CERAMICS

 Comes form Greek word "keramikos" meaning

burnt stuff. The desirable properties of ceramics
are normally achieved through a high temperature
heat treatment process (firing).
 Compounds between metallic and nonmetallic
elements (e.g.,Al2O3, NaCl, SiC, SiO2)
 The atomic bonding in ceramics is mixed, ionic and
covalent, the degree of ionic character depends
on the difference of electronegativity between
the cations (+) and anions (-)
% ionic character = {1 - exp[-(0.25)(XA - XB)2]} (100).

 Generally hard and brittle.

 Generally electrical and thermal insulators.
 Can be optically opaque, semi-transparent, or
transparent
 Traditional ceramics - based on clay (pottery,
bricks, tiles, porcelain, refractories), cement, &
glass.
 “New or Advanced" ceramics - consist of pure
oxides, carbides, nitrides, and non-silicate glasses
for electronic, computer, aerospace, biomedical,
and other specialized applications
 CERAMIC STRUCTURE
 Crystalline (predominantly ionic bonds)
 Non-crystalline (or amorphous)

Crystal Structures in Ceramics with

predominantly ionic bonding
Crystal structure is defined by
 Magnitude of the electrical charge on each ion
 Charge balance dictates chemical formula (Ca2+
and F- form CaF2).
 Relative sizes of the cations and anions.
Cations wants maximum possible number of
anion nearest neighbors and vice-versa.
 Stable ceramic crystal structures: anions
surrounding a cation are all in contact with
that cation.
 For a specific coordination number, there is a
critical or minimum cation-anion radius ratio
rC/rA for which this contact can be maintained.
 Some Common Ceramic Crystal
Structures
 AX-type - those which have equal number of
cations and anions. A denotes cation, and X for
anion. Examples : a.) Rock Salt (NaCl), b.) Zinc
blende (ZnS), c.) Cesium Chloride (CsCl)
 AmXp-type - If the charges on the cations and
the anions are not the same, the compound can
exist with chemical formula AmXp, where m
and/or p is not equal to 1. An example would be
AX2 ,which is a common crystal structure found
in flourite (CaF2)
 AmBnXp- type - It is also possible for ceramics
to have more than 1 type of cation. For 2 types
of cations (represented by A & B), the chemical
formula is designated as AmBnXp.
 Silicate Ceramics

 Composed mainly of silicon and oxygen, the two most abundant

elements in earth’s crust (rocks, soils, clays,sand)
 Basic building block : SiO44- tetrahedron
 Si-O bonding is largely covalent, but overall SiO4 block has
charge of –4
 Various silicate structures – different ways to arrange SiO4-4
blocks
 Window glasses
 Most common window glasses are
produced by adding other oxides
(e.g. CaO, Na2O) whose cations
are incorporated within SiO4
network.
 The cations break the tetrahedral
network and glasses melt at lower
temperature than pure amorphous
SiO2 because.
 A lower melting point makes it
easy to form glass to make, for
instance, bottles.
 Some other oxides (TiO2, Al2O3)
substitute for silicon and become
part of the network
Silica = silicon dioxide = SiO2
 Every oxygen atom is shared
by adjacent tetrahedra
 Silica can be crystalline (e.g.,
quartz) or amorphous, as in
glass (fused or vitreous
silica)
 Imperfections in Ceramics
Point defects in ionic crystals are charged. The coulombic forces
are very large and any charge imbalance has a strong tendency to
balance itself. Electroneutrality is a state that exist when there
are equal numbers of cation and anions. To maintain charge
neutrality, defects do not occur alone (as substitutional or
interstitial), but several point defects (defect structure) can be
created. There are two types of such defects :

 Schottky defect is a pair of anion

and cation vacancies
 Frenkel defect is a pair of cation
(positive ion) vacancy and a cation
interstitial. It may also be an
anion (negative ion) vacancy and
anion interstitial. However anions
are larger than cations and it is
not easy for an anion interstitial
to form.
 A ceramic material is said to be stoichiometric,
which is a state wherein there is an exact ratio of
cation-to-anion as predicted by its chemical formula.
 Example : NaCl is stoichiometric if the cation/anion
ration is 1:1.

 A ceramic material is non-stoichiometric if

there is deviation from the exact ratio. This may
occur in some materials in which 2 valence (or ionic)
states for one of the ion-types.
 Example : FeO in which Fe can be present in both
Fe2+ and Fe3+ states, depending on the temperature.
The formation of Fe3+ disrupts electroneutrality by
introducing excess +1 charge, which must be offset
by formation of some type of defects.
 Impurities in Ceramics
 Impurity atoms can exist as
either substitutional or
interstitial solid solutions
 Substitutional ions substitute
for ions of like type
 Interstitial ions are small K+

compared to host structure –

formation of anion Na+
interstitials is unlikely
K+ impurity
 Incorporation of ion with
different charge state
requires compensation by
point defects
 Solubilities higher if ion radii
and charges match closely
 Mechanical Properties
 Hard and strong, but brittle, low toughness and low
ductility. Low toughness due to pores and other
microscopic imperfections.
 Good wear resistance - most often utilized when abrasive
or cutting actions are required.
 Good high temperature mechanical properties.
 The compressive strength is typically ten times the tensile
strength, which make them good structural materials under
compression (e.g., bricks in houses, stone blocks in the
pyramids),
 For crystalline ceramics, slip (dislocation motion) is very
difficult because of covalent bonds,
 For non-crystalline ceramic, materials deform by viscous
flow, i.e. by breaking and reforming atomic bonds, allowing
ions/atoms to slide past each other (like in a liquid).
 Thermal Properties of Ceramics
 High melting temperature due to its high bond
energy, which is proportional to melting
temperature.
 Low thermal conductivities and thermal
coefficient of expansion due to its strong ionic-
covalent bond.
 Ceramics Classification (according to
Usage/Application)
Ceramic
Materials

Glasses Abrasives Clay Cements Refractories Advanced

Products Ceramics

Glasses Glass- Structural Whitewares Fireclay Silica Basic Special

Ceramics Clay Products
Glasses are the general classification of glassy or non-crystalline
silicates, which are sub-divided into :

* Glass or quartz in which some oxides (Na2O, CaO, K2O, Al2O3)

are added to influence and improve its quality. Familiar examples
are window glasses, drinking glasss, lenses, fiber-glass, etc

* Glass-Ceramics are non-crystalline glasses transformed

partially or totally to crystalline structure by devitrification
process (proper temperature-heat treatment). These materials
have high mechanical strength, low coefficient of expansion and
can with stand thermal shock. They perform better than ordinary
glass. Some of the commercial trade names are Corningware,
Vision, Cercor, etc.

Abrasives are ceramic materials that are hard, or wear resistant

and tough (not easily fractured) that are used to wear, grind, or
cut away other materials. They are used in several forms - as
loose grains or as coated abrasives (ie bonded to grinding wheels
or in sand papers and emery cloth).
Clay Products are one of the most widely used ceramic product
because of the great abundance of the raw material which is clay
(aluminum silicates - composed of Al2O3 and SiO2). The raw
materials are formed, dried and "fired" to a finished product..
Sub-classified as :

* Structural clay products - clay products used in

construction - building bricks, tiles, sewer pipes

* Whitewares - include pottery, porcelain, tableware, china,

plumbing fixtures (sanitary ware)

Cement are materials that when mixed with water form slurries or
paste that will subsequently set and harden. The most common is
Portland cement which is a mixture of clay and lime-bearing
minerals which are "calcined" and grind to fine powder with a
small amount of gypsum is added. Other familiar ceramic material
of this type is plaster of Paris. Hardening develop only at room
temperature.
Refractories are ceramics with capacity to withstand high
temperatures without melting or decomposing. It also has ability
to provide thermal insulation. Furnace brick is a common example.
Applications are as furnace lining in power generation,
metallurgical plants, foundries, glass manufacture, etc.
Sub-divided as :

* Fireclay are alumina-silica ceramic materials used in furnace

construction to confine hot atmosphere and protect structural
members from excessive temperature. Strength is not
necessarily important because structural loading is not required.

* Silica (or acid) refractories are primarily composed of silica

which is a high-temperature load bearing material, commonly used
in arch-roof of steel and glass furnaces. They are resistant to
silica-rich slag (acidic slag), but are easily attack by slag
containing CaO or MgO (basic slags).
 * Basic refractories are ceramic materials that are rich in
magnesia (MgO), and are termed basic. Basic refractories are
resistant to slags containing MgO or CaO (basic slags), but are
attack by slag containing silica. Most applications are in steel
open-hearth furnaces.

* Special refractories are ceramic materials that are used for

specialized application. These are high purity oxides (silica,
magnesia, beryllia, zirconia, mullite) and some carbides (SiC).

Advanced Ceramics are materials whose unique particular

properties (electrical, magnetic, optical, etc), or combinations of
these properties are exploited in a host of new products of
specilized applications, such as heat engine applications, ceramic
armours, electronic packaging, as superconductors, heat shields
of space shuttle, bio-materials - teeth implants and synthetic
bones, and many others.
Ceramics are useful to the medical world.
 bioceramic materials for repair and
replacement of human hips, knees, and other
body parts.
 Ceramics also are being used to replace
diseased heart valves.
 Use of ceramics for tooth replacement implants
and braces.
 Glass microspheres smaller than a human hair
are being used to deliver large, localized
amounts of radiation to diseased organs in the
body.
 Ceramics are one of the few materials that are
durable and stable enough to withstand the
corrosive effect of bodily fluids.
Application of Ceramics on the Space Shuttle : The
melting point of aluminum is 660 ° C. The tiles keep
the temperature of the aluminum shell of the shuttle
at or below 175 ° C while the exterior temperatures
can exceed 1400 ° C. The tiles cool off rapidly, so that
after exposure to such high temperatures they are
cool enough to be held in the bare hand in about 10
seconds. Surprisingly, the thickness of these ceramic
tiles varies from only 0.5 inches to 3.5 inches.
 Ceramics Fabrication/ Forming Techniques
Ceramics Fabrication Techniques

Glasses Forming Cementation Particulate

Process Process Forming Process

Pressing Drawing Blowing Fiber Powder Hydroplastic Slip Tape

Forming Pressing Forming Casting Casting

Hot Uniaxial Isostatic

Drying

Firing
Glass Network Modifiers
Most silicate glasses contain “Network Modifiers”. Network modifiers are oxides such
as Na2O and CaO which supply cations (positive ions) to the structure. The addition of
Na2O to a silica glassintroduces two Na+ ions, and produces two non-bridging oxygens
(i.e. induces oxygen bridge failure).

General Characteristics of Glasses

 Short range atomic order but no long-range order
 Structure is isotropic, so the properties are uniform in all directions
 Typically good electrical and thermal insulators
 Soften before melting, so they can be formed easily by various forming
techniques.
 Glass Forming Techniques

Pressing Drawing

Blowing
Fiber
Drawing
 Heat Treatment of Glasses
 Annealing at elevated temperatures is used to remove thermal
stresses that result from inhomogeneous temperatures during
cooling (similar to annealing of metals)

 Tempering - heating the glass above the glass transition

temperature but below the softening point and then quenched in an
air jet or oil bath.
The interior, which cools later than the outside, tries to contract
while in a plastic state after the exterior has already become rigid.
This causes residual compressive stresses on the surface and
tensile stresses inside.
In fracture, a crack has first to overcome the residual
compressive stress, making tempered glass less susceptible to
fracture. Tempering is used in automobile windshields, glass doors,
eyeglass lenses, etc.
Processing of Ceramics Using the Particulate
(Powder) Forming Techniques
Powder

Precursor Preparation

Drying
Precursor
(agglomerates/granules/ suspension, pastes)
Binder Burn-out
Forming *
(Pressing, Slip Casting, Extrusion) Sintering (Firing)

Green Compact Final Product

Illustration of Ceramic Forming Techniques/Methods
Die pressing - is accomplished by placing the powder into a die
and applying pressure to achieve a desired level of compaction.
Products : Insulating, dielectric, and magnetic ceramics for
electrical devices; Substrates, Capacitors.

Slip casting - the main steps are :

I.) Preparation od stable suspension (slip). Suspensions are
prepared by mixing ceramic powders and additives (binders,
dispersing agents) with liquid (water or solvent)
ii.) Pouring the slip into the porous mold (plaster of Paris)
iii.) When sufficient wall thickness is formed, the excess slip poured
out of the porous mold.
iv.) The cast material is allowed to dry in the mold, and then
removed.
v.) The dried product is fired (sintered)

Extrusion - the ceramic paste is placed in an evacuated cylinder,

the paste is then forced thru a die, As the shaped ceramic
paste exits from the extruder, it is supported on a suitable flat or
shaped surfaces to prevent distortion and cut into required
lengths.
 Sintering (or “Firing”)
 the final stage of ceramic processing in which porous powder
compacts are converted to the dense material.
 The driving force for the mass transport during the sintering process
is the reduction of the free energy of system (The decrease in surface
area and lowering of the surface free energy by the elimination of
solid-vapor interfaces).
 The driving force usually takes place with the formation of new, but
lower energy, solid-solid interfaces