Harish T.

M
Asst.Professor
Department of Mechanical Engineering
Federal Institute of Science and Technology (FISAT)

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Ceramics

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Introduction Ceramics
The wordceramicis originated from greek word
keromikos , which means burnt stuff.
Ceramics are compounds of metallic and non-metallic
elements.
Characteristics of ceramics are:
-high temperature stability
-high hardness
-brittleness
-high mechanical strength
-low elongation unde rapplication of stress
-low thermal and electrical conductivities.
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Classification Ceramics
Ceramics are classified in many ways. It is due to
divergence in composition , properties and applications.

Based on their composition, ceramics are:

-Oxides
-Carbides
-Nitrides
-Sulfides
-Fluorides
etc.

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 Classification Ceramics

Based on their specific applications ,ceramics are classified as:

-Glasses
-Clay products
-Refractories
-Abrasives
-Cements
-Advanced ceramics for special applications

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Classification Ceramics
Based on their engineering applications ,ceramics are
classified into two groups as:traditional and engineering
ceramics.

Traditional ceramicsmost made-up of clay ,silica and

feldspar

Engineering ceramicsthese consist of highly purified

aluminium oxide (Al2O3) , silicon carbide (SiC) and
silicon nitiride (Si3N4)

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 New generation ceramics: (Since better understanding
of the fundamental character of ceramics, and
parameters influencing their unique properties)

Impact: electronic, computer, communication, aerospace

and other industries.

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Crystalline Ceramics:
1) Silicates -- based on SiO2
- Ex. cement, pottery, clay, porcelain, bricks
- Si and O are very plentiful
2) Nonsilicate oxide ceramics
- Ex. alumina (Al2O3) - used for electronic;
- magnesia (MgO) - used as refractory;
-Uranium dioxide (UO2) - nuclear fuel;
-zirconia dioxide (ZrO2) - metal substitute
3) Nonoxides
- Ex. silicon carbide, SiC;
- silicon nitride, Si3N4
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CERAMIC STRUCTURES
Composed of electrically charged ions; not atoms. Partial or total ionic
bonding.
Cations: metallic ions, positively charged, since they have given up valence
electrons to non-metallic ions.
Anions: non-metallic ions, negatively charged.
CRYSTAL STRUCTURES: Influenced by two characteristics
1) Magnitude of the electrical charge on each of the component ions. The
crystal must be electrically neutral. ie., balancing of positive and negative
charges.
2) Relative sizes of Cations and Anions. Ionic radii: rccation and raanion
Since they give up electrons, Cations are usually smaller than Anions. : rc/ra
<1
Each ion desires to have as many nearest neighbours of the opposite
charge. Stable when anions are touching a cation.

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Factors that Determine Crystal Structure
1. Relative sizes of ions Formation of stable structures:
--maximize the # of oppositely charged ion neighbors
--when anions surrounding a cation are all in contact with
the cation.

- - - - - -
+ + +
- - - - - -
stable stable
unstable
2. Maintenance of
Charge Neutrality : F-
--Net charge in ceramic CaF : Ca 2+
2 cation + anions
should be zero.
--Reflected in chemical F-
formula:
AmXp
m, p values to achieve charge neutrality
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Crystal Structures in Ceramics with predominantly
ionic bonding
Crystal structure is defined by :
Magnitude of the electrical charge on each ion. Charge balance
dictates chemical formula (Ca2+ and F- form CaF2).
Relative sizes of the cations and anions. Cations wants maximum
possible number of anion nearest neighbors and vice-versa.
Stable ceramic crystal structures: anions surrounding a cation are
all in contact with that cation. For a specific coordination number
there is a critical or minimum cation anion radius ratio rC/rA for
which this contact can be maintained.

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Coordination Number

The number of adjacent atoms (ions) surrounding a

reference atom (ion) without overlap of electron
orbitals.(the number of equidistant neighbors to an
atom or ion in a unit cell crystal structure)
Radius ratio -- ratio of the radius of the central cation
to that of the surrounding anions; determines
coordination number and coordination geometry
(Table 12.1).
Critical or minimum radius ratio when all
surrounding anions just touch each other and the
central cation; determined by pure geometric
considerations

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Coordination Number
Also called ligancy
Depends on ion size (close packed)
Ideal: Like-sized atoms = 12
Calculated by considering the greatest number
of larger ions (radius R) that can be in contact
with the smaller one (radius r).

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Coordination Number

CN numbers for
ionic bonding

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 AX-type crystal structure

Rock salt structure

Sodium chloride (NaCl) is the most
common
Rc/Ra =0.414-0.732
CN=6 for both cations and anions
Unit cell: FCC arrangement of anions with
one cation at center of each of 12 cube
edges
Two interpenetrating FCC lattices
A unit cell of rock salt

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 AX-type crystal structure (continue)

Cesium chloride structure

CN=8, 8 anions at cube corners and 1 cation at center of cube,
simple cubic (not BCC)
Zinc Blende structure
CN=4, FCC structure of S with Zn at interior tetrahedral
positions

A unit cell of cesium chloride A unit cell of zinc blende

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 The AmXp type crystal structures

Fluorite (CaF2)
Rc/Ra=0.8, CN Ca=8, CN F=4
Ca atoms at center of cubes with F atoms
at cube corners, similar to CsCl, but only
1/2 of sites are filled with Ca atoms
Unit cell consists of 8 cubes

A unit cell of CaF2 (AX2)

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 The AmBnXp type crystal structures

Perovskite: Barium Titanate

Ba at cubic corner, O at center of 6
faces, Ti at body center
CNO=12, CNBa=6, and CN Ti=6
Large A cation and oxygen form an
FCC lattice Cubic--tetragonal at
1300C (Curie points)
Cubic -- orthrhombic and
rhombohedral at low T
A unit cell of perovskite crystal
structure (ABX3)

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Example: Predicting Structure of FeO

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Mechanical Properties of Ceramics

Ceramics are brittle. For brittle fracture stress

concentrators are very important. (measured fracture
strengths are significantly smaller than theoretical
predictions for perfect materials, ~ E/10 due to the
stress risers)
Fracture strength of ceramic may be greatly enhanced
by creating compressive stresses at surface (similar to
shot peening, case hardening in metals)
The compressive strength is typically ten times the
tensile strength. This makes ceramics good structural
materials under compression (e.g., bricks in houses,
stone blocks in the pyramids).

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Stress Strain curve of Ceramic

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