooper Pairs.

- Cooper Pairs are electrons which exchange phonons and become bound together.

- Bound electrons behave like bosons. Their wave-functions don’t obey Pauli exclusion rule
and thus they can all occupy the same quantum state.

- The BCS theory of Superconductivity states that bound photons have slightly lower
energy, which prevents lattice collisions and thus eliminates resistance.

- As long as kT < binding energy, then a current can flow without dissipation.
 The Critical Field
Critical magnetic field, HC is the minimum Element HC near 0K
magnetic field required to destroy (mT)
superconductivity at a given temperature. Nb 198
Pb 80.3
HC obeys a parabolic law of the form,
Sn 30.9
 T  2

H C  H 0 1 -   
  TC   H0

Normal
H0 – Critical field near 0 K
T - Temperature below TC HC
TC - Transition Temperature
Superconducting

T (K) TC
Effect of Electric Current
• Large electric current – induces magnetic
field – destroys superconductivity
• Induced Critical Current iC = 2πrHC
Persistent Current
• Steady current flows through a
superconducting ring without any decrease
in strength even after the removal of the
field provided T<TC.
  K.A. Muller J. G. Bednorz

 The Discovery of superconductivity in ceramic materials

 The Nobel Prize in Physics 1987

In April 1986, K. Alex Muller and George Bednorz at IBM in Switzerland,

detected superconductivity in (La-Ba)2CuO4 with a Tc up to 35 K, in contrast
to previous record of 23 K for which they were awarded the Nobel Prize.
 High-Tc Superconductivity – Road
Map

164 K @ 30 GPA

Paul Chu

Alex Müller and Georg Bednorz

5/4/2019 28
Introduction to YBa2Cu3O7-y (YBCO-123 Compound)

YBCO has BaO-CuO2-YCuO2-BaO-CuO layered sequence with two CuO2 planes per unit
cell separated by an Y atom. The CuO chains lie between the BaO layers.
The oxygen content can be varied from
y = 0 to y = 1 through removal of oxygen
from the CuO chain layer.
Fully oxygenated YBCO is a hole-doped
superconductor with Tc= 92 K.

Orthorhombic crystal structure;

a = 3.82 Å , b = 3.88 Å , & c = 11.68 Å
YBCO is an anisotropic hole-doped HTS material
High Temperature Superconductors
Has a Layered structure  quasi- 2D system

Copper Oxygen Planes

Other Layers

CuO2 layer

Electrons have higher mobility in the CuO2 layer

 SOLID STATE REACTION / CERAMIC METHOD
Solid state reaction is a method widely used for the preparation of polycrystalline solids (i.e., Powders). The starting material is a
mixture of solids. Solids do not usually react together at room temperature over normal time scales and it is necessary to heat them
to much higher temperatures, often 1000 to 1500 oC, in order for reaction to occur at an appreciable rate. Both thermodynamic and
kinetic factors are important; thermodynamic considerations show whether or not a particular reaction should occur; kinetic factors
determine the rate at which the reaction occurs.
The important factors that influence the rate of reaction between solids are,
1) Area of contact between the reacting solids & hence their surface areas.
2) The rate of nucleation of the product phase, and
3) Rate of diffusion of ions through various phases, especially product phase.

EXPERIMENTAL PROCEDURE
1) REAGENTS
2) MIXING
3) CONTAINER MATERIAL
4) HEAT TREATMENT

Mechanical Milling – To size reduce &/or for

mixing of starting materials to form a different
compound
Ball mill is a grinder for reducing hard materials to
powder. The grinding is carried out by the pounding
and rolling of a charge of steel or ceramic balls
carried within the cylinder which rotates at a desired
speed thus grinding or dispersing the materials.
 YBCO Superconductor Preparation
Steps
Numerous methods exist for preparing YBCO
superconductors. Most of them involve a four step
process. Following is a Solid State Reaction method
1. Mixing the Chemicals
2. Calcination (The initial firing)
3. Intermediate Firing(s) & Intermediate Grindings
4. The Final Oxygen Annealing
This method employs a series of mixing, grinding and heating cycles with varying temperatures and
time of heating schedules. Appropriate amount of yttrium oxide, barium carbonate and copper oxide
were weighed and mixed in stoichiometric ratios in an agate mortar. The mixture is then subjected
to calcination which promotes decomposition of carbonates, nitrates or other impurity phases,
leading to the formation of the desired phase of the superconducting YBCO compound. The
calcined powder so obtained was ground well and pressed in the form of pellets and sintered at high
temperatures. Sintering is one of the most important means to develop the microstructure by the
reduction in grain boundary volume and increase in contact region so as to form the desired phase.

Oxygen Annealing
 Mixing The Chemicals
The chemicals must be mixed in the proper proportions so that the
atomic ratios of yttrium, barium, and copper are [Link]. The proper
weight ratios for a small pellet are:

Yttrium oxide, Y2O3 = 1.13 grams

Barium carbonate, BaCO3 = 3.95 grams
Cupric oxide, CuO = 2.39 grams

The recommended procedure is to first use a mortar and pestle to

grind down any lumps or large particles in the chemical powders.
Suitable mixing agent can also be used to make a paste. The slurry
will reform into a powder as the mixing agent evaporates.
Heat the sample at 900 °C for 1 day to drive off unwanted CO2.

After the first heating, allow the sample to cool down, re-grind, and
re-heat for 1 day at 950 °C.

After second heating, re-grind, place in metal die and press into a
pellet using at 3 to 5 metric tons depending upon the size of pellet.

After pressing, heat the pellet at 450 °C in the presence of flowing O 2.

Flowing O2 is vital for the formation of crystal structure and oxygen

Stoichiometry to exhibit the actual TC around 92 K.
 Introduction to Bi2Sr2CanCun+1Ox (BSCCO)

Bi2Sr2CanCun+1Ox
Three polytypoids exist for n = 0, 1 and 2
For n = 0, we have Bi-2201 ; with TC = 10 K
Crystal structure of Bi2Sr2CalCu2O8 For n = 1, we have Bi-2212 ; with TC = 80 K
(2212 phase)
For n = 2, we have Bi-2223 ; with TC = 110 K

Apart from these, due to Sb doping, 4441 phase with TC of 140 K forms even
after first heating and coexists with the 2212 and 2223 phases.
 Comparison of BSCCO-2212 with YBCO

c = 30.643 Å
YBCO

b = 5.395 Å

a = 5.396 Å
α = 90o BSCCO-2212 Orthorhombic
 Intrinsic stacks of

Bi-2212 is highly layered with

insulating Bi-O blocks
intercalated between
superconducting CuO2 planes.

Electrons moving along c-axis

experiences a sequential of
potential barriers due to the
layered structure.

S-superconducting; I-insulating layers

S. Heim et al, Physica C, 367 (2002) 348.

 Best forming composition of Bi-2212 is Bi2.2Sr1.8Ca1Cu2O8
[Takeshi et al, Physica C 168(1990) 309-314]
Sample Preparation
Carbon free all oxide starting materials mixed uniformly in acetone or suitable medium
Powder annealed @ 800 C/12h  (grinding & forming a pellet) 825 C/12 h
(grinding & forming pellet) 825 C/2h and 800 C/10 h
(grinding & forming pellet-melt textured by sintering at 875 C/30 minutes & 800 C/10 h (two
times or as per requirement until single phase is formed)
All Annealing done in Air
2000
(1 1 5)

T110 - Target 0.014

1800
(2 0 0)

Orthorhombic
1600 0.012 T110 target
(0 1 9)

JCPDS # 44-0615
o
1400 875 C 2nd trial
0.010
(0 0 8)
Intensity (cps)

R (Ohm)
1200
(0 0 10)

0.008 Tcon = 89 K
(1 1 3)

1000
(2 0 12) (0 0 16)
(0 0 12)

(2 0 10)

(2 2 11) (3 1 7)

800 0.006
(2 0 13) (0 0 17)
(3 1 3)
(1 1 13)

600
(0 0 20)
(3 1 5)
(0 0 13)

0.004
(2 1 0)

Tc = 9 K
(2 2 8)
(2 0 8)

400
0.002
200 cool
Tcoff = 80 K
0 0.000
20 30 40 50 60 70 80 50 75 100 125 150 175 200 225 250 275 300
Two theta (degree) T (K)
 Bundling & cabling development to limit AC
losses

 Roebel bar conductor concepts

 Cable-in-conduit conductor
 Nb3Sn strand
already used in NbTi


 Applied in BSCCO-cable (SIEMENS)

 AC-loss optimized Multi stage twisted cable-

 in-conduit with central cooling channel,
 Rated current: 68 kA @ 11.8 T and 4.6 K

 AC - loss optimization is one of the most crucial points !

Wire Fabrication
Technique
The powder is packed into a cylinder made of
silver or silver alloy, drawn into long strands and
packed together as a group of fine filaments. Then
the silver-sheathed superconductor precursor is
heated, causing the powder to react chemically
and form superconducting material inside the
silver sheath. Making the superconducting
ceramic filaments thin and bundling them
together allows the wires to tolerate a certain
amount of bending.
 Applications of Superconductivity
Trade off between:
Cost Saving & Cost Increase

Zero resistance, no Need refrigeration,

energy lost, novel fabrication costs….
uses…
 Superconducting magnets
An electrical current in a wire creates a magnetic field around a
wire. The strength of the magnetic field increases as the current in a
wire increases. Because SC’s are able to carry large currents
without loss of energy, they are well suited for making
electromagnets strong magnets. When a SC is cooled below its Tc
and a magnetic field is increased around it, the magnetic field
remains around the SC. If the magnetic field is increased to a
critical value Hc the SC will turn normal.
A typical Nb3Sn SC magnet.
It produces 10.8 T with a current Support a very high current density with a very small resistance
of 146 A. Bore diameter is 3.8 cm.
Magnet can be operated even months at nearly constant field

Cross-section of multifilament
Nb-Ti of 1 mm overall diameter.
 Applications
• Large distance power transmission (ρ = 0)

• Switching device (easy destruction of superconductivity)

• Sensitive electrical equipment (small V variation large constant

current)

• Memory / Storage element (persistent current)

• Highly efficient small sized electrical generator &

transformer
 Medical Applications
• NMR – Nuclear Magnetic Resonance – Scanning
•Brain wave activity – brain tumour, defective cells
•Discriminate damaged cells from healthy cells
•Superconducting solenoids – magneto hydrodynamic
power generation – plasma maintenance
Uses of Superconductors : MRI
MRI allows doctors to see what is happening inside the
body without directly performing surgery.

• The development of superconductors has improved the field of MRI

as the superconducting magnet can be smaller and more efficient
than an equivalent conventional magnet.

• Radiofrequency receivers that are currently made of copper coils

can be replaced by superconducting receiver coils, increasing signal-
to-noise ratio by a factor of two.

• This change is especially important in low-strength MRI fields (based

on lower cost magnets), where weak fields mean weak signals.
Superconducting coils could boost the performance of these machines
by improving image quality and reducing measurement time.
Uses of Superconductors : Magnetic field sensing

• Compared with the rest of the body’s

low current operations, the heart is a
highly electric organ. Its faint magnetic
field (about 100 pico teslas) can be
measured with superconducting
quantum interference devices
(SQUIDs), the most sensitive magnetic
sensors known.

• When arranged in arrays, SQUIDs can

provide an image of the heart ’s
magnetic field and yield clues to
abnormal conduction patterns that are
the basis of some heart arrhythmias
(abnormal rhythms).
 Josephson Junction
• Consists of thin layer of insulating material placed between two
superconducting materials.
• Insulator acts as a barrier to the flow of electrons.
• When voltage applied current flowing between super conductors by
tunneling effect.
• Quantum tunnelling occurs when a particle moves through a space in
a manner forbidden by classical physics, due to the barrier involved

~ 2 nm
 SQUIDs
(Superconducting QUantum Interference Devices)

Principle :
Small change in magnetic field, produces variation in the flux quantum.

Construction:
The SQUID device consists of two superconductors separated by thin
insulating layers to form two parallel Josephson junctions.
The phase of the wave function in left and right branches is
different because of the penetrating flux.
Applied Uses of Superconductors
Electric generators made with superconducting wire are far more
efficient than conventional generators wound with copper wire.
– Their efficiency is above 99% and their size about half that of
conventional generators.
– They make lucrative ventures for power utilities.

Recently, power utilities have begun to use superconductor-based

transformers and "fault limiters".
– Superconducting fault limiters can respond within a few
milli-seconds to limit thousands of amperes of current – such
as after a lightning strike.

An idealized application for superconductors is to employ them in

transmission of commercial power to cities.
– BUT, due to the high cost and impracticality of cooling miles
of superconducting wire to cryogenic temperatures, this has
only happened with short "test runs".

Superconducting material takes up less space.

– In one instance 250 pounds of superconducting wire replaced
18,000 pounds of copper cable, making it over 7000% more
space-efficient.
 Uses of Superconductors : Levitation
'Mag-Lev' trains have been under development for the past two
decades
Superconducting magnets are used create a strong magnetic force
to levitate the vehicles and guide them within the bounds of the
guide way. The system takes advantage of the naturally stabilizing
effect provided by electromagnet induction. No controlling devices
are needed to keep the train on its guide way. The magnetic
levitation force is ideal for supporting a train at very high speeds.
Maglev trains have to perform the following functions to operate at high speeds
1. Leviation
2. Propulsion
3. Lateral Guidance
MLX01 Test Vehicle
2003 581 km/h

2005 tested passing at relative 1026 km/h

 Magnetic Levitation – Meissner
Effect

MLX01 Test Vehicle

2003 581 km/h 361 mph

2005 80,000+ riders
2005 tested at relative 1026 km/h

Maglev in Germany
32 km track
550,000 km since 1984
Design speed 550 km/h
Regularly operated at 420 km/h
[Link]
 THANK YOU

53
5/4/2019
 PRINCIPLE OF MAGNET LEVITATION
•The passing of the superconducting magnets by figure eight
levitation coils on the side of the tract induces a current in the
coils and creates a magnetic field. This pushes the train upward
so that it can levitate 10 cm above the track.
The train does not levitate until it reaches 50 mph, so it is
•
equipped with retractable wheels.
 PRINCIPLE OF PROPULSION
•The propulsion coils located on the sidewalls on both sides of the
guideway are energized by a three-phase alternating current from a
substation, creating a shifting magnetic field on the guideway.
•The on-board superconducting magnets are attracted and pushed by the
shifting field, propelling the Maglev vehicle.
Braking is accomplished by sending an alternating current in the reverse
•
direction so that it is slowed by attractive and repulsive forces.
SQUID
superconducting quantum interference device
o

i left i right
 ~ o e  ~ o e
 Flux Quantization
Magnetic flux around a closed superconducting
current loop must be quantized

One fluxon