Ceramics

Classification and Properties of Ceramic

Materials
Assistant Professor
Dr. Sarika Singh
Dept. of Chemistry
Manipal University, Jaipur
Structure and Properties of Ceramics

 Crystal Structures

 Silicate Ceramics

 Allotropes of Carbon

 Classification of ceramics

 Imperfections in Ceramics
 What are ceramics?

 comes from the Greece word keramicos, which means

burnt stuff
 broadly classed as inorganic, non-metallic materials
 usually a compound, or a combination of compounds,
between metallic and nonmetallic elements (mainly, O,
N, C, B)
 bonds are either totally ionic, or combination of ionic and
covalent
Typical Characteristics of Ceramic Materials
 brittle

 everlasting !!!

 load bearing ??!!

 Hard, wear-resistant, electrically and thermally insulating,

refractory, chemically stable, durable, non-magnetic.

BUT These properties are not common to ALL ceramics !!

 Some exceptions
 ZrO2 toughened
 Al2O3 (cutting tools)
 YBa2Cu3O7 (superconductor)
 (Ba,Sr)0.6Fe2O3 (magnet)

New “high-performance” ceramics properties (e.g.,

high toughness, conductive)
v need to understand structure-property relation
 unusual properties (e.g., high toughness, conductive)

 need to understand structure-property relation

 Common properties
 High melting point and high refractoriness (except glass)

 Generally electrical and thermal insulators

 Generally hard and strong with low plasticity
 Low fracture toughness (brittle)
 Chemically inert
 Many are low cost (bricks)

 Wide range of appearance

 Ceramic Structure
 It is compose of ceramics structure with more than one type of atoms
(cations, anions).
 Complex structures, based on BCC, FCC, and HCP.
 Structures are named based on the first mineral that is discovered to
have the structure. (e.g., rocksalt structure)
 It has low packing density (because of large anions)
 Silicate Structures
 It is compose of silicon and oxygen atom which are
the two most common abundant elements in earth
crust

 Basic building block: SiO44- which has tetrahedron

structure SiO44- tetrahedron

 Si-O bonding is largely covalent, but overall SiO4

block has charge of -4.

 Various silicate structures are formed by different

ways of arranging SiO44- blocks
Orthosilicates
 A wide variety minerals contains discrete SiO44- tetrahedral i.e they do not
share the corner like
 MSiO4 or M2SiO4
 ZrSiO4 or Zn2SiO4 (willemite)

SiO44-
 Pyrosilicates: Two tetrahedral unit of (SiO4)4- joined by sharing of one
corner and resulting the unit of (Si2O7)6-
Ex: Ln2Si2O7 (Ln =lanthanide) and Sc2Si2O7

(Si2O7)6-

Cyclic silicates: Two oxygen atoms per

tetrahedron are shared, ring structured may
formed. The general formula is (SiO3)n2n
Ex: (Si3O9)6-
(Si3O9)6-
like: Ca3Si3O9 (Wollastonite)
(Si6O18)12-
 2n-
Chain silicates: (SiO3)n
Simple chain silicates or pyroxenes are formed by sharing of oxygen atom of the
two corner of each tetrahedron with the other tetrahedron

2n-
(SiO3)n
2n-
Sheet silicates: (Si2O5)n
Sharing of three corner of oxygen atoms with the other tetrahedron
1. Clay minerals (kaolinite)
2. Asbestos (white)
3. Micas
Sheets Silicate

2n-
(Si2O5)n
Three dimensional sheet silicates:
Sharing of all the four corner of SiO4 with the other tetrahedron form 3D lattice
of formula SiO2
Ex: Quartz
 Classification of Ceramics
 very “traditional” (clay-based and silica-based ceramics used
for construction and other applications)
 but also are new HIGH-TECH ceramics
1. optical (transparency) (opto-electronics)
2. electronic (piezoelectric, sensor, superconductor)
3. thermo-mechanical (engine material)
4. wear-resisting (cutting tool)

In 1974, the U.S. market for the ceramic industry was estimated at $20
million. Today, the U.S. market is estimated to be over $500 billion
 Classification based on COMPOSITION
 Silicate Ceramics: presence of glassy phase in a porous structure
clay ceramics (mullite – 3Al2O3.2SiO2)
silica ceramics (cordierite – 2MgO.2Al2O3.2SiO2)
 Oxide Ceramics: dominant crystalline phase, with small glassy
phase
single oxide (Al2O3), modified oxide (zirconia toughened alumina)
mixed oxide (mullite, BaTiO3)
 Non-oxide Ceramics: carbon, SiC, BN,
Glass-ceramics: partially crystallised glass SiO2-Li2O
 Classification based on APPLICATIONS
Glasses based on SiO2, with High-performance Advanced
additions to reduce m.p. or give Ceramics special ceramics having
special properties improved toughness, wear
 containers resistance, electrical properties, etc.
 cutting tool  sensor
 households
 bearing  grinding
 optical glasses
 superconductor  laser

Traditional Vitreous Ceramics clay-based products

Natural Ceramics
 porcelain  bricks
 rocks & minerals,
 sanitary ware  refractories
 including ice;
 tiles
 bones
 Cement & Concrete
 a complex ceramics with many phases
 structural
 composite
 A crystalline materials is that the constituents ions are arranged in
regular three dimensional pattern.
“An ideal crystal is that which have same unit cell and contains same points
throughout the crystal lattice”
 The details structure of crystalline materials are misleading.

 Since the atom and ions have considerable degree of thermal vibration in the
molecules. As the temperature increase, the amount of thermal vibration
increase and if the thermal vibration of one the molecule becomes large
enough, it jump from out of its lattice site. This constitute the point defects.
 Many of the useful properties in ceramics that results from
- Missing of atoms
-impurities present in the crystal
-existence of defects
 Imperfections in Ceramics
The term imperfection or defect is described as any deviation of ideally
perfect crystal from the periodic arrangements of its constituents.
Two types of defects are generally observed in the crystals:
• Point defect
• Line defects

 Point defects: defined as deviations from the perfect atomic

arrangement. It may occurs from

 Missing atoms  Extra atom at interstitial position

 Substitution of ions
Points defect can be results of
 imperfect packing during original crystallization
OR
 thermal vibration of atoms at elevated temperature

The most common point defects are

 Schottky defects and
 Frankel defects

Stoichiometric defects: Stoichiometric defect may be defined by ionic

compounds wherein there is exact ratio of cation to anion as predicted by
chemical formula. Schottky and Frenkel defect are an example of stoichiometric
defects
 Schottky defects: Schottky defect consist of a pair of hole i.e
absent of cation and anion in the crystal lattices.

 Defects mainly occurs in highly ionic

compounds where the cation and anion
are in similar size

Example: NaCl, CsCl, KCl and KBr

 These types of defects occurs in Co-

ordination no. 6 or 8 compounds Schottky defect.
 The number of schottky defect formed per cm-3 (Ns) is given by

where N is the number of site per cm-3 that could left vacant
Qs is the work necessary to form Schottky defect.
k is Boltzmann’s constant and T is the absolute temperature
Frankel defects: Frankel defect consist of hole (i.e vacant site) and ion
occupy at interstitial position of the lattice site.

 Metal are usually smaller than anion and

occupying an interstitial positions.

 This types of defect is favoured by a large

difference in the size between cation and anion
and ionic compounds consists of co-ordination no.
4 or 6
 . Example: ZnS, AgBr, AgCl, AgI Frenkel defect.
The number of Frenkel defects, formed per cm-3 (Nf) is given by

𝑄𝑓
Nf = 𝑁𝑁 ′ exp (- )
2𝑘𝑇

where N is the number of site per cm-3 that could left vacant
N is the number alternative interstitial position per cm-3
Qf is the work necessary to form Frankel defect.
k is Boltzmann’s constant and T is the absolute temperature
 Nonstoichiometric Defects
 The ratio of the number of atoms of one kind to the number of atoms of
the other kind does not correspond exactly to the ideal whole number ratio
implied by the formula.
Example: FeO, FeS, the ratio of Fe: O, Fe: S is not exactly 1: 1 (e.g. Fe0.84O-
Fe0.94O, Fe0.9S).
 If the ratio is not exactly 1: 1, there must be either
 Excess of metal ions, or
 Deficiency of metal ions

 Electrical neutrality is maintained either by having extra electrons in the

structure, or changing the charge on some of the metal ions.
 Metal excess
This may occur in two different ways.
F-centres
 A negative ion may be absent from its lattice site, leaving a 'hole' which
is occupied by an electron, thereby maintaining the electrical balance
 This is rather similar to a Schottky defect in that there are 'holes' and
not interstitial ions, but only one 'hole' is formed rather than a pair.
 This type of defect is formed by crystals which would be expected to
form Schottky defects.
 General formula is AX1-α , where α is a small fraction.
 Nonstoichiometric form of NaCl is yellow,
 nonstoichiometric form of KCl is blue-lilac in color.
 F-centre

Metal excess defects because of absent anion.

 The crystal lattice has vacant anion sites, which are occupied by electrons. Anion
sites occupied by electrons in this way are called F-centres.

 These F-centres are associated with the colour of the compound and the more
F-centres present, the greater the intensity of the coloration.
 Interstitial ions and electrons
 Metal excess defects also occur when an extra positive ion occupies an
interstitial position in the lattice and electrical neutrality is maintained by
the inclusion of an interstitial electron.

 The general formula is A1+αX·

 This type of defect is rather like a Frenkel

defect in that ions occupy interstitial positions,
but there are no 'holes and there are also
interstitial electrons.

 Ions are different in size and have a low

coordination number
Examples: ZnO, CdO, Fe2O3 and Cr2O3. Metal excess defects interstitial cations.
 Metal deficiency
Metal-deficient compounds is represented by the general
formula A1-αX .
Metal deficiency can occur in two ways-
Positive ions absent
 If a positive ion is absent from its lattice site, the charges
can be balanced by an adjacent metal ion having an
extra positive charge.

Examples: FeO, NiO, FeS

 Fe2+ is missing from its lattice site in FeO, then there
must be two Fe3+ ions somewhere in the lattice to
balance the electrical charges.
Metal deficiency caused
by missing positive ion
 Extra interstitial negative ions
The general formula AX1+α .

 In principle it might be possible to have an extra

negative ion in an interstitial position and to balance
the charges by means of an extra charge on an
adjacent metal ion.

 However; since negative ions are usually large it would

be difficult to fit them into interstitial positions.

 No examples of crystals containing such negative

interstitial ions are known at present. Metal deficiency caused
by interstitial negative ions.
 Problem: Calculate the number of Schottky defects per cubic meter in potassium
chloride at the energy required to form each Schottky defect is 2.6 eV, while the
density for KCl (at 500 0C) is 1.955g/cm3. (k= 8.62 eV/K)
Atomic weights for potassium and chlorine (i.e., 39.10 and 35.45 g/mol), respectively.
Solution:
N (number of lattice sites per cubic meter)
Problem: Calculate the equilibrium number of vacancies per cubic meter
for copper at 100 0C. The energy for vacancy formation is 0.9 eV/atom; the
atomic weight and density (at 1000C) for copper are 63.5 g/mol and 8.40
g/cm3, respectively.

Problem: Calculate the fraction of lattice sites that are Schottky defects for
sodium chloride at its melting temperature (801°C). Assume an energy for
defect formation of 2.3 eV.
Solution:
Problems: If electroneutrality is to be preserved, what point defects are
possible in NaCl when a Ca2+ substitutes for an Na + ion? How many of these
defects exist for every Ca2+ ion?

Solution: Replacement of an Na+ by a Ca2+ ion introduces one extra positive

charge. Electroneutrality is maintained when either a single positive charge
is eliminated or another single negative charge is added. Removal of a
positive charge is accomplished by the formation of one Na+ vacancy.
Alternatively, a Cl- interstitial will supply an additional negative charge,
negating the effect of each Ca2+ ion. However, as mentioned above, the
formation of this defect is highly unlikely.
 Problems: If cupric oxide (CuO) is exposed to reducing atmospheres at elevated
temperatures, some of the Cu2+ ions will become Cu+.
(a) Under these conditions, name one crystalline defect that you would expect to
form in order to maintain charge neutrality.
(b) How many Cu+ ions are required for the creation of each defect?
(c) How would you express the chemical formula for this nonstoichiometric
material?

Solution
(a) For a Cu2+O2- compound in which a small fraction of the copper ions exist as
Cu+, for each Cu+ formed there is one less positive charge introduced (or one
more negative charge). In order to maintain charge neutrality, we must either
add an additional positive charge or subtract a negative charge. This may be
accomplished be either creating Cu2+ interstitials or O2- vacancies.
(b) There will be two Cu+ ions required for each of these defects.

(c) The chemical formula for this nonstoichiometric material is Cu1+δO

or CuO1-δ, where x is some small fraction.
Problems: Calculate the activation energy for vacancy formation in aluminum, given
that the equilibrium number of vacancies at 500°C (773 K) is 7.57 × 1023 m-3 . The
atomic weight and density (at 500°C) for aluminum are, respectively, 26.98 g/mol
and 2.62 g/cm3 .

Solution:
Problem: Would you expect Frenkel defects for anions to exist in ionic
ceramics in relatively large concentrations? Why or why not?
Solution: Frenkel defects for anions would not exist in appreciable
concentrations because the anion is quite large and is highly unlikely to exist
as an interstitial.