IMPERFECTIONS & APPLICATION

OF CERAMIC

 Assumed: ceramic perfect order exists

throughout crystalline materials on an
atomic scale, however, such an idealized
solid does not exist
All contain large numbers of various
defects or imperfections
Many of the properties of materials are
sensitive to deviations from crystalline
perfection; the inuence is not always
adverse
crystalline defect a lattice irregularity
having one or more of its dimensions on
the order of an atomic diameter
Classication : point defects(those
associated with one or two atomic
positions), linear (or one-dimensional)
defects, as well as interfacial defects and
impurities in solids

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
Type: vacancies, interstitial & substitutional

vacancies

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
All crystalline solids contain vacancies and, in fact, it is not
possible to create such a material that is free of these
defects.

Interstitial defect
An (self) 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.

 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.

Substitutional Defects

introduced when one atom or ion is replaced by a different

type of atom or ion which 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.

Impurities in ceramics
impurity or foreign atoms will always be present, and
some will exist as crystalline point defects.
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 (ne-grained
polycrystalline)
Process involves nucleation & growth stage
(30-90 % crystallinity)
A nucleation agent (frequently TiO2) is
addded to promote crystallization
Because there is usually no pressing and
sintering, glass-ceramics have, unlike
sintered ceramics, no pores
share many properties with both glasses and
ceramics
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 hightemperature 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 rening, 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.
Porosity must be controlled to produce a suitable refractory brick.
Strength, load-bearing capacity increase with porosity reduction.
At the same time, resistance to thermal shock are diminished.
the optimum porosity depends on the conditions of service

Abrasives

used to wear, grind, or cut

away other material, which
necessarily is softer.
Properties: hardness/wear
resistance, tough, not
easily fractured
Diamond, silicon carbide,
tungsten carbide,
aluminium oxide, silica
sand
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
One important difference is that the
cementitious bond develops at room
temperature
The properties of portland cement, including
setting time and nal strength, to a large
degree depend on its composition.