STRUCTURES OF CERAMICS

REFF:
Materials Science & Engineering; An Introduction
Callister, W. D, Jr, 2007, John Wiley & Sons
Fundamental of Ceramics, Barsoum, M. W., 2003, McGraw-Hill
Engineering Materials 2; An Introduction to Microstructures,
Processing and Design, Ashby, M. F and Jones, D. R. H, 1986,
Pergamon Press

Introduction
CERAMICS: Greek keramikos = burn stuff
solid compounds formed by heat (&/P) applications followed by
cooling
desirable properties are achieved through high-T process (firing)
Firing causes irreversible transformation resulting a material that
has lost its plasticity & no longer capable to rehydrate
at least 2 elements; 1 is a non-metal, the other may be (a)
metal(s) or (an)other non

valence
The valence of an atom is the number of electrons in an atom that
participate in bonding or chemical reactions
Usually, the valence is the number of electrons in the outer s and p energy
levels.
The number of covalent bonds is determined by the number of valence
electrons
For N valence electrons, an atom can bond with other atoms 8 N
For example, N= 7 for chlorine, and 8 - N= 1, which means that one Cl
atom can bond to only one other atom.
The valence of an atom is related to the ability of the atom to enter into
chemical combination with other elements
Examples of the valence are:
Mg: 1s2 2s2 2p6 3s2 valence = 2

electronegativity

It is possible to have interatomic bonds that are partially ionic and partially covalent
the degree of either bond type depends on the relative positions of the constituent
atoms in the periodic table or the difference in their electronegativities.
Electronegativity (e greed) the tendency of an atom to gain an electron; the
power of atom to attract electrons to itself
Atoms with almost completely lled outer energy levelssuch as chlorineare
strongly electronegative and readily accept electrons.
However, atom with nearly empty outer levelssuch as sodiumreadily give up
electrons and have low electronegativity.
The wider the separation (both horizontally and vertically) from the lower left to the
upper-right-hand corner (i.e.,the greater the difference in electronegativity) in
general the more ionic the bond.
Conversely, the closer the atoms are together (i.e., the smaller the difference in
electronegativity), the greater the degree of covalency.
If the electronegativity difference between them (x)is large (indicating 1 element is
greedier than other), e attracted to the more electronegative element ion attract
each other
In general x > 1.7 ionic
x < 1.7 covalent

IONIC BONDING

When one atom may donate its valence electrons to a different atom, lling
the outer energy shell of the second atom
Both atoms now have lled/emptied outer energy levels, but both have
acquired an electrical charge and behave as ions.
The atom that contributes the electrons is left with a net positive charge and
is called a cation, while the atom that accepts the electrons acquires a net
negative charge and is called an anion.
The oppositely charged ions are then attracted to one another and produce
the ionic bond.

 Occured by transfer electron;

form between very active metallic & non metallic elements
Atoms of a metallic element easily give up their valence electrons to the
nonmetallic atoms
to form AX ionic bonding, A loses e easily, X accepts e without too much
energy input
It follows that for ionic materials to be stable, all positive ions must have
as nearest neighbors negatively charged ions in a three dimensional
scheme, and vice versa
The predominant bonding in ceramic materials is ionic.

COVALENT BONDING
the sharing of covalent bonding electrons between adjacent atoms.
Two atoms will each contribute at least one electron to the bond, and the shared
electrons may be considered to belong to both atoms.
forms when atoms have the same electronegativity energies of bonding electrons of
A & X are comparable
If the electron energy of the atoms is different transfer energy (ionic bonding)
Each instance of sharing represents one covalent bond
e.g: silicon atom, has a valence of four, obtains eight electrons in its outer energy shell
by sharing its electrons with four surrounding silicon atoms
each silicon atom is
bonded to 4 neighboring atoms by 4 covalent bonds
Many nonmetallic elemental molecules (H2, Cl2, F2 etc) as well as molecules
containing dissimilar atoms, such as CH4,H2O, HNO3, and HF, are covalently

 Characteristics of ions which affect crystal structure:

1. magnitude of electrical charged of each ions
Crystal electrically neutral
(+) charges must be balanced by an equal number of ()
chemical formula indicates ratio of + to
Ex CaF2 calcium ions (+2) & fluoride (-)
2. relative size of + and ion
Involve size/ionic radii (rc & ra)
Metalic elements give up electrons when ionized cations are smaller than
anions rc/ra <1
Each cation prefers as many neighbour anions, anions also desire a maximum
number of cation.

Stable structures require that cations and anions are in touch

Coordination number

the number of atoms touching a particular atom, or the number of nearest

neighbors for that particular atom.
number of anions neighbors for a cation) related to rc/ra
This is one indication of how tightly and effisiently atoms are packed together.
For ionic solids, the coordination number of cations is dened as the number of
nearest anions.
The coordination number of anions is the number of nearest cations.

 Table: Coordination numbers

and geometries for various
rc/ra
red cation
whte anion
Common coordination
numbers for ceramic: 4, 6 and
8
rc/ra>1 coordinate no. 12

The size of an ion depend several factors, e.g:

1. coordination number
Ionic radius increase as the number of opposite charge neighbor ions
increases
ionic radii for (coord no. 4<6<8)
2. charge on an ion
Removing e from atom/ion, the remaining valence electrons become more
tightly bound to the nucleus decrease ionic radius
Ionic size increases when electrons are added to an atom or ion
Radii for Fe: Fe2+: Fe3+ = 0.124: 0.077: 0.069

Atom arrangement

1 unit cell: the smallest group of atoms form a repetitive pattern in describing crystal
structure
represent crystal stucture

 Types of atomic or ionic arrangements:

1.No Order
These materials randomly llup whatever space is available to them.
In monoatomic gases, such as argon (Ar) atoms or ions have no orderly
arrangement.
2. Short-Range Order (SRO)
A material displays short-range order (SRO) if the special arrangement of the
atoms extends only to the atoms nearest neighbors
Amorphous/glassy/non crystalline material; e.g. glass
3. Long-Range Order (LRO)
the special atomic arrangement extends repeat periodicity >>bond length
over much larger ~>100 nm up to few cm
The atoms or ions in these materials form a regular repetitive, gridlike pattern, in
three dimension
crystalline materials; e.g. ceramics

SRO-non crystalline solid

lack a systematic and regular arrangement

arrangement of atoms over relatively large atomic distances.
also called amorphous or supercooled liquids, inasmuch as their atomic structure
resembles that of a liquid.
Whether a crystalline or amorphous solid forms depends on the ease with which a
random atomic structure in the liquid can transform to an ordered state during
solidication
An amorphous condition may be illustrated by comparison of the crystalline and
noncrystalline structures of the ceramic compound silicon dioxide (SiO2), which may
exist in both states.

Crystal structure

based on the unit cell geometry only.

Within this framework, an x, y, z coordinate system is established with its origin at
one of the unit cell corners; each of the x, y, and z axes coincides with one of the
three parallelepiped edges that extend from this corner.
The unit cell geometry is completely dened in terms of six parameters: the three
edge lengths a, b, and c, and the three interaxial angles a, , and .
These seven crystal systems are cubic, tetragonal, hexagonal, orthorhombic,
rhombohedral (also called trigonal), monoclinic, and triclinic
The cubic system, for which a = b = c and a = = = 90 , has the greatest degree of
symmetry. Least symmetry is displayed by the triclinic system, since a b c and a
.

Single crystal

when the periodic and repeated arrangement of atoms is perfect or extends

throughout the entirety of the specimen without interruption, the result is a single
crystal.
All unit cells interlock in the same way and have the same single crystal orientation.

Polycrystalline material

A polycrystalline material is comprised of many crystals with varying orientations

in space. These crystals in a polycrystalline material are known as grains.
The borders between tiny crystals, where the crystals are in misalignment and are
known as grain boundaries.

 Stages in the solidication of a polycrystalline:

Initially, small crystals or nuclei form at various positions. These have
random crystallographic orientations. The small grains grow by the
successive addition from the surrounding liquid of atoms to the structure
of each. The extremities of adjacent grains impinge on one another as the
solidication process approaches completion.

Type of crystal structure

AX: structure of NaCl, CsCl, ZnS
AmXp
AmBnXp

AX-type crystal structures

equal number of A (cation) & X (anion)

Referred as AX
3 structures: rock salt, CsCl and ZnS
Ionic & or covalent bonding
Ionic MgO; 2 e of A transferred to X, result in Mg2+ & O2Covalent ZnS; sharing elektron

Rock salt (NaCl) structure

The most common AX crystal
structure
Electrostatic attraction between
Na+ & Cl- hold the crystal together
Max. electrostatic interaction
each Na+ has 6 Cl-, no Na+
neighbours (vice versa)
Coordination number for both + &
- is 6 (octahedral)
1 unit cell generated from FCC
of anion with 1 cation in cubic
center & 1 at centered of each of
12 cube edge
NaCl, MgO, MnS, LiF and FeO

Cesium cloride (CsCl) stucture

Coordination number
for both ions is 8 (cubic)
The anions are at each
of the corners of a cube
Single cation is at the
cube center
This structure is
possible when the
anion and the cation
have the same valence

Zinc Blende (ZnS) structure

Coordinate number for both
ions is 4 (tetrahedral)
all corner and face positions
of the cubic cell are
occupied by S atoms
the Zn atoms fill interior
tetrahedral positions
Each Zn atom bonded to 4 S
atoms, vice versa
Most often the atomic
bonding is highly covalent
ZnS, ZnTe, and SiC

AmXp Type crystal structures

Charges of + & - are not the
same, m p
Example: AX2 CaF2
Ca ion at the centers of cube,
F ion in the corner
1 unit cell consists of 8 cubes

AmBnXp Type crystal structure

2 types of cation, A & B

Chemical formula AxBnXp
Ex. BaTiO3
Ba2+ ions are situated at all 8
corners of the cube, single
Ti4+ is at the centre, O2- ions
is at the centre of 6 faces

silica
The most simple: silicon
dioxide/silica
Pure silica no metal ions, every
oxygen becomes a bridge between
2 silicon atoms
Every corner oxygen atom is shared
by adjacent tetrahedra
The materials electrically neutral,
all atoms have stable electronic
structures
Ratio Si to O 1:2 (indicated by
chemical formula)
If tetrahedras are arranged in a
regular & order crystalline

SILICATE CERAMIC

Silicates are composed primarily of silicon and oxygen, abundant elements in

earths crush; soil, rock, clay
Each silicon atom bond strongly to 4 oxygen atom
Basic unit in all silicates tetrahedron (oxygen are situated at the corners, oxygen
is at the centre)
The main types of silicate ceramics: 1) alumosilicates (kaolin- or clay-based ceramic
such as porcelain and bricks; system K2O-Al2O3-SiO2) and 2) magnesium silicates
(talc-based technical ceramics; system MgO-Al2O3-SiO2).
Silicate ceramics are conventionally subdivided into coarse or fine and, according
to water absorption, into dense (< 2 % for fine and < 6 % for coarse) or porous
ceramics (> 2% and > 6 %, respectively).

Silica Glasses
A.k.a fused silica/vitreous silica
As a result, glasses are mechanically rigid like solids, yet have the
disordered arrangement of molecules like liquids
noncrystalline solid or glass, high randomness
Basic unit tetrahedron (same as the crystalline)
Pure silica forms glass with high softening T (1200 C)

Great strength and stability, low thermal expansion but hard to work with
because high in viscosity

 Commercial glasses silica glasses

add with other metal oxide to reduce
viscosity
E.g. CaO, Na2O add positive ion to
the structure &break up the network
network modifiers
Add 1 Na2O molecules introduces 2
Na+, each attaches to 1 oxygen of
tetrahedron non bridging