 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 contain oxygen
as an impurity)
 Dopants  elements/compounds that are deliberately added,
in known concentrations, at specific locations in the
microstructure, with an intended beneficial 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 effect of
dopants on the properties of materials is useful.
 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
 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.
 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 fit 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 cation–vacancy and a cation–interstitial 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.
 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
 The glasses are a familiar group
of ceramics; e.g. containers,
lenses, window and fiberglass
 Non crystalline silicates with
other oxide (e.g. CaO, Na2O,
K2O & Al2O3) influence the
glass properties.
 A typical soda–lime glass
consists of approximately 70
wt% SiO3, the balance being
mainly NaO (soda) and CaO
(lime)
 Optical transparency & relative
ease to fabricated
 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
 Very popular products (abundant, inexpensive, easy to be
formed)
 Contain nonplastic ingredient which affect the change that
take place during the drying and firing processes  the
characteristics of the finished piece
 two broad classifications: the structural clay products and
the whitewares.
 Structural clay products include bricks, tiles, and sewer
pipes—applications in which structural integrity is important.
 whiteware ceramics become white after the high-temperature
firing group are porcelain, pottery, tableware, china, and
plumbing fixtures, sanitary ware
 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 classifications:
 For many commercial materials, the raw ingredients consist
of both large and fine particles, which may have different
compositions.
 Upon firing, the fine 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 fired.
 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.
 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 first 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.
 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 fired
 The properties of portland cement,
including setting time and final
strength, to a large degree depend
 on its composition.