IMPERFECTIONS & APPLICATION

OF CERAMIC

Point defect
Point defects are localized disruptions in an otherwise perfect atomic or
ionic arrangements in a crystal structure.
may be introduced by movement of the atoms or ions when they gain
energy by heating, during processing of the material or by introduction
of other atoms.
The distinction between an impurity and a dopant :
Impurities element/compounds that are present from raw materials or
processing (e.g. Si single crystals grown in quartz crucibles contain
oxygen as an impurity)
Dopants elements/compounds that are deliberately added, in known
concentrations, at specic locations in the microstructure, with an
intended benecial effect on properties or processing (e.g. P & B are
added to Si crystals to improve or alter the electrical properties of pure
silicon
the effect of impurities is deleterious, whereas the eect of dopants on
the properties of materials is useful.

2 type of point defects:

1) imperfection
defective structure: atom may remove, add,
or displace
determined by T, P & composition
2) impurity, can occur in two ways:
i) an interstitial impurity atom occupies an
interstitial site
ii) an impurity atom replaces an atom in the
perfect lattice

Imperfections in ceramics

crystalline defect a lattice irregularity having one or more

of its dimensions on the order of an atomic diameter

The simplest of the point defects is a vacancy, or vacant

lattice site

A vacancy is produced when an atom or an ion is missing

from its normal site in the crystal structure

Interstitial defect

An interstitial defect is formed when an extra atom or ion is

inserted into the crystal structure at a normally
unoccupied position

Interstitial atoms or ions, although much smaller than the

atoms or ions located at the lattice points, are still larger
than the interstitial sites that they occupy.

Consequently, the surrounding crystal region is compressed

and distorted.

Interstitial atoms such as hydrogen are often present as

impurities; whereas carbon atoms are intentionally added
to iron to produce steel.

Unlike vacancies, once introduced, the number of interstitial

atoms or ions in the structure remains nearly constant,
even when the temperature is changed.

Substitutional Defects

introduced when one atom or ion is replaced by a different type of

atom or ion

occupy the normal lattice sites.

may either be larger than the normal atoms or ions, in which case the
surrounding interatomic spacings are reduced, or smaller causing the
surrounding atoms to have larger interatomic spacings.

alter the interatomic distances in the surrounding crystal.

introduced either as an impurity or as a deliberate addition

once introduced, the defects is relatively temp. independent

Examples dopants such a (P) or boron (B) into Si.

Whether atoms or ions go into interstitial or substitutional sites

depends upon the size and valence of guest atoms or ions compared to
the size and valence of host ions.

The size of the available sites also plays a role in this.

 Atomic defects involving host atoms

for each ion vacancies & interstitial are possible
since ceramic materials contain ions of at least two kinds (+ & -),
defects for each ion type may occur
NaCl : Na & Cl each interstitials & vacancies
highly improbable that there would be appreciable concentrations
of anion (Cl) interstitials.
The anion is relatively large, and to t into a small interstitial
position, substantial strains on the surrounding ions must be
introduced.

Because the atoms exist as charged ions, when defect

structures are considered, conditions of electroneutrality
must be maintained.
Electroneutrality the state when there are equal
numbers of positive and negative charges from the ions.
consequently, defects in ceramics do not occur alone

in AX materials, defect is a cation vacancy anion vacancy

pair known as a Schottky defect

created by removing one cation and one anion from the

interior of the crystal and then placing them both at an
external surface.

Since both cations and anions have the same charge, and
since for every anion vacancy there exists a cation vacancy,
the charge neutrality of the crystal is maintained

 Defect of a cationvacancy and a cationinterstitial pair a

Frenkel defect
formed by a cation leaving its normal position vacant and
moving into an interstitial site.
There is no change in charge because the cation maintains
the same positive charge as an interstitial.

 The ratio of cations to anions is not altered by the

formation of either a Frenkel or a Schottky defect
If no other defects are present, the material is said to be
stoichiometric.
Stoichiometry as a state for ionic compounds
wherein there is the exact ratio of cations to anions
predicted by the chemical formula.
For example, NaCl is stoichiometric if the ratio of Na+
ions to Cl ions is exactly 1:1.
A ceramic compound is nonstoichiometric if there is any
deviation from this exact ratio

 Nonstoichiometry may occur for some ceramic materials in which two

valence (or ionic) states exist for one of the ion types.
Iron oxide (FeO) can be present in both Fe2+ and Fe3+ states; depends
on temperature and the ambient oxygen pressure.
The formation of an Fe3+ ion disrupts the electroneutrality of the crystal
by introducing an excess +1 charge, which must be offset by some type
of defect.
This may be accomplished by the formation of one Fe2+ vacancy (or
the removal of two positive charges) for every two Fe3+ ions that are
formed
The crystal is no longer stoichiometric because there is one more O ion
than Fe ion; however, the crystal remains electrically neutral.

Impurities in ceramics
Type: solid solutions of both substitutional and
interstitial
For an interstitial, the ionic radius of the impurity
must be relatively small in comparison to the
anion.
A substitutional impurity will substitute for the
host ion (c/a) to which it is most similar in an
electrical sense:
if the impurity atom normally forms a cation in a
ceramic material, it most probably will substitute
for a host cation.
For example, in NaCl, impurity Ca2+ and O2
ions would most likely substitute for Na+ and Cl
ions, respectively.

 To achieve any appreciable solid solubility of

substituting impurity atoms, the ionic size and charge
must be very nearly the same as those of one of the
host ions
For an impurity ion having a charge different from the
host ion for which it substitutes, the crystal must
compensate for this difference in charge so that
electroneutrality is maintained with the solid.
One way this is accomplished is by the formation
vacancies or interstitials of both ion types

APPLICATIONS

Glasses

The glasses are a familiar group

of ceramics; e.g. containers,
lenses, window and berglass

Non crystalline silicates with

other oxide (e.g. CaO, Na2O,
K2O & Al2O3) inuence the
glass properties.

A typical sodalime glass

consists of approximately 70 wt
% SiO3, the balance being
mainly NaO (soda) and CaO
(lime)

Optical transparency & relative

ease to fabricated

Glass Ceramics

Glass can be transformed to crystalline by high T heat

treatment crystallisation

Product: glass-ceramics (fine-grained polycrystalline)

Process involves nucleation & growth stage

A nucleation agent (frequently TiO2) is addded to promote

crystallization;

Commonly used as ovenware, tableware, oven window etc

Clay Products

Very popular products (abundant, inexpensive, easy to be

formed)

Contain nonplastic ingredient which affect the change that

take place during the drying and ring processes the
characteristics of the nished piece

two broad classications: the structural clay products and

the whitewares.

Structural clay products include bricks, tiles, and sewer

pipesapplications in which structural integrity is
important.

whiteware ceramics become white after the

high-temperature ring group are porcelain, pottery,
tableware, china, and plumbing xtures, sanitary ware

Refractories

Properties: the capacity to withstand high temperatures

without melting or decomposing, endure at high T, capacity
to remain inert in severe enviroment, provide thermal
insulation
Common product bricks
Application: metal refining, glass manufacturing,
metallurgical heat treatment, power generation
the performance of a refractory ceramic, to a large degree,
depends on composition.
there are several classications:

For many commercial materials, the raw ingredients consist

of both large and ne particles, which may have different
compositions.

Upon ring, the ne particles normally are involved in the

formation of a bonding phase, which is responsible for the
increased strength of the brick

The service temperature is normally below that at which

the refractory piece was red.

the optimum porosity depends on the conditions of service.

Porosity is one microstructural variable that must be

controlled to produce a suitable refractory brick. Strength,
load-bearing capacity, and resistance to attack by

corrosive materials all increase with porosity reduction.

At the same time, thermal insulation characteristics and

resistance to thermal shock are diminished.

Abrasives

used to wear, grind, or cut

away other material, which
necessarily is softer.

Properties: hardness/wear
resistance, tough

Diamond; silicon carbide,

tungsten carbide,
aluminium oxide, silica
sand, diamonds

used in several forms: 1)

bonded to grinding wheels,
2) as coated abrasives,
and 3) as loose grains.

In the rst case, the abrasive particles are bonded to a

wheel by means of a glassy ceramic or an organic resin

Coated abrasives are those in which an abrasive powder is

coated on some type of paper or cloth material; sandpaper
is probably the most familiar example. Wood, metals,
ceramics, and plastics are all frequently ground and
polished using this form of abrasive.

Grinding, lapping, and polishing wheels often employ loose

abrasive grains that are delivered in some type of oil- or
water-based vehicle.

Cements

cement, plaster cement of paris, and

lime

Characteristic: form paste when

mixed with water subsequently set &
hardens

act as a bonding phase that

chemically binds particulate
aggregates into a single cohesive
structure at Tr

the role of the cement is similar to

that of the glassy bonding phase that
forms when clay products and some
refractory bricks are red

The properties of portland cement,

including setting time and nal
strength, to a large degree depend on
its composition.