Department of Metallurgical and Materials Engineering

Subject: Engineering Ceramic (MME-312)

Title: Ceramic Materials
Submitted to: Dr. Muhammad Asif Rafiq
Submitted by: Raza Ali (2018-MM-34)
Date: December 1st, 2020

University of Engineering and Technology, Lahore

 Table of Contents
Introduction of Ceramics……………………………………………………………………2
Definition……………………………………………………………………………..2
General Properties…………………………………………………………………….2
Classification of Ceramics…………………………………………………………….3
Applications of Ceramics…………………………………………………………..…7
Atomic Bonding in Ceramics……………………………………………………………......8
Ionic Bonding………………………………………………………………………….8
Covalent Bonding………………………………………………………………….......8
Mixed Bonding…………………………………………………………………….......9
Structure of Ceramics……………………………………………………………………….10
Factors determining crystal structure………………………………………………….10
Types of Crystal Structure……………………………………………………………..11
Polymorphs and Allotropes…………………………………………………………....15
Density of Ceramics…………………………………………………………………...18
Processing of Ceramics……………………………………………………………………...19
Making Powder………………………………………………………………………..19
Characterization of Powder……………………………………………………………22
Shaping…………………………………………………………………………….......23
Sintering……………………………………………………………………………......25
Superconductors……………………………………………………………………………..30
BCS Theory……………………………………………………………………………30
High temperature superconductors…………………………………………………….31
Types of superconductors……………………………………………………………...32
Applications of superconductors…………………………………………………........32
References…………………………………………………………………………………...33

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 Ceramic Materials
Introduction of Ceramics
Definition
The word ceramic is derived from the Greek word keramos, which means “potter’s clay” or
“pottery.” Its origin is a Sanskrit term meaning “to burn.” So the early Greeks used “keramos”
when describing products obtained by heating clay-containing materials.
Ceramics are compounds between metallic or metalloids and nonmetallic elements; they are
most frequently oxides, nitrides, and carbides.
We can also define ceramics by their processing conditions as well and that definition is:
Ceramics can be defined as solid compounds that are formed by the application of heat, and
sometimes heat and pressure, comprising at least two elements provided one of them is a non-
metal or a nonmetallic elemental solid. The other element(s) may be a metal(s) or another
nonmetallic elemental solid(s).
For example, common ceramic materials include aluminum oxide or alumina (Al2O3), silicon
dioxide or silica (SiO2), silicon carbide (SiC), silicon nitride (Si3N4) and in addition the
traditional ceramics—those composed of clay minerals (e.g. porcelain) as well as cement and
glass.

General properties of Ceramics

With regard to mechanical behavior, ceramic materials are relatively stiff and strong—stiffness
and strength are comparable to those of the metals.

Figure 1: Bar chart of room temperature stiffness (i.e., elastic modulus)

values for various metals, ceramics, polymers, and composite materials.

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 Figure 2: Bar chart of room temperature strength (i.e., tensile strength)
values for various metals, ceramics, polymers, and composite materials.

Ceramics are stronger in compression than in tension, whereas metals have comparable tensile
and compressive strengths. This difference is important when we use ceramic components for
load-bearing applications. Ceramics generally have low toughness.
Ceramic materials are typically insulative to the passage of heat and electricity (i.e. have low
electrical conductivities) because the valence electrons are tied up in bonds and are not free as
they are in metals.
Ceramics are more resistant to high temperatures and harsh environments than metals and
polymers. Pyrex glass is used widely in chemistry laboratories specifically because it is
resistant to many corrosive chemicals, stable at high temperatures (it does not soften until 1100
K), and is resistant to thermal shock because of its low coefficient of thermal expansion (33 ×
10−7 K−1).
With regard to optical characteristics, ceramics may be transparent, translucent, or opaque.
Many ceramics are transparent because they have a large Eg. Examples include sapphire watch
covers, precious stones, and optical fibers.
Ceramics are non-magnetic but some of the oxide ceramics (e.g., Fe3O4) exhibit magnetic
behavior.

Classification of Ceramics
Ceramics are broadly classified into two types which are as follows:
 Traditional ceramics
 Advanced ceramics

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Traditional Ceramics
Traditional ceramics are characterized by mostly silicate-based porous microstructures that are
quite coarse, non-uniform and multiphase.
They are typically formed by mixing clays and feldspars, followed by forming either by slip
casting or on a potter's wheel, firing in a flame kiln to sinter them, and finally glazing.

Figure 3: Processing steps of traditional ceramics

Traditional ceramics include high-volume items such bricks and tiles, toilet bowls (white-
wares) and pottery. They also include abrasives, cements, refractories and glasses.
Traditional clay-based ceramics have been used for over 25,000 years. Applications of
traditional ceramics are shown in figures below:

Figure 4 & 5: Applications of traditional Ceramics

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Advanced Ceramics
Ceramics composed of chemically prepared powders such as alumina, silicon carbide etc. are
known as advanced ceramics.
Advanced ceramics include newer materials such as laser host materials, piezoelectric
ceramics, ceramics for dynamic random access memories (DRAMs) etc., often produced in
small quantities with higher prices
Advanced ceramics are also referred to as “special,” “technical,” or “engineering” ceramics.
They exhibit superior mechanical properties, corrosion/oxidation resistance, or electrical,
optical, and/or magnetic properties.
Advanced ceramics have generally been developed within the last 100 years.

Figure 6: Processing steps of advanced ceramics

Applications of advanced ceramics are shown in figure below:

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 Figure 7: Applications of Advanced Ceramics
A comparison between the processing steps of traditional and advanced ceramics is as follows:

Figure 8: A comparison of different aspects

of traditional and advanced ceramics.

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Applications of Ceramics
Traditional ceramics like glass, bricks, tiles etc. are used in construction applications. While
advanced ceramics are used in Thermal, Electrical and dielectric, Magnetic and
superconductive, Optical, Nuclear applications, Chemical and Mechanical applications.
In thermal applications they are used as Insulation (High-temperature furnace linings for
insulation such as SiO2, A12O3, and ZrO2), Refractoriness (High-temperature furnace linings
for insulation and containment of molten metals and slags) and Thermal conductivity (Heat
sinks for electronic packages such as A1N).
In Electrical and dielectric applications they are used as Conductivity (SiC, ZrO2, MoSi2),
Ferroelectricity (Ba-titanate-based materials), Low-voltage insulators (porcelain, steatite,
forsterite), Insulators in electronic applications (Al2O3, A1N), Ion-conducting (ZrO2, A12O3
etc.) and Semiconducting (oxides of Fe, Co, Mn) etc.

Figure 9 & 10: Applications of Ceramics

Figure 11: Market Revenue of Ceramics by Application in 2018

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Atomic Bonding in Ceramics
The properties of any solid and the way its atoms are arranged are determined primarily by the
nature and directionality of the interatomic bonds holding the solid together. Consequently, to
understand variations in properties, it is imperative to appreciate how and why a solid is "glued"
together means by which type of bond solid atoms are joined with each other.
Atomic bonding is chemical bonding. Chemical bonding is the physical process that is
responsible for the interactions between atoms and molecules.
Very broadly speaking, ceramics can be classified as being either ionic or covalently bonded.
However, bonding in ceramics is neither purely covalent nor purely ionic but a mixture of both.

Ionic Bonding
Ionic bond formed by the complete transfer of electron from one atom to another atom. Ionic
bonded solids are made up of charged particles — positively charged ions, called cations, and
negatively charged ions, called anions. Their mutual attraction holds the solid together.
Ionic compounds generally form between very active metallic elements and active nonmetals.
The requirements for an AB ionic bond to form are that A be able to lose electrons easily and
B be able to accept electrons without too much energy input.

Figure 12: Ionic Bond formation of NaCl

This restricts ionic bonding to mostly metals from groups IA, IIA, and part of IIIA as well as
some of the transition metals and the most active nonmetals of groups VIIA and VIA.

Covalent Bonding
Covalent bond forms by the mutual sharing of electron between two atoms. For covalent
bonding to occur ionic bonding must be unfavorable. This is tantamount to saying that the
energies of the bonding electrons of A and B must be comparable because if the electron energy
on one of the atoms is much lower than that on the other then electron transfer from one to the
other would occur and ionic bonds would tend to form instead.
H2, O2, CH4 etc. also formed by covalent bonds. An example of covalent bonding present in
water is shown in figure 13.

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 Figure 13: Covalent Bond formation of H2O
Mixed Bonding
In mixed bonding both ionic and covalent bonds are present. In ceramics we do not usually
have pure ionic bonds or pure covalent bonds but rather a mixture of two types of bonding.
Even so it is still often convenient and a frequent practice to call predominantly ionically
bonded ceramics “ionic ceramics” and predominantly covalently bonded ceramics “covalent
ceramics.”
From the series of electronegativity values we can form some general rules about bonding.
 Two atoms of similar electronegativity will from a covalent bond.
 When the electro-negativities differ the bond is partially ionic.
The ionic character of a bond increases with the difference in electronegativity of the two atoms
as shown
Fraction of ionic character = 1 − exp[−0.25 (XM − XX) 2]
XM and XX represent the electro-negativities of M and X (keeping the cation/anion labeling).

Figure 14: Ionic and Covalent Character of different Ceramics Compounds

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Structures of Ceramics
For those ceramic materials for which the atomic bonding is predominantly ionic, the crystal
structures may be thought of as being composed of electrically charged ions instead of atoms.

Factors Determining the Crystal Structure

Two characteristics of the component ions in crystalline ceramic materials influence the crystal
structure
The magnitude of the electrical charge on each of the component ions
The crystal must be electrically neutral i.e. all the cation positive charges must be balanced by
an equal number of anion negative charges. The chemical formula of a compound indicates the
ratio of cations to anions or the composition that achieves this charge balance. For example, in
calcium fluoride, each calcium ion has a +2 charge (Ca2+), and associated with each fluorine
ion is a single negative charge (F-). Thus, there must be twice as many F- as Ca2+ ions, which
is reflected in the chemical formula CaF2.
The relative sizes of the cations and anions
The second criterion involves the sizes or ionic radii of the cations and anions, rC and rA,
respectively. Because the metallic elements give up electrons when ionized, cations are
ordinarily smaller than anions and consequently the ratio rC/rA is less than unity. Each cation
prefers to have as many nearest-neighbor anions as possible. The anions also desire a maximum
number of cation nearest neighbors. Stable ceramic crystal structures form when those anions
surrounding a cation are all in contact with that cation.
The size of an ion depends on several factors. One of these is coordination number: ionic radius
tends to increase as the number of nearest-neighbor ions of opposite charge increases.
In addition, the charge on an ion will influence its radius. For example, the radii for Fe2+ and
Fe3+ are 0.077nm and 0.069 nm, respectively, which values may be contrasted to the radius of
an iron atom—0.124 nm.

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Figure 15: Coordination Numbers and Geometries for Various Cation–Anion Radius Ratios (rC/rA)

Types of Crystal Structures

AX-Type Crystal Structures
Some of the common ceramic materials are those in which there are equal numbers of cations
and anions. These are often referred to as AX compounds, where A denotes the cation and X
the anion. There are several different crystal structures for AX compounds; each is typically
named after a common material that assumes the particular structure.
 Rock Salt Structure

The most common AX crystal structure is the sodium chloride (NaCl) or rock salt type. The
coordination number for both cations and anions is 6 and therefore the cation–anion radius ratio
is between approximately 0.414 and 0.732. A unit cell for this crystal structure is generated
from an FCC arrangement of anions with one cation situated at the cube center and one at the
center of each of the 12 cube edges.
Some common ceramic materials that form with this crystal structure are NaCl, MgO, MnS,
LiF and FeO.

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 Figure 16: AX type crystal structure of NaCl

 Cesium Chloride Structure

A unit cell for the cesium chloride (CsCl) crystal structure is shown in figure below. The
coordination number is 8 for both ion types. The anions are located at each of the corners of a
cube, whereas the cube center is a single cation. Interchange of anions with cations and vice
versa produces the same crystal structure. This is not a BCC crystal structure because ions of
two different kinds are involved.

Figure 17: AX type crystal structure of CsCl

 Zinc Blende Structure

A third AX structure is one in which the coordination number is 4 i.e. all ions are tetrahedrally
coordinated. This is called the zinc blende, or sphalerite structure after the mineralogical term
for zinc sulfide (ZnS). A unit cell is presented in figure below. All corner and face positions of
the cubic cell are occupied by S atoms, whereas the Zn atoms fill interior tetrahedral positions.
Most often the atomic bonding is highly covalent in compounds exhibiting this crystal structure
which include ZnS, ZnTe and SiC.

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 Figure 18: AX type crystal structure of Zinc Blende
(ZnS)

AmXp-Type Crystal Structures

If the charges on the cations and anions are not the same, a compound can exist with the
chemical formula AmXp , where m and/or p is not equal to 1. An example is AX2, for which a
common crystal structure is found in fluorite (CaF2). The ionic radii ratio rC/rA for CaF2 is about
0.8, which gives a coordination number of 8. Calcium ions are positioned at the centers of
cubes, with fluorine ions at the corners. The chemical formula shows that there are only half
as many Ca2+ ions as F- ions, and therefore the crystal structure is similar to CsCl except that
only half the center cube positions are occupied by Ca2+ ions. One unit cell consists of eight
cubes. Other compounds with this crystal structure include ZrO2 (cubic), UO2, PuO2 and ThO2.

Figure 19: AmXp type crystal structure of CaF2

AmBnXp-Type Crystal Structures

It is also possible for ceramic compounds to have more than one type of cation; for two types
of cations (represented by A and B), their chemical formula may be designated as A mBnXp.
Barium titanate (BaTiO3), having both Ba2+ and Ti4+ cations, falls into this classification. This
material has a perovskite crystal structure. A unit cell of this structure is shown in figure below.

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Ba2+ ions are situated at all eight corners of the cube and a single Ti4+ is at the cube center, with
O2 ions located at the center of each of the six faces.

Figure 20: AmBnXp type crystal structure (perovskite structure) of BaTiO3

Summary of these crystal structures along with examples is given in table below:

Figure 21: Summary of Some Common Ceramic Crystal Structures

 Spinel Structure
The spinel structure is one of the AmBnXp types. This structure is named after the naturally
occurring mineral MgAl2O4. Where the A and B cations are in the +2 and +3 oxidation states
respectively.
The structure is shown in figure below, cations occupy one-eighth of the tetrahedral sites and
one-half of the octahedral sites
When the A2+ ions exclusively occupy the tetrahedral sites and the B3+ ions occupy the
octahedral sites, the spinel is called a normal spinel. Usually the larger cations tend to populate
the larger octahedral sites and vice versa. In the inverse spinel, the A2+ ions and one-half the
B3+ ions occupy the octahedral sites while the other half of the B3+ ions occupy the tetrahedral
sites.

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 Figure 22: AmBnXp type crystal structure (spinal structure)

Polymorphs and Allotropes

Materials that have the same chemical composition but different crystal structures are known
as polymorphs of each other.
Many ceramic materials show this behavior for example SiO2, BN, BaTiO3, ZrO2 and BeO.
When an element exists in different solid phases we refer to the phases as allotropes.
Polymorphs and Allotropes of Carbon
Polymorphs and allotropes of carbon are as follows:
 Diamond
Diamond is a metastable carbon polymorph at room temperature and atmospheric pressure. Its
crystal structure is a variant of the zinc blende structure in which carbon atoms occupy all
positions (both Zn and S). The unit cell for diamond is shown in figure below. Each carbon
atom has undergone sp3 hybridization so that it bonds (tetra-hedrally) to four other carbons;
these are extremely strong covalent bonds. The crystal structure of diamond is appropriately
called the diamond cubic crystal structure.

Figure 23: A unit cell for the diamond cubic crystal structure.

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  Graphite
Another polymorph of carbon graphite has a crystal structure distinctly different from that of
diamond. Furthermore, it is a stable polymorph at ambient temperature and pressure. For the
graphite structure, carbon atoms are located at corners of interlocking regular hexagons that lie
in parallel (basal) planes. Within these planes (layers or sheets), sp2 hybrid orbitals bond each
carbon atom to three other adjacent and coplanar carbons atoms. These bonds are strong
covalent ones. This hexagonal configuration assumed by sp2 bonded carbon atoms.
Furthermore, each atom’s fourth bonding electron is delocalized (i.e. does not belong to a
specific atom or bond). Rather, its orbital becomes part of a molecular orbital that extends over
adjacent atoms and resides between layers. Furthermore, interlayer bonds are directed
perpendicular to these planes (i.e. in the c direction) and are of the weak van der Waals type.

Figure 24: The structure of graphite.

 Fullerenes
One type of fullerene discovered in 1985 consists of a hollow spherical cluster of 60 carbon
atoms. A single molecule is denoted by C60. Carbon atoms bond together so as to form both
hexagonal (six-carbon atom) and pentagonal (five-carbon atom) geometrical configurations.
One such molecule, shown in figure below and this molecule is found to consist of 20 hexagons
and 12 pentagons which are arrayed such that no two pentagons share a common side. The
molecular surface thus exhibits the symmetry of a soccer ball.
In the solid state, the C60 units form a crystalline structure and pack together in a face centered
cubic array.
Uses and potential applications of fullerenes include antioxidants in personal care products,
biopharmaceuticals, catalysts, organic solar cells, long-life batteries, high temperature
superconductors and molecular magnets.

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 Figure 25: The structure of a C60 fullerene molecule
 Carbon Nanotubes
Each nanotube is a single molecule composed of millions of atoms. The length of this molecule
is much greater (on the order of thousands of times greater) than its diameter.
Its structure consists of a single sheet of graphite (i.e. graphene) that is rolled into a tube.
Nanotubes are extremely strong and stiff and relatively ductile. For single-walled nanotubes,
measured tensile strengths range between 13 and 53GPa.
Elastic modulus values are on the order of one terapascal (1TPa = 103GPa), with fracture strains
between about 5% and 20%. Furthermore, nanotubes have relatively low densities.
Carbon nanotubes also have unique and structure-sensitive electrical characteristics.
Depending on the orientation of the hexagonal units in the graphene plane (i.e. tube wall) with
the tube axis, the nanotube may behave electrically as either a metal or a semiconductor.
Other potential applications are varied and numerous, and include the following:
 More efficient solar cells
 Better capacitors to replace batteries
 Heat removal applications
 Cancer treatments (target and destroy cancer cells)
 Biomaterial applications (e.g. artificial skin, monitor and evaluate engineered tissues)
 Body armor
 Municipal water-treatment plants (more efficient removal of pollutants and
contaminants)

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 Figure 26: The structure of a single-walled carbon nanotube

Density Computation for Ceramics

It is possible to compute the theoretical density of a crystalline ceramic material from unit cell
data. Formula is as follows:

Where n’ = the number of formula units within the unit cell

ΣAC = the sum of the atomic weights of all cations in the formula unit
ΣAA = the sum of the atomic weights of all anions in the formula unit
VC = the unit cell volume
NA = Avogadro’s number, 6.022*1023 formula units/mol
By formula unit, we mean all the ions that are included in the chemical formula unit. For
example, for BaTiO3, a formula unit consists of one barium ion, one titanium ion and three
oxygen ions.

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Processing of Ceramics
Many of the metal-forming operations rely on casting and/or techniques that involve some form
of plastic deformation. Because ceramic materials have relatively high melting temperatures,
then casting is normally impractical. Furthermore, in most instances the brittleness of these
materials precludes deformation. So, Ceramics are manufactured by the techniques employed
in powder metallurgy.
Steps which are generally involved in the processing of ceramics are shown below:

Figure 27: Steps involved in the processing of Ceramics

Making Powders
Many methods are available for the preparation of ceramic powders. These can be divided into
just three basic types:
Mechanical
Mechanical methods use coarse-grained materials that have generally been derived from
naturally occurring minerals. They are subjected to a series of processes collectively referred
to as comminution in which the particle size is gradually reduced. The final step is known as
milling which produces particles of the desired size. Mechanical methods of powder production
are used widely in the production of traditional ceramic products where high purity powders
are not required and cost is one of the most important requirements
Chemical
Chemical methods such as sol-gel processing offer several advantages over mechanical
methods because they allow exceptional control over particle morphology and purity. Chemical
processes are used widely in the production of advanced ceramic materials.
Vapor Phase
Vapor-phase processes can be used to produce ceramic powders. They tend to be expensive
but offer many advantages such as the ability to produce particles of non-oxides. Vapor phase
techniques are also used to produce nanoparticles.
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Different methods of making powders are as follows:
 Powders by Precipitation
To cause precipitation it is necessary to produce a supersaturated solution. This can be achieved
by changing the pH or the temperature. A larger quantity of a soluble component (for example,
a metal salt) can be dissolved in a solution at high temperature than at a lower temperature. At
a super saturation that exceeds the concentration threshold for homogeneous nucleation, a large
number of nuclei form suddenly. Their formation lowers the solution concentration below the
concentration at which nucleation occurs but enough excess solute remains for the existing
nuclei to grow. If the solution is kept uniform growth of all the particles proceeds at the same
rate, producing powders with extremely uniform size distribution.
Precipitation of mixed oxides is possible. For example, in the fabrication of nickel ferrite (a
magnetic ceramic used for memories) a mixed aqueous solution of iron and nickel sulfates is
used. The solution is kept at about 80°C and precipitation occurs when the pH is increased to
around 11 with ammonium hydroxide. A mixed hydroxide precipitates, which is washed to
remove the residual sulfate and dried to a powder with a particle size between 50nm and 1μm.
In the figure calcium zirconium aluminate powder has been prepared by precipitation method.

Figure 28: Powder by precipitation method

 Powder by Spray Drying
Spray drying is an example of powder production from solution. It is used widely for preparing
ferrites, titanates and other electrical ceramics. Fine droplets produced by an atomizer are
sprayed into a drying chamber and the powder is collected. There are different types of
atomizers. One uses ultrasonic atomization in which the solution is passed over a rapidly
vibrating piezoelectric membrane. Droplet sizes in the range of 10μm to over 100μm can be
produced.
In the drying chamber, the flow pattern of the hot air determines the completeness of moisture
removal and the maximum temperature that the particles experience. Finally the particles are
carried out of the chamber in the air stream and captured in a bag or another form of collector.
The particles produced by spray drying are often agglomerated with a primary particle size less
than 0.1μm.

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 Figure 29: Spray dryers: (a) Centrifugal atomizer with co-current air
flow. (b) Nozzle atomizer using mixed-flow conditions.

 Powder by Sol-Gel Method

Defined as the conversion of a precursor solution into an inorganic solid via inorganic
polymerization reactions induced by water.
Powders can be obtained via a sol-gel process using metal alkoxides or a combination of metal
alkoxides and metal salts.
In general, the sol-gel process consists of the following steps:
 Preparation of a homogeneous solution
 Conversion of the homogeneous solution into a sol by treatment with a suitable reagent
(generally water with or without any acid/base)
 Aging
 Shaping
 Thermal treatment/sintering
It can produce powders with a high surface area which allows sintering to nearly full density
at much lower temperatures than are normally required when the particles have been made by
other techniques.
The cost of the raw materials limits the use of the sol-gel method in producing many ceramic
powders except for those used for specialty applications.

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 Figure 30: Overview of Sol-gel process

Characterization of Powder
The physical characteristics of the powders
 State of agglomeration
Agglomeration of powder particles should be avoided.
 Size and shape of the particles
The particles can be spheroid, equiaxed, plates, fibers or needles. We prefer
spherical shape particles as these leads to more green density and homogenous structure.
 Particle size distribution and specific surface area
There should be range of particle sizes because if there are only one particle size then
structure will be porous. There should be proper distribution of sizes. The particle size and the
size distribution must ensure at the same time a compact, homogenous and reactive stacking
on sintering. Surface area plays its role in reactivity which in-turn plays its role in densification
during sintering.
Chemical characteristics of the powders
 Degree of purity
 Surface of the particles
These are important in terms of flow during the shaping and arrangement of the particles in the
green part. These factors also play part in sintering.

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Shaping
Once the constituent powders have been prepared in the desired purity and particle size most
ceramic products must be fabricated into useful shapes. Many shaping methods are used for
ceramic products and these can be grouped into three basic categories, which are not
necessarily independent.
1. Powder compaction: dry pressing, hot pressing, cold isostatic pressing etc.
2. Casting: using a mold with the ceramic or containing a liquid or slurry.
3. Plastic forming: extrusion, injection molding etc. (using pressure to shape the green
ceramic).
Powder compaction is simply the pressing of a free flowing powder. The powder may be dry
pressed (i.e., without the addition of a binder) or pressed with the addition of a small amount
of a suitable binder. The pressure is applied either uniaxially or isostatically. The choice of
pressing method depends on the shape of the final product. We make simple shapes by applying
the pressure uniaxially, more complex shapes require isostatic pressing.
Uniaxial Pressing
For uniaxial pressing, the powder is compacted in a metal die by pressure that is applied in a
single direction. The formed piece takes on the configuration of the die and platens through
which the pressure is applied.
This method is confined to shapes that are relatively simple. However, production rates are
high and the process is inexpensive. The steps involved in one technique are illustrated in figure
below.

Figure 31: Schematic representation of the steps in uniaxial powder pressing

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(a) The die cavity is filled with powder.
(b) The powder is compacted by means of pressure applied to the top die.
(c) The compacted piece is ejected by rising action of the bottom punch.
(d) The fill shoe pushes away the compacted piece and the fill step is repeated.
Isotactic Pressing
For isostatic pressing, the powdered material is contained in a rubber envelope and the pressure
is applied iso-statically by a fluid (i.e. it has the same magnitude in all directions).
More complicated shapes are possible than with uniaxial pressing. However, the isostatic
technique is more time consuming and expensive.
There are two types of isostatic pressing. One is cold isostatic pressing while other is hot
isostatic pressing.
 Cold Isostatic Pressing
Powder is weighed into a rubber bag and a metal mandrel is inserted that makes a seal with the
mouth of the rubber bag. The sealed bag is placed inside a high-pressure chamber that is filled
with a fluid (normally a soluble oil/ water mixture) and is hydrostatically pressed. The pressures
used can vary from about 20 MPa up to 1 GPa depending upon the press and the application.
Once pressing is complete the pressure is released slowly. The mold is removed from the
pressure chamber and the pressed component is removed from the mold.

Figure 32: A wet-bag isostatic pressing system.

 Hot Isostatic Pressing

The hot isostatic press (HIP) uses the simultaneous application of heat and pressure. A furnace
is constructed within a high-pressure vessel and the objects to be pressed are placed inside.
Temperatures can be up to 2000°C and pressures are typically in the range of 30–100 MPa. A
gas is used as the pressure medium. Argon is the most common gas that is used but oxidizing
and reactive gases can also be used.

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It produces dense materials without growing the grains but it is costly.

Figure 33: A hot isostatic pressing apparatus.

 Slip Casting
Slip is poured into a plaster mold wherein the plaster sucks the water out of the slip and begins
to solidify around the edge. Once a thickness is achieved the remaining liquid clay is poured
out. After some time the “casting” in the mold hardens and can be removed.
Slip casting relies entirely on the capillary action of plaster. A ceramic product made by slip
casting is hollow.
Slip casting is a low cost way to produce complex shapes and in the traditional pottery industry
it is the accepted method for the production of teapots, jugs and figurines. Large articles such
as wash-hand basins and other white-wares are also mass produced by slip casting. It is the
standard method used to make alumina crucibles and has been successfully used to make
complex structural ceramic components such as gas-turbine rotors.

Sintering
A firing operation is required after the pressing operation. During firing the formed piece
shrinks and experiences a reduction of porosity and an improvement in mechanical integrity.
These changes occur by the coalescence of the powder particles into a denser mass in a process
termed sintering.
After pressing many of the powder particles touch one another fig. 34 (a). During the initial
sintering stage, necks form along the contact regions between adjacent particles. In addition, a
grain boundary forms within each neck, and every interstice between particles becomes a pore
fig. 34 (b). As sintering progresses, the pores become smaller and more spherical fig. 34 (c).

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The driving force for sintering is the reduction in total particle surface area; surface energies
are larger in magnitude than grain boundary energies. Sintering is carried out below the melting
temperature, so that a liquid phase is normally not present.
The mass transport that is necessary to effect the changes during sintering is accomplished by
atomic diffusion from the bulk particles to the neck regions.

Figure 34: Microstructural changes that occur during Sintering

Driving Force for Sintering
The macroscopic driving force operative during sintering is the reduction of the excess energy
associated with surfaces. This can happen by (1) reduction of the total surface area by an
increase in the average size of the particles, which leads to coarsening and/or (2) the elimination
of solid/vapor interfaces and the creation of grain boundary area, followed by grain growth,
which leads to densification. These two mechanisms are usually in competition. If the atomic
processes that lead to densification dominate, the pores get smaller and disappear with time
and the compact shrinks. But if the atomic processes that lead to coarsening are faster, both the
pores and grains get larger with time.

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 Figure 35: Collection of particles can lower its energy, (a) Densification followed
by grain growth (b) Coarsening where the large grains grow at the expense of the
smaller ones.
Types of Sintering
Sintering can occur in the presence or absence of a liquid phase. In the former case, it is called
liquid-phase sintering.
In the absence of a liquid phase, the process is referred to as solid-state sintering.
 Liquid-Phase Sintering
The term liquid-phase sintering is used to describe the sintering process when a proportion of
the material being sintered is in the liquid state.
During liquid-phase sintering, the compositions of the starting solids are such as to result in the
formation of a liquid phase upon heating. The liquid formed has to have an appreciable
solubility of the solid phase and wet the solid.

Figure 36: Liquid Phase Sintering

Upon melting, a wetting liquid will penetrate between grains and exert an attractive force,
pulling them together. The combination of these forces and the lubricating effect of the liquid
as it penetrates between grains leads to the following three mechanisms that operate in
succession:
Particle rearrangement
Densification results from particle rearrangement under the influence of capillary forces and
the filling of pores by the liquid phase. This process is very rapid, and if during the early stages
of sintering, the liquid flows and completely fills the finer pores between the particles, 100
percent densification can result almost instantaneously.

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Solution re-precipitation
At points where the particles touch, the capillary forces generated will increase the chemical
potential of the atoms at the point of contact relative to areas that are not in contact. This
chemical potential gradient induces the dissolution of atoms at the contact points and their re-
precipitation away from the area between the two particles, which naturally leads to shrinkage
and densification. In addition to densification, coarsening will occur simultaneously by the
dissolution of the finer particles and their re-precipitation on the larger particles.
Solid-state sintering
Once a rigid skeleton is formed, liquid-phase sintering stops and solid-state sintering takes
over, and the overall shrinkage or densification rates are significantly reduced.

Figure 37: Shrinkage evolution of different stages of Liquid phase sintering

Relative to the other two processes, particle rearrangement is the fastest, occurring in the time
scale of minutes. The other two processes take longer since they depend on diffusion through
the liquid or solid.
 Solid State Sintering
Only solid phases present at the sintering temperature. Predominant mechanism is mass
transport (densification). Solid-state diffusion occurs in this type of sintering.
The process of solid state sintering is described in figure below:

Figure 38: Liquid Phase Sintering

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The factors which affect solid state sintering are as follows:
 Temperature: Since diffusion is responsible for sintering, clearly increasing
temperature will greatly enhance the sintering kinetics, because D is thermally
activated. Increasing the temperature usually enhances the bulk diffusion mechanisms
which lead to densification.
 Green density: Usually a correlation exists between the green density and the final
density, since higher the green density, less pore volume has to be eliminated.
 Uniformity of green microstructure: More important than the green density is the
uniformity of the green microstructure and the lack of agglomerates.
 Size distribution: Narrow grain size distributions will decrease the propensity for
abnormal grain growth.
Thermodynamics of Sintering
Thermodynamics for sintering are its driving force which is the excess of free energy of
surfaces and interfaces. For solid state sintering
dG = γsvdAsv + γssdAss
G-Gibbs free energy
γsv - solid-vapour surface energy
γss - solid-solid surface energy
Asv - solid-vapour surface area
Ass- solid-solid surface area
The directions for the matter transport will obey the principle of minimization of the potentials
gradients, i.e. Atoms will move from convex and plane surfaces to the concave ones and the
vacancies will move in the opposite directions.

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Superconductors
Superconductivity refers to the phenomenon when the resistance of a body drop to zero and
there is a diamagnetic field associated with that body. There are two properties that a material
must possess to be considered a superconductor:
1. ρ = 0
2. B = 0
Zero resistivity is observed in a superconductor at all temperatures below a critical temperature,
Tc. This is represented in a figure below. In the superconducting state an induced current will
flow indefinitely without loss. This behavior has been demonstrated experimentally when a
current has been run through a closed ring of a superconducting metal for over two and a half
years without any measurable decay. Superconductivity has been observed in all the classes of
materials: metals, ceramics, and polymers.

Figure 39: Plot of ρ versus T for a superconductor.

Examples of superconductors include Al, Cd, Hg, Nb, Ti, U, V, Nb3Sn, Nb3Ge, MgB2, UPt3
etc.

BCS Theory
The BCS theory (after Bardeen, Cooper, and Schrieffer) provides an explanation for
superconductivity at low temperatures. The theory is complicated, but the basis is that there
exists an attractive force between electrons that have about the same energy. This force causes
them, under the right circumstances, to move in pairs. These are the so-called Cooper pairs.
The criterion for superconductivity is that this attraction should be greater than the natural
repulsion between like charges. Tc corresponds to the binding energy needed to hold the Cooper
pairs together in a superconducting state.

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The origin of the attractive force is that in a lattice of positive ions, an electron will attract the
positive ions toward itself. In this region the lattice will be slightly denser as shown in figure
below. To a passing electron the local lattice distortion will appear as an increase in positive
charge density and it will be attracted toward it. The two electrons pair up in this way through
their interaction with the lattice.
The BCS theory predicts an ultimate limiting value of Tc of 30 K for electron pairing via lattice
vibrations (phonons).

Figure 40: Lattice distortion around a free electron,

which leads to the formation of Cooper pairs

High temperature Super Conductors

High-temperature superconductors (HTSC) are usually defined as having a Tc above the boiling
temperature of liquid nitrogen. The earliest nonmetallic superconductors were NbO and NbN.
Both materials have a rock-salt crystal structure.
Superconductivity in a multicomponent oxide was first observed in SrTiO3. Although Tc was
determined to be only 0.3 K, SrTiO3 has the very important perovskite structure.
The beginning of HTSC started in 1986 with the discovery of superconductivity in the
compound La2BaCuO4, which has Tc nearly 38 K.
Superconductivity essentially takes place within the CuO2 planes. The Cu–O chains can be
considered as a “charge reservoir” that is needed to transfer charge into the CuO2 planes.
Charge carriers are added by doping: adding oxygen to YBa2Cu3O6, which enters the
compound as O2− and forms Cu–O chains. To maintain charge balance, electrons are removed
from the Cu–O planes and the remaining holes are mobile (hence conduction) and form Cooper
pairs below Tc.

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Types of Super Conductors
There are two types of superconductors.
Type-I Superconductors
The superconductivity exists only below critical temperature and below a critical magnetic
field strength. They are called Type I superconductors (Soft Superconductors).
Pure metals like Cd, Pb, Ti, Al etc. are type- I superconductors.
Type- II Superconductors
They were found to have much higher critical fields and therefore could carry much higher
current densities while remaining in the superconducting state.
Useful for applications requiring high magnetic fields, such as Magnetic Resonance Imaging
(MRI) machines.
Nb3Sn, NbN, NbTi, V3Ga, V3S are examples of type- II superconductors.

Applications of Superconductors
There are many applications of superconductors few of them are given below [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.
 An area where superconductors can perform a life-saving function is in the field of bio-
magnetism. 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. Magnetic Resonance Imaging
(MRI) was actually discovered in the mid 1940's. But, the first MRI exam on a human
being was not performed until July 3, 1977. And, it took almost five hours to produce
one image.
 The Korean Superconductivity Group within KRISS has carried bio-magnetic
technology a step further with the development of a double-relaxation
oscillation. SQUID (Superconducting Quantum Interference Device) for use in
Magnetoencephalography. SQUID's are capable of sensing a change in a magnetic field
over a billion times weaker than the force that moves the needle on a compass. With
this technology, the body can be probed to certain depths without the need for the strong
magnetic fields associated with MRI's.
 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.
 Superconductors have also found widespread applications in the military.
HTSC SQUIDS are being used by the U.S. navy to detect mines and submarines. And,
significantly smaller motors are being built for navy ships using superconducting wire
and tape.

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  Another impetus to the wider use of superconductors is political in nature. The
reduction of green-house gas (GHG) emissions has becoming a topical issue due to the
Kyoto Protocol which requires the European Union (EU) to reduce its emissions by
8%. Physicists in Finland have calculated that the EU could reduce carbon dioxide
emissions by up to 53 million tons if high-temperature superconductors were used in
power plants.

References
[1] Superconductor Uses (superconductors.org) last checked (Dec 1st, 2020)
 Fundamentals of Ceramics by M.W. Barsoum.
 Ceramic Materials Science and Engineering by C. Barry Carter and M. Grant Norton.
 MATERIALS SCIENCE and ENGINEERING (An Introduction 9th edition) William
D. Callister, Jr. David G. Rethwisch

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