Crystalline Structures

Classification of Solids
SOLID MATERIALS

AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

Single Crystal

Does not have

any crystalline
structure
Has a unique Many crystals have the
crystalline structure same crystalline structure
 Crystalline Solid
 Crystalline Solids are the solid form of a substance
where :
the atoms or molecules are arranged in a
definite, repeating pattern in three
dimensions.
 Crystalline Solid
 Single crystals have an atomic structure which
repeats periodically across its whole volume. Even
at infinite length scales, each atom is related to
every other equivalent atom in the structure by
translational symmetry
i.e. single repeating pattern

Single Pyrite
Crystal

Amorphous
Solid

Single Crystal
 Polycrystalline Solid
 Polycrystalline materials are made up of an aggregate of many
small single crystals (also called crystallites or grains).
 The grains are usually 100 nm – 100 microns
in diameter. Polycrystals with grains that are
<10 nm in diameter are called nanocrystalline.
i.e. repeating pattern
nano → macro

Polycrystalline
Pyrite form
Polycrystal (Grain)
 Amorphous Solid
 Amorphous (non-crystalline) Solid is composed of
randomly orientated atoms, ions, or
molecules which do not form defined
patterns or lattice structures.
 The Unit Cell

Unit cell:
smallest
repetitive
volume which
contains the
complete lattice
pattern of a
crystal. A crystal lattice
implies a degree
of symmetry in
the arrangement
 Think of the shoeboxes as the unit cells of the shoe store

Another way to visualize crystal structure

MEE10001 Master Notes
  Rectangular solids
 Regular and repeating pattern
 Opposite sides of each box must
be parallel

What shoeboxes have in common with unit cells

MEE10001 Master Notes
 Metallic Crystal Structure
Let’s start from metallic crystal structure
 Consist only one type of atom
 Metallic bonding
– Non-directional
– Geometry is the major
influence
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 Many engineering materials
are metals
 Metal crystal structures are comparatively simple,
and therefore easy to understand as a starting point
for our studies

All metals have some form of crystal structure and

fall into three (or four) crystal structures descriptors.
 Metallic Crystal Structures
Table 3.1 Atomic Radii and Crystal Structures for 16 Metals

Allows the design of alloys from similar and

dissimilar structures
Metallic Crystal Structure – Unit Cells
Hard sphere model  sphere represents an atom ion core
1. Simple cube (SC)
Very rarely found

2. Faced-centered cubic (FCC)

Many metals Al, Ag, Au, Cu, Pt

3. Body-centered cubic (BCC)

Many metals α-Fe, Cr, Mo, W

4. Hexagonal close-packed (HCP)

Many metals Co, Mg, Ti, Zn
Metallic Crystal Structure – Unit Cells
SC
Identify properties (1-4) for all
FCC

elements or alloy structure for

• Simple cube (SC),
• Face-centered cube (FCC),
• Body-centered cube (BCC), and
• Hexagonal close-packed (HCP) BCC

Properties
1. Geometry-lattice constant “a0”⇒ edge length
2. Equivalent atoms in a unit cell
3. Atomic packing factor APF ⇒ % atoms
4. Co-ordination number
 Simple Cubic Structure (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions (directions along which atoms
touch each other) are cube edges.
• Perhaps the simplest cubic system Lattice
constant ao
is simple cubic structure.

“wire frame Cube edges

model showing
atom centres”

Hard sphere model

(Courtesy P.M. Anderson)
 Simple Cubic Structure (SC)
e.g. Polonium, Z = 84
 Hard Sphere Model  Reduced Sphere Model

Lattice constant ao Lattice constant ao

lattice constant of 3.36 Å
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http://www.webelements.com/webelements/elements/text/Po/key.html
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 Simple Cubic Structure (SC)
1. Geometry-Cell dimensions
• Very open structure
• Easy to visualize
• Pure metals do not usually form
simple cubic crystals

Lattice constant a0 =f(Radius) (Courtesy P.M. Anderson)

R R Atoms are assumed to

touch along face edges
Lattice parameter is a constant

a0
a0 = 2R
??
 Simple Cubic Structure (SC)
2. Equivalent atoms in a unit cell

Adapted from Fig 3.24,

Callister 8e

• Corner atoms are shared among eight cells

• A total of how many whole atoms may be
assigned to a SC unit cell???? 1
∴ 8 × =1 atom
8
(Courtesy P.M. Anderson)
 Simple Cubic Structure (SC)
3. Atomic Packing Factor (APF)
 The fraction of the cell that is filled up with atom
(The rest is empty)
 % of atom in a unit cell
 In crystalline materials,
Total volume of atoms in a unit cell (Vs )
Atomic Packing Factor =
Volume of one unit cell (Vc )

• APF of a crystal structure is dimensionless and always

less than unity (< 1).
• Assume that atoms are rigid spheres.
 Simple Cubic Structure (SC)
3. Atomic Packing Factor (APF) Adapted from Fig 3.24,
Callister 8e
Vsphere
A.P.F. =
Vcell
4 3
# atoms × π r a0
= 3
a03
r a0 = ?2r
4 3 4
1 atom × π r π
A.P.F. = ? 3 = 3 = 0.52
( 2r )
3
8
 Simple Cubic Structure (SC)
4. Coordination Number
• the number of nearest neighbours to any atom.
• the number of other atoms directly linked to
that specified atom.
• Indicates how tightly and efficiently
atoms are packed together.

∴ What is coordination number for SC?

Coordination Number for SC = 6
 Face-Centered Cubic Structure (FCC)
• Most compact structure
• Most common metal structure
• e.g.: Al, Cu, Au, Pt, Pb, Ni
Atoms are arranged at the
corners and centre of
each cube face of the cell.

Atoms are assumed to

touch along face diagonals

Hard sphere
Reduced
model
sphere
model

Lattice constant ao Aggregate of

many atoms
Adapted from Fig 3.1,
(Courtesy P.M. Anderson)
Callister 7e
 Face-Centered Cubic Structure (FCC)
1. Geometry-Cell dimensions
 The cube length or lattice parameter, a, is related to the
atomic radius R, in the cell: Lattice parameter, a =f(Radius)

Atoms are
assumed to
touch along a
a0 face diagonals

a
a0 =
4R a +a
2 2

a = a0 4R
R=r Lattice constant a0= a= = 2 2R
2
 Face-Centered Cubic Structure (FCC)
2. Equivalent atoms in a unit cell

• Corner atoms are shared

among eight cells
• Face-centered atoms are
shared among two cells

A total of how many whole atoms may be assigned

to a FCC unit cell???? ∴ Number of atoms in a unit cell
 1  1
=  8 ×  +  6 ×  = 4 atoms/unit cell
 8  2
8 corners 6 faces
Face-Centered Cubic Structure (FCC)
3. Atomic Packing Factor (APF)
4 3
# atoms × π r
A.P.F. = 3
Vcell
4 3
4 atoms × π r
A.P.F. = ? 3
a = ?2
( 2 2r )
3 2R

4 Vcell = a 3
4× π
= 3
= 0.74
( )
3
2 2
Face-Centered Cubic Structure (FCC)
4. Coordination Number
• the number of nearest neighbours to
any atom.
∴ What is coordination number for FCC?
Coordination Number
for FCC = 4 top
+ 4 bottom
+ 4 middle

= 12
Body-Centered Cubic Structure (BCC)
1. Geometry-Cell dimensions
• Close packed directions are cube diagonals.
• Moderately compact
• e.g. Cr, Fe (α), Mo, Ta, W

Lattice constant ao Reduced Aggregate of

Hard sphere
sphere many atoms
model
model
Adapted from Fig 3.2,
(Courtesy P.M. Anderson)
Callister 7e
Body-Centered Cubic Structure (BCC)
1. Geometry-Cell dimensions

 The cube length or lattice parameter, a, is

related to the atomic radius R, in the cell:

Atoms are assumed

to touch along body
R diagonals a

??

4R
a
a = a0 = ??
Unit cell side, a0 = f(R) 3
Adapted from Fig 3.2 (a),
Callister 7e
 Body-Centered Cubic Structure (BCC)
2. Equivalent atoms in a unit cell

• Centre atom is alone in cell

• Corner atoms are shared
among eight cells

Adapted from Fig 3.2 (a),

Callister 7e ∴ Number of atoms in a BCC unit cell
 1
=1 +  8 ×  =2 atoms/unit cell
 8
Body-Centered Cubic Structure (BCC)
3. Atomic Packing Factor (APF)
4 3
# atoms × π r
A.P.F. = 3
Vcell r

A.P.F. = ?0.68
a
Body-Centered Cubic Structure (BCC)
4. Coordination Number

Each center atom is surrounded by the

eight corner atoms
∴Coordination Number for BCC = 8
Hexagonal Close-Packed Structure (HCP)
1. Geometry-Cell dimensions
• Exhibits Non-Cubic Symmetry
on a & c axes
– c:a Ratio ≈ 1.633
• Built up in an A-B Stacking Pattern
c

A
B
a A
B
a A
a = 2R
??
Adapted from Fig 3.3, Callister 8e
Hexagonal Close-Packed Structure (HCP)
2. Equivalent atoms in a unit cell
Atoms per Cell =?
 1
 12 ×  corners
 6
 1
c  2 ×  top/bottom
 2

3 middle

a
Number of atoms in a HCP
unit cell = 6
Hexagonal Close-Packed Structure (HCP)
3. Atomic Packing Factor (APF)
4 3
# atoms × π r
A.P.F. = 3
≠ a3 c
Vcell
a = 2r
4
6 atoms × π r 3 a c ≈ 1.633a
= 3 a
3a 2 cos 30°× c a 30°
Area of a parellelogram
h = h×a
4 3 60° = a cos 30°× a
6 atoms × π r
3 = a 2 cos 30°
=
h
cos 30° =

3 ( 2r ) ( cos 30° )(1.633 × 2r )

2 a

Total Base Area =

3 × a 2 cos 30°

Thus APF = 0.74 volume=

of HCP base area × height
Hexagonal Close-Packed Structure (HCP)
3. Atomic Packing Factor (APF)
4 3
# atoms × π r
A.P.F. = 3
≠ a3 c
Vcell
4 a = 2r
6 atoms × π r 3 a c ≈ 1.633a
= 3
3a 2 c sin 60° Area of a triangle
1
a = ab sin C
4 3 2
6 atoms × π r 60°
a =
1 2
a sin 60°
= 3 2 c
3 ( 2r ) (1.633 × 2r )( sin 60° )
2

volume=
of HCP base area × height
1 
Thus APF = 0.74 = 6 ×  a 2 sin 60°  × c
2 
 Maximum Packing Factor
The maximum packing factor occurs in
close-packed structures
• FCC and HCP have the same APF, which is 0.74
• 0.74 means 74% of the unit cell are filled with atoms.
• In a HCP structure, each unit cell contains six atoms,
resulting a very efficient packing.
 Hexagonal Close-Packed

Metals, including Be,

Mg, Ti, Co, and Zn.
 Face-Centered Cubic
Hexagonal Close-Packed Structure (HCP)
4. Coordination Number
• For 3 stacking planes below, consider the
CENTRE atom
• Observe the centre atom’s
nearest neighbours
• 6 Surrounding in centre plane
• 3 Touching from below
• 3 Touching from above

Thus,
Coordination Number for HCP
= 6 + 3 + 3 =12
 Atomic Packing in Ceramics

Similar
to
metals-
but
ceramics
have two
or more
different
atoms
(a): Hexagonal unit cell (b): Cubic unit cell with
with a W-C atom pair a Si-C atom pair
associated associated with each
with each lattice point lattice point
 Comparison of Crystal Structures
Crystal Lattice Atoms per Packing Coordination
Structure constant, a0 Cell Factor Number
Simple Cubic a0 = 2r
(SC)
1 0.52 6
Body-Centered a0 =
4r
Cubic (BCC)
2 0.68 8
3
Face-Centered
a0 = 2 2 r 4 0.74 12
Cubic (FCC)
Hexagonal a0 = 2r
Close-Packed
c0 ≈ 1.633a0
6 0.74 12
(HCP)
 Density Computations
 Density of a material can be determined theoretically
from the knowledge of its crystal structure (from its
unit cell information)
Mass mass of the unit cell
Density =
Volume
unit cell volume, Vc

Number of atoms Mass

=Mass × g
unit cell atom mol

Mass Atomic Weight, A

=
atom Avogadro's Number, N A
g mol 6.022 ×1023 atoms
= ×
mol atoms mol
 Theoretical Density, ρ
The theoretical density of a material can be calculated using
the properties of the crystal structure HOW?

Mass of Atoms in Unit Cell

Density = ρ =
Total Volume of Unit Cell
nA
ρ=
Vc N A
where n = number of atoms/unit cell
A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = 6.022 x 1023 atoms/mol (Avogadro’s number)

 The macro scale densities are calculated by weight &

physical measure of pieces of crystals
 Theoretical Density Computations
Copper has an atomic radius of 0.128 nm, an FCC crystal
structure, and an atomic weight of 63.5 g/mol. Compute its
theoretical density and compare the answer with its
measured density. FCC n=4
nA A = 63.5 g/mol
ρ=
Vc N A =r 0.128 ×10−7 cm

( 4 atoms/unit cell )( 63.5 g/mol ) a=2 2 r

=
16 2 ( 0.128 ×10−7 cm )3 /unit cell  ( 6.022 ×1023 atoms/mol ) Vc = a 3
 
( )
3
= 2 2r
= 8.89 g/cm 3
= 16 2 r 3

Theoretically determined value of ρCu = 8.89 g/cm3

Actual value of ρCu is 8.94 g/cm3
 Theoretical Density Computations
Chromium has an atomic radius of 0.125 nm, an BCC
crystal structure, and an atomic weight of 52.0 g/mol.
Compute its theoretical density and compare the answer
with its measured density. BCC

a
 Densities of Material Classes
ρmetals > ρceramic > ρpolymer
Why?
Metals have...
• close-packing (metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing (often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values
Data from Table B1, Callister 6e.
 Summary
• Atoms may assemble into crystalline or amorphous
structures.
• Common metallic crystal structures are FCC, BCC,
and HCP.
• The maximum packing factor occurs in close packed
structures.
• FCC and HCP crystal structures have the same
coordination number and atomic packing factor.
• We can predict the density of a material, provided
we know the atomic weight, atomic radius, and
crystal geometry (e.g., FCC, BCC, HCP).