Chapter: 2

Ceramic
conductors
Instructor: Segenet Dagmawi
 High-temperature heating elements and electrodes
 In the high-temperature, most materials either oxidize or melt.

 In oxidizing environments where oxidation-resistant metal alloys fails.

 For the high-temperature heating (Joule heating) materials necessitate

high resistivity and strength at high temp..

 Highly resistive elements necessitate high voltage power supplies which lead
to difficulties in furnace design since refractories all become conductive when
hot so current leakage and often an accompanying risk of thermal
breakdown
 At elevated temperatures, the thermal energy can excite the electrons in the
material, allowing them to move more freely. This process increases the
electrical conductivity.
Cont.

 In a reducing atmospheres, graphite or refractory metals such as molybdenum

and tungsten can be used, while platinum and its alloys can be used in air up to

1500℃.

 Ceramics allow the use of air atmospheres at relatively low cost.

 Electric conductivity in ceramics, as in most materials, is of two types:

Ionic Conductivity: In some refractory materials, ions (charged particles) can move

through the lattice structure at high temperatures, contributing to conductivity.

Electronic Conductivity: In materials like graphite-containing refractories,

electrons become the primary charge carriers at elevated temperatures.

 Electronic conduction is the passage of free electrons through a material.

 In ceramics the ionic bonds holding the atoms together do not allow for
free electrons movement.
Cont..
 Impurities of differing valence may act as donors or acceptors of electrons,
these impurities may act as centers for polarons, Electronically conductive
ceramics have applications resistors, electrodes, and heating elements.

 Ionic conduction consists of the transit of ions (atoms of positive or negative

charge) from one site to another via point defects called vacancies in the
crystal lattice.

 With increasing temperature, vacancies become mobile, and certain

ceramics exhibit what is known as fast ionic conduction. These ceramics
are especially useful in gas sensors, fuel cells, and batteries
 Silicon carbide
 Silicon carbide (SiC) is a hard material and, because of a protective oxide layer, is
stable in air up to 1650℃.
- Application :

Abrasives for cutting and grinding.

Furnace heating elements due to its high thermal conductivity.

Varistors, which protect electrical circuits by controlling voltage surges

 SiC is covalently bonded with a structure similar to that of diamond.

- α-SiC : hexagonal form (band gap of ~3 eV)

-β-SiC : cubic form (Pure cubic β-SiC is a semiconductor with a band gap of
approximately 2.2eV)

 Important property : high strength, at high temperatures, high thermal conductivity and
low thermal expansivity, thermal shock resistance hardness (approximately 9 on the Mohs
scale).
 There are three principal methods of manufacturing SiC heating elements
1. Pressureless sintering (recrystallization),
2. Reaction-bonding; and
3. In situ formation of SiC from carbon and SiO
 SiC can be used up to about 1650℃ in air, because SiC rely on a thin native
passivating silica film for their protection against oxidation.
 Below approximately 800℃ the resistance from batch to batch is determined by
impurities.
 At 600°C, silicon carbide (SiC) behaves as an intrinsic semiconductor
NTCR means that as the temperature increases, the resistance decreases.

Why?:When SiC becomes an intrinsic semiconductor at high temperatures (like

600°C), more electrons are thermally excited into the conduction band.This increase in
charge carriers reduces the material’s resistance.

 For SiC resistivity value at 1000 0C of about 10-3 𝜴𝒎 is a requirement as

heating element
 Molybdenum disilicide
 Molybdenum disilicide (MoSi2) has been developed as a heating element for use in air at

temperature above 1500℃.

 It forms a protective silicon dioxide (SiO₂) layer when exposed to oxygen, which
prevents further oxidation (like a built-in shield against rust at high temperatures).

 Its crystal structure consists of metallic molybdenum atoms bonded with covalent
silicon atoms, creating a hybrid material.
 Fabrication of molybdenum disilicide (MoSi2)

-A mixture of fine MoSi2 powder with a carefully chosen clay is extruded into rods of suitable
diameters for the thermal sections and heating zones.

-The rods are dried, sintered and cut to various lengths.

 MoSi2 heating element will soften at high temperatures and therefore is usually
mounted vertically

 The best grade of MoSi2 element is capable of operating up to 1800 ℃.

 Lanthanum chromite
 LaCrO3 combines a melt point of 2500℃ with high electronic
conductivity (about 100Sm-1 at 1400℃) and resistance to corrosion.
 Good Electrical Conductivity at High Temperatures: It exhibits p-type
conductivity, meaning the movement of positively charged "holes"
contributes to electrical conduction.
 Synthesized by conventional techniques, Sintering takes place in a
reducing atmosphere at temperatures close to 1700℃ and is followed by
an anneal in oxygen that establishes the high conductivity.
 with substation of Strontium acts as a sintering aid as well as promoting
conductivity, and cobalt can be added to limit grain growth.
 Satisfactory conductivity is maintained up to 1800℃ in air but falls off at
low oxygen pressures so that the upper temperature limit is reduced to
1400℃ when the pressure is reduced to 0.1 Pa.
 Tin oxide
 Tin oxide (SnO2) has found applications in high-Temperature conductor,
ohmic resistors, transparent thin-film electrodes and gas sensors.
 Crystal structure : tetragonal rutile structure.
 It is wide band gap semiconductor which the band gap at 0K is 3.7eV, and therefore
pure stoichiometric SnO2 is a good insulator at room temperature when its resistivity
is probably of the order of 106Ωm.
 Conductivity is achieved by oxygen deficiency and/or doping of group V (Sb) to
form n-type conductivity.
 An important application of SnO2 in ceramic form is in conducting electrodes (high
conductivity) for melting special glasses, such as those used for optical components
(glass with lead oxide ) and lead ‘crystal’ tableware. SnO2 are resistance to corrosion
by the glass, and avoid discolouring
 synthesized mixing oxide powder, together with binders, is commonly
isostatically pressed and fired in oxidizing conditions at approximately
1400 0C
 Tin oxide's unique properties of
 Transparency,
 Conductivity, and
 Responsiveness to electrical fields.
 Zirconia
 Zirconia (ZrO2) have ionic conduction and improves with a defect
(oxygen vacancies ).
 The ‘Nurnst filament’, one used as a light source, consisted of zirconia (ZrO2) doped
with thoria and ceria these stabilize the crystal structure of zirconia and enhance its
conductivity, allowing it to withstand higher temperatures.
 The Nernst filament was an early type of electric light bulb filament These
dopants are added to improve the material's electrical and thermal properties.
 Materials like zirconia (ZrO₂) have a unique property where their resistance
decreases as temperature increases. This is referred to as a Negative
Temperature Coefficient of Resistance (NTCR).
 When zirconia is at room temperature, its resistance is high. At high resistance,
Joule heating (where heat is generated by the flow of electric current) is
inefficient because the material cannot effectively conduct electricity, and the
current cannot generate enough heat.
 Ohmic Resistors
 Ohmic resistors are resistors that obey Ohm's Law, which states that the voltage
across a resistor is directly proportional to the current flowing through it, provided
the temperature remains constant. The relationship is given by:
V=I×RV
 Ohmic resistors have a constant resistance that does not change with the applied
voltage or the current passing through them, assuming temperature remains stable.
This is a key feature of materials or resistors that obey Ohm's Law.

 Most resistors for electrical and electronic applications are required to be ohmic and
to have small temperature coefficients of resistance(TCR).
The Temperature Coefficient of Resistance (TCR) is a measure of how the resistance
of a material changes with temperature..
 The major requirement in electronics is for resistor in the range 103-108 Ω, while
materials with suitable electrical properties usually have resistivities less than10-
6Ωm.
 Thin films Ohmic Resistors

 Thin films of thickness typically 10nm are readily formed in a vacuum

chamber by evaporation, ‘sputtering’, or chemical vapor deposition
(CVD).
 Many metals and metal alloys can be evaporated from the molten
state and condensed onto suitable substrates.
 Ni-Cr alloys with resistivity values of about 10-6Ωm are deposited in thin-film
form and provide a basis for the manufacture of high-value resistors.
 Production thin-film oxide process is applied ‘sputtering’ forming plazma.
 SnO2, In2O3 and mixtures of these oxides, e.g. 90In2O3–10SnO2, are
deposited as transparent conductive films by sputtering for electro-optical
application
 Indium tin oxide (ITO) films are also commonly deposited by CVD in the
manufacture of film resistors on glass and steatite substrates.
 Thick films Ohmic Resistors

 Rather thicker films with thicknesses typically in the range 10-15um are
made by what is termed the ‘thick-film’ or ‘silk-screen’ technique.
 Silk screening is a well-established method for printing artwork.
 The screen is held taut in a frame that is fixed 1-3mm above the surface to be
printed. A print of a stiff creamy consistency is swept across the screen
by a hard rubber squeegee with sufficient pressure to force the screen,
now loaded with paint, into contact with the underlying surface.
 a conductive powder and mixing it with powdered glazes and an organic
vehicle that imparts the necessary rheological properties.
 A carefully firing ensures the organic solvents evaporation (100–
150 0C), the remaining organic compounds evaporate or are burned out
(200 – 450 0C) and, finally, the inorganic glass and active resistive
components mature and bond to the substrate (850 0C for about 10 min)
 Voltage-dependent resistors(VDR) (Varistors)
A VDR, also called a varistor, is an electronic component that protects circuits from
sudden high voltage spikes. It works by changing its resistance depending on the
voltage applied.
 Resistor which offers a high resistance at low voltages and a low resistance at
high voltages

 e.g SiC and ZnO, resistance is controlled by the region in which the ceramic grains
contact one another.
 IGLs of varying thickness between grains that differ in size controls the
voltage contact.
 Cont.
 Practice the high-current paths are likely to be via those particles
separated only by the thinnest IGLs

Actual idealized microstructure

 In ZnO varistors is governed by electron states that are formed on the surfaces
of crystals as a consequence of the discontinuity

 In ZnO varistors, the electrical behavior is governed by the formation of electron

states on the surfaces of the ZnO crystals. This phenomenon occurs due to the
discontinuity at the grain boundaries. These grain boundaries act as potential
barriers that regulate the flow of current through the material.
Cont.
 Limitations on the performance of a VDR arise from its secondary
properties.
Capacitance
Permittivity
Inductance
 The effectiveness with which a VDR absorbs depends on its
speed of response. voltage-sensitive material is generally adequate,
being typically 0.5 ns.
 Another application of VDRs is the suppression of sparks in
switches and relay contacts in highly inductive circuits
Energy stored in inductance
Energy stored in capacitors
 Thermistors
 A thermistor is a resistor that measures
temperature by its resistance.
 Thermally sensitive resistors, are electric resistors
whose resistive properties vary with temperature,
made of high temperature coefficients of
resistance (TCR)

There are two main types of thermistors:

Negative Temperature Coefficient (NTC)
The most common type of thermistor, NTC thermistors have a resistance that decreases
as the temperature increases.
Positive Temperature Coefficient (PTC)
PTC thermistors have a resistance that increases as the temperature increases.
 Cont..
 Under normal temperatures there is an energy barrier to moving electrons from
site to site. As thermal energy rises with temperature, however, the ability of
electrons to surmount this barrier increases, so that resistivity goes down

 Using solid solutions in these materials (that is, a large number of foreign ions
can substitute for the host ions in the crystal structure), so that the resistances and
temperature coefficients can be tailored over wide ranges.

 Have an application of temperature sensors and as temperature

compensation resistors, fuel-level sensors in gas tanks
 Gas sensors

 Carbon monoxide sensors:

 Tin oxide also is used in carbon monoxide gas sensors for home and
industry. Adsorption of carbon monoxide at contacts between particles
of SnO2 produces local charge states that alter the electric properties
(e.g resistance, capacitance) of the porous, polycrystalline material.

 When life-threatening concentrations of carbon monoxide are detected,

an alarm is triggered.

 By changing the temperature of operation, the sensor can

be made selective for a variety of reducing gas species (such as
hydrogen, carbon monoxide, and hydrocarbons).
 Galvanic applications refer to the use of galvanic cells or principles in various
technologies and processes. A galvanic cell is a device that generates electricity
from chemical reactions.
 Other galvanic applications of conductive ceramics are in batteries and fuel
cells. Batteries convert chemical energy into electricity.
BATTERIES
They are electrochemical cells connected in series Batteries are Store houses of
electrical energy
They are used as a source of direct electric current at constant voltage.

They are classified into two types

i) Primary cell

ii) Secondary cell

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 Differences between Primary and secondary batteries:

Primary cells Secondary cells

1. These are non-rechargeable 1. These are rechargeable and
and meant for a single use meant for multi cycle use.
and to be discarded after use.
2. Cell reaction is not reversible. 2. Cell reaction can be reversed.
3. Cannot be rechargeable.
4. Less expensive. 3. Can be rechargeable.
5. Can be used as long as the 4. expensive.
materials are active in their 5. Can be used again and again
composition. by recharging the cell.
Eg: Leclanche cell, ‘Li’ Eg; Lead- acid cell, Ni-cd
Cells. cells.

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PRIMARY CELL OR LECLANCHE CELL
In this cell the reactions are irreversible
It is also known as Dry cell

Anode- Zinc container

Cathode- Carbon rod

Anode reaction
Zn→ Zn2++2e-

Cathode reaction
2NH4++2MnO2+2e- → Mn2O3+2NH3+H2O

Cell reaction
2MnO2+2NH4Cl+Zn→ Zn(NH3)2Cl2 + Mn2O3
+H2O 22
Lead Storage battery
Anode reaction
Pb+HSO4-→ PbSO4+H++2e-

Cathode reaction
PbO2+HSO4-+3H++2e- → PbSO4+2H2O

Cell reaction
Pb+PbO2+ 2H++2HSO4-→ 2PbSO4+2H2O

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 Pb +PbO2 +H2SO4 PbSO4(s)+H2O
Lead Acid Recharging
Low self-discharge
40% in one year (three months for Ni-Cd)

No memory

Cannot be stored when discharged

Limited number of full discharges

Danger of overheating during charging

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Applications

1.Automobile and construction equipment.

2. Standby / backup system.

3. For engine batteries

Advantages:-
Low cost, long life cycle, Ability to withstand mistreatment,
perform well in high and low temperature.

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4.Lithium-ion battery (Li-ion Battery)
Components of a Li-ion Battery
Li-ion batteries are secondary batteries.
• The battery consists of a anode of Lithium, dissolved as ions, into a carbon.
• The cathode material is made up from Lithium liberating compounds, typically the three
electro-active oxide materials,
•Lithium Cobalt-oxide (LiCoO2 )
•Lithium Manganese-oxide (LiMn2O4 )
•Lithium Nickel-oxide (LiNiO2)
Electrolyte: A lithium salt (like lithium hexafluorophosphate)
dissolved in a solvent, which allows for the movement of
lithium ions between the electrodes.
Separator: A porous membrane that prevents
direct contact between the anode and cathode
while allowing lithium ions to pass through.
Principle
 During the charge and discharge processes, lithium ions are
inserted or extracted from interstitial space between atomic
layers within the active material of the battery.

 Simply, the Li-ion is transfers between anode and cathode

through lithium Electrolyte.
 Since neither the anode nor the cathode materials
essentially change, the operation is safer than that of a
Lithium metal battery.
The chemical reaction that takes place inside the battery is as
follows, during charge and discharge operation:

27
Charging Process:
 When the battery is charged, an external power source (like a
charger) applies a voltage across the electrodes.
 Lithium ions move from the cathode to the anode through the
electrolyte.
 This process involves the oxidation of the cathode material,
which releases lithium ions. At the anode, lithium ions are
intercalated (inserted) into the graphite structure, storing energy
in the form of chemical potential.
Discharging Process:
 When the battery is connected to a device and discharges, the
process reverses.
 Lithium ions move from the anode back to the cathode through
the electrolyte. During this process, the anode undergoes
reduction as it loses lithium ions.
 The movement of ions generates a flow of electrons in the
external circuit, which powers the connected device.
 Li- ion Electrolyte

Li-Ion battery Principle

29
Advantages
 They have high energy density than other rechargeable
batteries

They are less weight

 They produce high voltage out about 4 V as compared with

other batteries.

 They have improved safety, i.e. more resistance to over

voltage.
No liquid electrolyte means they are immune
from leaking. .

Fast charge and discharge rate

Disadvantage
 They are expensive 30
Applications

 The Li-ion batteries are used in cameras, calculators

 They are used in cardiac pacemakers and other

implantable device

 They are used in telecommunication equipment,

instruments, portable radios and TVs, pagers

 They are used to operate laptop computers and

mobile phones and aerospace application

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32
 FUEL CELLS
The cell that converts energy of combustion of fuels like
Hydrogen, Methane to electrical energy. Fuels are usually gas
or liquid, with oxygen as the oxidant..…

Different fuel cells are The direct conversion of chemical

energy to electrical energy has 100%.

The cell representation is as follows.

Fuel/electrode//electrolyte//electrode//oxidant

Types of Fuels:

1.Hydrogen – Oxygen Fuel cell

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 LIMITATIONS OF FUEL CELLS
 Large weight and volume of hydrogen gas fuel storage
system

 High cost of Hydrogen gas, technological advances should

bring the cost down

 Lack of infrastructure for distribution and marketing of

Hydrogen gas.

 Most basic fuel cells suffer from carbon di oxide leakages

and should be prevented from entering the cell and reacting
with the electrolyte.

34
 Hydrogen-Oxygen or Alkaline fuel cell
 In this fuel cell, electrolyte is 25-30% aqueous KOH.This cell make use of
high purity of hydrogen as fuel &oxygen as oxidant.

 The reaction between H2-O2 takes place to produce water &excess electrons
produces the electric current.

35
 Reactions:
At anode:2H2+4OH- 
4H2O+4e-
At cathode: O2+2H2O +4e-  4OH-

Net reaction: 2H2+O2  2H2O

The product discharged is water &standard emf is 1.23volts.

1.These are used as auxillary energy source in space, vehicles,
Applications:
submarines & military vehicles.

2.The product in this cell is water &it is used as valuable fresh

water &source for astronauts.
36
Reactions:
• At anode:CH3OH + 6OH-  CO2+5H2O+6e-

At cathode:3/2O2 + 3H2O + 6e-  6OH-

Net reaction:CH3OH +3/2O2  CO2 +2H2O

Advantages :
1.These cells are reasonably stable at all environmental
conditions.

2.Easy to transport.

3.Do not require complex steam reforming operations.

37
 Energy density: Energy density
is the amount of energy stored
per unit volume or mass of the
supercapacitor.
Power density: Power density is
the rate at which energy can be
delivered per unit volume or
mass of the supercapacitor.

C∆V 2 E
E 2 P△ t

=
Figure 2: Ragone plot—comparison of the performance of different energy =
storage devices.
https://images.app.goo.gl/Vwwuy1mMe4P9GL5e7
39
 Cyclic Voltammetry and Corresponding Charge–discharge Profiles for
Various Energy Storage Materials.
Electrochemical characterizations refer to a set of techniques and methods used to study the
electrochemical properties and behaviors of materials, interfaces, and reactions.
Cyclic Voltammetry (CV)
Electrochemical Impedance Spectroscopy (EIS)
Galvanometric Charge–discharge

 An electrolyte is influenced by:

 Ion concentration,

 Ionic size, type, and

 Interaction with the

electrode material
 Conductivity

How?

Figure: (a) Cyclic voltammograms and corresponding charge-discharge profiles for various types of energy storage materials (b) Classification of hyb
supercapacitors according to their design or working mechanism and (c) schematic diagram of a battery–supercapacitor hybrid system, (Patra et al., 2021)
 Superconductors
 Superconductivity is the complete disappearance of electric resistance in
materials that are cooled to extremely low temperatures.
 The temperature at which resistance ceases is referred to as the transition

temperature, or critical temperature TC, 0 K being absolute zero, the

temperature at which all atomic motion ceases.

 The best ceramic conductors are the so-called high T superconductors, materials
that lose their resistance at much higher Tc critical temperatures than their metal
alloy counterparts. Most high T ceramics are layered structures, with
two dimensional Tc copper-oxygen sheets along which superconduction takes place.
 Higher transition temperatures is one of the advantage of
ceramics superconductors
 Difficulty to process (in contrast to metal alloy superconductors), and notoriously
Cont.
 Yttrium barium copper oxide ceramic, YBa2Cu3O7, had been discovered to have

a Tc higher than 77 K, the boiling point of nitrogen (-195.8° C, or -320.4° F).

This finding raised the possibility of practical superconductors being cooled by
liquid nitrogen as opposed to conventional superconducting materials, which
have to be cooled by more expensive liquid helium.

 In hospitals and clinics small superconducting magnets are used in

magnetic resonance imaging (MRI) apparatuses, where they generate the
large magnetic fields necessary to excite and then image atomic nuclei in body
tissues.
END