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
 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 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 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
• 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
 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 atom’s 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 solidification 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
• 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 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
 SILICATE CERAMIC
• materials composed primarily of silicon and oxygen → abundant in earth
• the bulk of soils, rocks, clays, and sand
• Rather than characterizing the crystal
• arrangements of an SiO4 tetrahedron
• Each atom of silicon is bonded to four oxygen atoms, which are situated at the
corners of the tetrahedron; the silicon atom is positioned at the center.
• treated as a negatively charged entity.
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 material’s 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
 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