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 stuf
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
Atom arrangement
1 unit cell: the smallest group of atoms form a repetitive pattern in
describing crystal structure represent crystal stucture
Characteristics of ions which afect 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 defined 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
blue cation
red 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
Crystal structure
Solid materials may be classified according to the regularity with
which atoms or ions are arranged with respect to one another. :
1.No Order=amorphous
These materials randomly fillup 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 solidification
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.
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 solidification 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+
& O2 Covalent ZnS; sharing elektron
Rock salt (NaCl) structure
The most common AX
crystal structure
Electrostatic attraction
between Na+ & Cl- hold the
crystal together
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
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
