MME 467

Ceramics for Advanced Applications

Lecture 03
Crystal Structure of Ceramics Part-2

Md. Rafiqul Islam

Lecturer
Department of MME, BUET, Dhaka
Classification of Ceramic Structures

1. AX - type Structures
Rocksalt, CsCl, and ZnS

2. AX2 - type Structures

Fluorite, Rutile

3. AmBnOp - type Structures

Spinel, Perovskite
 STRUCTURE OF SOME
BINARY IONIC CERAMICS

Cesium Chloride Structures

 Anions in simple cubic arrangement, with

cations in interstices at the cube centres.
 The radius ratio is 0.94 (>0.732).
 The coordination number is 8 for both anions and cations.
 Cubic structure.

 Ceramics having this structure:

CsBr, TlCl, TlBr
 Rocksalt Structure

 A close-packed FCC array of larger anions,

with an FCC array of smaller cations
occupying the octahedral sites.

 It has 1:1 (AX - type) stoichiometry with

the coordination number is 6 for both
cations and anions.

Crystal structure of NaCl

 The radius ratio is (0.102 pm/0.181 pm) =
0.563
(which lies between 0.732 and 0.414).

 Example of rocksalt ceramic structure:

MgO, CaO, BaO, CdO, MnO, FeO, NiO,
all other halides of Na, Li, K and Rb,
CsF, AgCl.
 Zinc Blende Structure

 Zinc sulfide (ZnS) is a unique compound

that forms two types of crystalline
structures.
Wurtzite – hexagonal structure
Zinc blende (a.k.a. sphalerite) – cubic

 The radius ratio is 0.34.

 In order to satisfy the MX stoichiometry, only one half of

the tetrahedral sites are needed to fill with divalent
cations.
 Oxides and sulfides with smaller cations that prefer
tetrahedral coordination tend to form this structure, e.g., ZnS,
ZnO and BeO, as well as covalent compound such SiC, BN and
GaAs.
 Fluorite Structures

 The crystal will show stoichiometry as MX2.

 CaF2 is known as fluorite. The radius ratio is ~ 0.8. The Ca2+ should
have CN=8 and F- ions should have CN=4
 Calcium ions are positioned at the centers of cubes, with fluorine ions
at the corners.
 The structure is based on FCC close-packing of the cations with all
tetrahedral interstices filled by anions
 Examples: CaF2 (the mineral fluorite), BaF2, ZrO2 , UO2 and CeO2,
 Antifluorite Structures
 In antifluorite strucutre, the rC/ra ratio is close to 1, which renders it’s
cubic arrangement.
 The anions are in FCC arrangement and all tetrahedral sites are filled
by cation. The coordination numbers of cation and anion are 4 and 8,
respectively.

 The chemical stoichiometry is M2X. The connectivity of the tetrahedra

is completely edge sharing;
 Examples: Oxides of alkaline metals such as Li2O, Na2O and K2O etc
 Corundum Structures

 Structure named after compound Al2O3 . Other examples of

corundum structure: Fe2O3 and Cr2O3 .

 Two-third of the available OH sites are filled by cation. The OH

sites form a hexagonal array with the same spacing of the
oxygen layer.

Filling of 2/3 of the octahedral sites in the basal plane of corundum. Only one
close- packed anion plane is shown.
 Rutile Structures

 Rutile is one polymorph of the mineral TiO2

(anatase and brookite are being the other structures)

 The structure is based on quasi-HCP packing of oxygen

atoms with cation fill one-half of the available OH site.
 The radius ratio is 0.745/1.26 = 0.591. OH sites are too large for Ti 4+
ions

 The atoms do relax from their

positions since partial occupancy
of highly charged Ti4+ .
 The rutile structure has (6,3)-coordination. Observe that none
of the TH holes are occupied. The titanium(IV) ions lie in OH
holes.

 
 Arrangement of Ti4+ causes anisotropic diffusion of cation; along
the c-axis is much faster than in the a-axis direction.
 Perovskite Structure

 Many ternary compounds of formula ABO3 (A and B cations

differ considerably in size) crystallize in the perovskite (mineral
BaTiO3) structure.

 An FCC-derivative structure in which the larger A (Ba) cation

and oxygen anion together form the FCC lattice.

 The smaller B (Ti) cation occupies the octahedral sites and has
only oxygen as its nearest neighbours.

 The perovskite family includes:

1. titanate compounds (CaTiO3, BaTiO3, SrTiO3 and PbTiO3),
2. zirconate compounds (PbZrO3 and BaZrO3), and
3. other compounds such as BiFeO3 , LaGaO3 , LaAlO3 and KNbO3 .

Perovskite (BaTiO3) structure
Many of these compounds
crystallize in several
polymorphous modifications
having slightly distorted
perovskite structures.
For example, BaTiO3
compound can transform to
tetragonal, orthorhombic, or
rhombohedral modifications
as temperature decreases.
In each case, the displacive
transformation is
accomplished by a shift in the
titanium atom positions.
Structure of Barium Titanate

In BaTiO3 unit cell, Ti4+

and Ba2+ are shielded
form one another.
 
The bond strength of
Ti4+ and Ba2+ are 4/6
and 2/12, respectively,
thus oxygen ion need
to coordinate with four
Ba2+ and two Ti4+.

Ion position in high temperature cubic form of BaTiO3.

For BaTiO3, the oxygen octahedron coordinating Ti is larger than necessary,
being expanded by the large Ba nearest neighbours.
This is causing Ti to be unstable and displace from body centered position.
Ti atoms can shift in its position relative to O atoms surrounding it, and O
atoms can shift relative to Ba atoms at the centre of the cube.
The consequence is change of crystal symmetry, yielding
noncentrosymmetric crystal and creating net electric dipole along the c-axis.

In the room-temperature tetragonal distortion of BaTiO3, it turns out that Ti

moves towards an O atom, while the O atoms move in the opposite direction by
about the same amount, causing a total displacement of Ti4+ is about 0.15 Å.
A more drastic displacement of ions occurs in the tetragonal modification of
PbTiO3, where both O and Ti ions are placed in the same direction relative to Pb
atoms.
The axial ratio c/a is 1.04 in BaTiO3 and 1.06 in PbTiO3, and both crystals
contains electric dipoles parallel to [001].
These crystals are, therefore, said to be polarized along the c axis, and
possess ferroelectric properties.
Ion positions on (100) planes for (A) tetragonal BaTiO3 , and (B) PbTiO3.
Below room temperature, a further shifting of atoms occurs and dipoles are
produced along [110] directions. This produced orthorhombic structure of
BaTiO3.
 
Finally at 193 K, another shift occurs so that polarization direction is parallel
to [111] direction and a rhombohedral structure results.
 
All of these polymorphs of BaTiO3 possess ferroelectric properties.
 
Typical examples of application:
speakers,
microphone,
sonar transducers,
ultrasonic cleaner,
actuators for high- precession positioning.