Structures of Metals and

Ceramics

Materials Science

Dr. Y. ElEl-Shazly

Crystalline

Structure.
Non
Non--Crystalline Structure (Amorphous)

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Dr. Y. ElEl-Shazly

Crystalline vs. Amorphous

A

crystalline material is the one in which the

atoms are situated
i
d in
i a repeating
i or periodic
i di
array over large atomic distances (long range
order).
Amorphous solids lack a systematic and regular
g
of atoms over relativelyy large
g
arrangement
atomic distances (non(non-crystalline, supersuper-cooled
liquid).
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Dr. Y. ElEl-Shazly

Rapid cooling through the freezing temperature

favours the formation of a noncrystalline solid.

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Dr. Y. ElEl-Shazly

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Dr. Y. ElEl-Shazly

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Crystalline Structure
Crystalline Material is one in which the atoms are
situated in a repeating or periodic array over large
atomic distances.
All metals, many ceramic materials, and certain
polymers form crystalline structures under normal
solidification conditions.

Atomic
At i

Hard
H d Sphere
S h M
Model:
d l atoms or ions
i
are

thought of as being solid spheres having well defined

diameters touching its neighbours.
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Dr. Y. ElEl-Shazly

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Dr. Y. ElEl-Shazly

Lattice: A three-dimensional array of points (spheres)

coinciding with atom positions.
positions

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Dr. Y. ElEl-Shazly

Periodicity and Pattern

The long range repetition of the same atomic arrangement

is conveniently described by a regular grid called lattice.
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Dr. Y. ElEl-Shazly
Pattern * Lattice
= Structure

Unit Cell

The basic repetitive unit is called the Unit Cell.

Cell.

The Unit cell is chosen to represent the symmetry of

the crystal structure, wherein all the atom positions in
the crystal may be generated by translations of the unit
cell integral distances along each of its edges.

More than a single

g unit cell mayy be chosen for a
particular crystal structure; however, we generally use
the unit cell having the highest level of geometrical
symmetry..
symmetry

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Dr. Y. ElEl-Shazly

Lattice Parameters
The unit cell geometry is completely defined in
terms of six p
parameters (Lattice Parameters)):
z

the three edges length a, b and c.

the three inter
inter--axial angles , and .

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Dr. Y. ElEl-Shazly

Metallic Crystal Structure

Metallic

non-directional no restrictions as

tto the
th number
b andd position
iti off nearest-neighbor
t i hb
atoms relatively large numbers of nearest
neighbors dense atomic pickings' for most
metallic crystal structures.
Three relatively simple crystal structures are
found for most of the common metals: facecentered cubic, body-centered cubic,
and hexagonal close-packed.
Materials Science

Dr. Y. ElEl-Shazly

Coordination Number:

the number of atoms

forming a polyhedron around a central atom in a
crystal structure.
structure

Packing Factor (APF): the fraction

volume of atoms in a unit cell (assuming the
hard sphere
p
model))

Atomic

APF =
Materials Science

volume of atoms in a unit cell

total unit cell volume
Dr. Y. ElEl-Shazly

Body Centred Cubic

Atoms

are located at all eight corners and a

single
i l atom at the
h cube
b centre.

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Dr. Y. ElEl-Shazly

The unit cell length a and the atomic radius R are

related through:

a=

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4R
3

Dr. Y. ElEl-Shazly

Two atoms are associated with the BCC unit cell

1
8x + 1x1 = 2
8

The coordination number for the BCC crystal structure

is 8; each centre atom has as nearest neighbours its
eight corner atoms.

The

atomic packing for the BCC unit cell is:

4

2 R 3
3
= 3 = 0.68
a

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Dr. Y. ElEl-Shazly

Face--Centered Cubic Crystal Structure

Face
(FCC)
Cubic

geometry with
atoms located
l
d at each
h
of the corners and
the centers of all
cube faces.

Materials Science

Dr. Y. ElEl-Shazly

The unit cell length a and the atomic radius R

are related through:

a = 2R 2

Materials Science

Dr. Y. ElEl-Shazly

Four atoms are associated with the FCC unit cell.

8x

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1
8

+ 6x

1
=4
2

Dr. Y. ElEl-Shazly

10

The coordination number for FCC crystal structure is

12.
The
Th atomic
i packing
ki factor
f
(APF) for
f the
h FCC unit
i cellll
is:

4 R 3
3
= 3 = 0.74
a

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Dr. Y. ElEl-Shazly

The Hexagonal CloseClose-Packed crystal

structure (HCP)
The top and bottom faces of the unit cell consist of six atoms that
form regular hexagons and surround a single atom in the center.
Another plane that provides three additional atoms to the unit
cell is situated between the top and the bottom planes.

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Dr. Y. ElEl-Shazly

11

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Dr. Y. ElEl-Shazly

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12

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13

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Dr. Y. ElEl-Shazly

The coordination number for the HCP crystal

structure is the same as for the FCC: 12

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Dr. Y. ElEl-Shazly

14

The equivalence of six atoms is contained in each unit

cell:
1
6

Materials Science

x12 +

1
2

x2 + 1x3 = 6

Dr. Y. ElEl-Shazly

If a and c represent, respectively, the short and long unit

cell dimensions, the ratio c/a should be 1.633; however,
for some HCP metals this ratio deviates from the ideal
value.
value

APF=
APF
= 0.74
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Dr. Y. ElEl-Shazly

15

Density computations
=

Number of atoms per unit cell*Atomic weight

Volume of unit cell*Avogadro's number

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Dr. Y. ElEl-Shazly

Copper has an atomic radius of 0.128 nm (1.28), an

FCC crystal structure
structure, and an atomic weight of 63.5
63 5
g/mol.
Compute its theoretical density and compare the answer
with its measured density.
=

Materials Science

Number
N
b off atoms
t
per unit
it cell*Atomic
ll*At i weight
i ht
Volume of unit cell*Avogadro's number

Dr. Y. ElEl-Shazly

16

BCC

FCC

HCP

Number of
atoms per UC

Coordination
Number

12

12

Atomic
Packing Factor

0.68

0.74

0.74

a(R)

4R
3

4R
2

a=2R, c/a=1.63

Crystalline
Lattice

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Dr. Y. ElEl-Shazly

Ceramic Crystal Structure

More than one element.
Ionic
I i + Covalent
C l bonding.
b di
Electrically neutral.
The relative ionic radii of the cations and anions: For a
specific coordination number, there is a critical or
cationanion
minimum rC/rA ratio for which this cation
contact is established.

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Dr. Y. ElEl-Shazly

17

Materials Science

Dr. Y. ElEl-Shazly

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Dr. Y. ElEl-Shazly

18

AX-TYPE CRYSTAL STRUCTURES

Some of the common ceramic materials are those in

which there are equal numbers of cations and anions.
anions
These are often referred to as AX compounds, where A
denotes the cation and X the anion.

Rock

Salt Structure
Cesium Chloride Structure
Zinc Blende Structure

Materials Science

Dr. Y. ElEl-Shazly

Rock Salt Structure

The coordination number for both cations and anions
is 6
The cationanion radius ratio is between approximately
0.414 and 0.732.

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Dr. Y. ElEl-Shazly

19

Materials Science

Dr. Y. ElEl-Shazly

Cesium Chloride Structure

The coordination number is 8 for both ion types.
The
Th anions
i
are located
l
d at each
h off the
h corners off a cube,
b
whereas the cube center is a single cation, and vice
versa.

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Dr. Y. ElEl-Shazly

20

Zinc Blende Structure

sphalerite
The coordination number is 4; that is, all ions are
tetrahedrally coordinated.
coordinated
Most often the atomic bonding is highly covalent in
compounds exhibiting this crystal structure

Materials Science

Dr. Y. ElEl-Shazly

AmXp-TYPE CRYSTAL
STRUCTURES
If the charges on the cations and anions are not the
same a compound can exist with the chemical formula
same,
AmXp , where m and/or p 1.
CaF2

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Dr. Y. ElEl-Shazly

21

AmBnXp-TYPE CRYSTAL
STRUCTURES
Barium titanate (BaTiO3)
Perovskite
P
ki crystall structure

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Dr. Y. ElEl-Shazly

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Dr. Y. ElEl-Shazly

22

Ceramics Density
=

n / ( AC + AA )
VC N A

n the number of formula units within the unit cell

AC the sum of the atomic weights of all cations in the

formula unit
AA the sum of the atomic weights of all anions in the
formula unit
VC the unit cell volume
NA Avogadros number

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Dr. Y. ElEl-Shazly

SILICATE CERAMICS
Each atom of silicon is bonded to four oxygen atoms,
which are situated at the corners of the tetrahedron.
tetrahedron
Often the silicates are not considered to be ionic
because there is a significant covalent character to the
interatomic SiO bonds
Various silicate structures arise from the different ways
in which the SiO444- units can be combined into one-,
one
two-, and three-dimensional arrangements.

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Dr. Y. ElEl-Shazly

23

Materials Science

Dr. Y. ElEl-Shazly

SILICA
The most simple silicate material.
Crystalline
C
lli structure:There
Th are three
h primary
i
polymorphic crystalline forms of silica: quartz,
cristobalite and tridymite.
The atoms are not closely packed together - relatively
low densities.

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Dr. Y. ElEl-Shazly

24

Quartz
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Dr. Y. ElEl-Shazly

Unit cell of cristobslite

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Dr. Y. ElEl-Shazly

25

POLYMORPHISM AND
ALLOTROPY
Polymorphism: A phenomenon where some metals
metals,

as well as nonmetals, may have more than one crystal

structure.
When found in elemental solids, the condition is often
Allotropy.
termed Allotropy

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Dr. Y. ElEl-Shazly

THE SILICATES
For

the various silicate minerals, one, two, or

4
three
h off the
h corner oxygen atoms off the
h SiO44tetrahedra are shared by other tetrahedra to
form some rather complex structures.
Positively charged cations such as Ca2+, Mg2+,
and Al3+ serve two roles:
z

they compensate the negative charges from the

SiO44- units so that charge neutrality is achieved;
these cations ionically bond the SiO44- tetrahedra
together.

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Dr. Y. ElEl-Shazly

26

Materials Science

Dr. Y. ElEl-Shazly

Layered Silicate

A two
two--dimensional sheet or layered structure
can also be produced by the sharing of three
oxygen ions in each of the tetrahedra
tetrahedra..
For this structure the repeating unit formula may
be represented by (Si2O5)2 Electroneutrality is established by a second
planar sheet structure having an excess of
cations,, which bond to these unbonded oxygen
cations
atoms from the Si2O5 sheet.
Basic structure of the clays and other minerals.
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Dr. Y. ElEl-Shazly

27

Materials Science

Dr. Y. ElEl-Shazly

Kaolinite
Al2(Si2O5)(OH)4
(Si2O5)2- /

Al2(OH)42+

The bonding within this two-layered sheet is strong and

intermediate ionic-covalent, adjacent sheets are only
loosely bound to one another by weak Van der Waals
forces.

Materials Science

Dr. Y. ElEl-Shazly

28

Materials Science

Dr. Y. ElEl-Shazly

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Dr. Y. ElEl-Shazly

29

CARBON
Diamond, Graphite, Fullerene, Carbon nanotubes
nanotubes..
DIAMOND:
DIAMOND a variant
i off the
h zinc
i blende,
bl d in
i which
hi h
carbon atoms occupy all positions
GRAPHITE: layers of hexagonally arranged carbon
atoms. Within the layers, each carbon atom is bonded
to three coplanar neighbor atoms by strong covalent
bonds The fourth bonding electron participates in a
bonds.
weak Van der Waals type of bond between the layers.

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Dr. Y. ElEl-Shazly

Diamond
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30

Graphite
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Fullerene
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Carbon Nanotube
Dr. Y. ElEl-Shazly

31

Single crystal and polycrystalline

structure

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Dr. Y. ElEl-Shazly

Most crystalline solids are composed of a collection of

many small crystals or grains.

Such materials are termed polycrystalline

polycrystalline.

The crystallographic orientation varies from grain to

grain.

The region where two grain meets is called a grain

boundary.

The grain boundary: the boundary separating two

small grains or crystals having different crystallographic
orientations in polycrystalline materials.

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Dr. Y. ElEl-Shazly

32

Isotropy and Anisotropy

Isotropic material: having properties which do
not vary
r with
ith dire
direction.
tion
In a single crystal, the physical and mechanical
properties often differ with orientation: atoms should
be able to slip over one another or distort in relation to
one another easier in some directions than others.
When the properties of a material vary with different
orientations, the material is said to be Anisotropic.

Materials Science

Dr. Y. ElEl-Shazly

For many polycrystalline materials, the crystallographic

orientations of the individual grains are totally random.
random
Under these circumstances, even though each grain
may be anisotropic.

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Dr. Y. ElEl-Shazly

33

Crystalline vs. Amorphous

A

crystalline material is the one in which the

atoms are situated
i
d in
i a repeating
i or periodic
i di
array over large atomic distances (long range
order).
Amorphous solids lack a systematic and regular
g
of atoms over relativelyy large
g
arrangement
atomic distances (non(non-crystalline, supersuper-cooled
liquid).
Materials Science

Dr. Y. ElEl-Shazly

Rapid cooling through the freezing temperature

favours the formation of a nonnon-crystalline solid.

Materials Science

Dr. Y. ElEl-Shazly

34

Silica Glasses
Noncrystalline

silica fused silica Vitreous

silica.
ili
Network

formers: polyhedral oxide structures

that can form glassy structures: SiO2; B2O3;

GeO2.
Network modifiers: Oxides that do not form
form polyhedral networks. Rather their cations
are incorporated with and modify the SiO44network. CaO;
CaO; Na2O.
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Dr. Y. ElEl-Shazly

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Dr. Y. ElEl-Shazly

35

 Intermediates:

Oxides that substitute for

silicon and become part of and stabilize the
network.
The addition of these modifiers and
intermediates lowers the melting point and
viscosity of a glass, and makes it easier to form
at lower temperatures

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Dr. Y. ElEl-Shazly

36