CRYSTAL STRUCTURE

and GEOMETRY
Space
lattice
Unit cell
Cubic
system
APF
Density
calculatio

Miller indices
Positions
Directions
Planes
Linear & planar
density
Structure
mapping
XRD, SEM, TEM

INTRODUCTION
Significant property differences
exist between the crystalline
and non-crystalline materials
having the same composition
Properties of some materials are directly related
to their crystal structures.
Crystallography is the branch of science that
deals with the geometric description of crystals
and their internal arrangement.
2

Materials and Packing

SOLID

CYSTALLINE
-due to orderly structure of their atoms molecules or
ions possess well defined shaped.
Examples: metal, ceramic, polymer, alloy

AMORPHOUS
-poor or no long range order and do not
solidify with symmetry or cystalline solids

CRYSTALLINE
-atoms/ion arranged in a pattern that repeat itself in 3 dimensions
and they form a solid that has long range order (LRO)
AMORPHOUS
-atoms/ions are not arranged in a long range order, periodic and
repeatable manner and possess only short range order (SRO)

Materials and Packing

Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers

crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.

Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.

Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems
(Table 3.1 Smith)
*stress on CUBIC only
14 crystal lattices
(Bravais lattices)
a, b, and c are the lattice constants
6

An imaginary network of lines, with atoms at

intersection of lines, representing the
arrangement of atoms is called space lattice.

Unit cell is that block of

atoms which repeats itself
to form space lattice.

 7 different types of unit cells necessary to

create all point lattices.
August Bravais (1811-1863) derived 14
possible unit cells to describe all possible
lattice networks. *We learn 3 only. See Fig 3.2
Smith
In the cubic system, the 3 types of unit cells
are
Simple Cubic
Body Centered (BCC)
Face Centered (FCC)

The 14 Bravais

7 Types of Unit Cells

Cubic Unit Cell
a=b=c
= = = 900

Simple

Body Centered

Figure 3.2

Face centered

Tetragonal
a

=b c
= = = 900

Simple

Body Centered
10

 Orthorhombic
a b c
= = = 900

Simple

Base Centered
Body
Centered

Face
Centered

Rhombohedral
a

=b = c
= = 900

Simple
11

 Hexagonal
a b c
= = = 900

Simple

Monoclinic
a b c
= = = 900

Simple

Triclinic
a b c
= = = 900

Figure 3.2

Simple
12

PRINCIPAL METALLIC CRYSTAL

STRUCTURES
90% of the metals have either: Body Centered
Cubic (BCC), Face Centered Cubic (FCC) or
Hexagonal Close Packed (HCP) crystal
structure.
**HCP is denser version of simple hexagonal
crystal structure.

13

Simple Cubic

Number of atoms in a unit cell?

1/8th of an atom are at the cube corners
=
8 corners (1/8 atom)
=
1
14

Atomic Packing Factor (APF)

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
atoms
unit cell

a
R=0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.23,
Callister 7e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell

**APF for a simple cubic structure = 0.52

15

ATOMIC PACKING FACTOR

(APF)
It is the fraction of solid sphere volume in
a unit cell, assuming the atomic hard
sphere model.
It is the maximum packing possible for
spheres all having the same diameter.
Atomic Packing Factor =

Volume of atoms in unit cell, Va

Volume of unit cell, Vc

**The higher the APF, Crystal structure is more packed.

16

SIMPLE CUBIC

where
This means that SC 52%
packed with 1 atom.
(48% empty space).
It is not a closed-packed
structure.
17

Body Centered Cubic Structure (BCC)

Represented as one atom at each corner of cube and one
at the center of cube.

(Courtesy P.M. Anderson)

--Note: All atoms are identical; the

center atom is shaded differently
only for ease of viewing.

Adapted from Fig. 3.2,

Callister 7e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

18

Body Centered Cubic (BCC)

Crystal Structure

ex: Cr, W, Fe (), Tantalum, Molybdenum

19

 Each unit cell has eight 1/8

atom at corners and 1
full atom at the center.
Therefore each unit cell has

(8x1/8 ) + 1 = 2 atoms

Atoms contact each

other at cube diagonal

Relationship between cube side length (a)

and atomic radius (R) :

Therefore, lattice
constant, a =

4R
3

20

Formula check!
Calculate 2 a
Calculate 3 a
X 2 a2 a2
X 2a

4R X 2 a 2
4 R 2 ( 2a ) 2 a 2
4 R 2 3a 2
2

4R
3

21

Atomic Packing Factor: BCC

3a

a
2a

Adapted from
Fig. 3.2(a), Callister 7e.

Close-packed directions:
length = 4R = 3 a

atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
3
a
22
unit cell

Example Question: BCC

Calculate the APF for the BCC unit cell, assuming the atoms to be hard
spheres

This means that BCC 68%

packed with 2 atoms.
(32% empty space).
BCC is not a closedpacked structure.
APF for a body-centered cubic structure = 0.68
WHAT DOES THIS MEAN?
23

Example Problem
Iron (Fe) at 20C is a BCC with atoms of atomic
radius 0.124 nm. Determine the lattice constant,
a of the cube edge of the iron unit cell.
4R=3 a
a = 4R/3

24

Solution
Solution:

a =

4R
3

= 0.2864 nm

25

Table 3.2 (Smith) Selected metals which have the BCC crystal
structure at room temperature (20C) and their lattice constants
and atomic radii
Metal

Lattice constant a, nm

*Atomic radii R, nm

Chromium

0.289

0.125

Iron

0.287

0.124

Molybdenum

0.315

0.136

Potassium

0.533

0.231

Sodium

0.429

0.186

Tantalum

0.330

0.143

Tungsten

0.316

0.137

Vanadium

0.304

0.132

*Calculated from lattice constant using equation

4R = 3 a

26

Face Centered Cubic (FCC)

Crystal Structure
FCC structure is represented as one atom each at
the corner of cube and at the center of each cube
face.

Adapted from Fig. 3.1, Callister 7e.

(Courtesy P.M. Anderson)

--Note: All atoms are identical; the face-centered atoms are shaded differently for
ease of viewing.

27

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag

4 atoms/unit cell 6 face x 1/2 atom + 8 corners x 1/8 atom

28

Face Centered Cubic (FCC)

Crystal Structure
Each unit cell has eight
1/8th atom at corners and
six atoms at the center of
six faces.
Therefore each unit cell
has:

(8 x 1/8)+ (6 x ) = 4 atoms/unit cell

29

Relationship between cube edge

length and atomic radius for FCC
a2 + a2 = 2 a

4R
2
30

Atomic Packing Factor: FCC

Close-packed directions:
length = 4R = 2 a

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell

atoms
2a

unit cell
APF =

a
Adapted from
Fig. 3.1(a),
Callister 7e.

4
3

( 2a/4) 3
a3

volume
atom
volume
unit cell
31

Face Centered Cubic

4 3
Va (4) R
3
4R

Vc a
3

2
APF 0.74

APF for a FCC structure = 0.74

(maximum achievable APF)

32

APF of FCC
APF = 0.74, which is greater than BCC
(0.68)
This means that 74% of the FCC unit cell
volume is filled by 4 atoms.
Atoms in FCC are packed as close
together as possible.
It is a close-packed structure.
26% is empty space.
33

Hexagonal Close-Packed Structure

(HCP)
The HCP structure is represented as an
atom at each of 12 corners of a hexagonal
prism, 2 atoms at top and bottom face and
3 atoms in between top and bottom face.

34

Hexagonal Close-Packed Structure

(HCP)
ABAB... Stacking Sequence
3D Projection

APF = 0.74

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer
Adapted from Fig. 3.3(a),
Callister 7e.

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn
35

Hexagonal Close-Packed Structure

(HCP)
Each unit cell has six 1/6th
atoms at each of top and
bottom layer, two half
atoms at top and bottom
layer and 3 full atoms at
the middle layer.
Therefore each HCP unit
cell has:

(2 x 6 x 1/6) + (2 x ) + 3 = 6 atoms

36

Class Exercise
1. Iron has an atomic radius of 0.124 nm
and a BCC crystal structure. Show that
APF for iron is 0.68.
2. Calculate the atomic radius of Nickel
having the lattice constant of 0.352422
nm and FCC crystal structure.
37

Densities of Material Classes

In general
metals > ceramics > polymers
30
Why?
Metals have...

Ceramics have...
less dense packing
often lighter elements

Polymers have...

(g/cm3 )

close-packing
(metallic bonding)
often large atomic masses

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

Metals/
Alloys

20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3
2
1

0.5
0.4
0.3

Titanium
Aluminum
Magnesium

Graphite/
Ceramics/
Semicond

Polymers

Composites/
fibers

Based on data in Table B1, Callister

*GFRE, CFRE, & AFRE are Glass,
Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
60% volume fraction of aligned fibers
in an epoxy matrix).
Zirconia
Al oxide
Diamond
Si nitride
Glass -soda
Concrete
Silicon
Graphite

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

Glass fibers
GFRE*
Carbon fibers
CFRE*
Aramid fibers
AFRE*

Wood
Data from Table B1, Callister 7e.

38

Density Calculation

mass unitcell

volume unitcell

n MW

Vc N A

Where:
n
=
MW =
Vc =

number of atoms per unit cell

molecular/atomic weight (g/mol)
Volume of a unit cell (m3)

NA

Avogadros No. (6.022 X 1023)

39

Theoretical Density,
Density = =
=

where

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.023 x 1023 atoms/mol
40

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
atoms
unit cell

=
volume
unit cell

a
2 52.00

a3 6.023 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

41

Volume Density

Volume density of metal =

Mass/Unit cell
Volume/Unit cell

Example:- Copper (FCC) has atomic mass of 63.54

g/mol and atomic radius of 0.1278 nm. Determine
volume density of copper.

42

Volume Density

Volume density of metal =

Mass/Unit cell
Volume/Unit cell

Example:- Copper (FCC) has atomic mass of 63.54

g/mol and atomic radius of 0.1278 nm.
a=

4R

4 0.1278nm

= 0.361 nm

Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3

FCC unit cell has 4 atoms.

v
v

(4atoms / unitcell )(63.54 g / mol )

4.7 10 29 (volume / unitcell ) 6.023 10 23 atoms / mol

m
g
8.98 3
V
cm
43

Polymorphism and Allotropy

Some materials may exist in more than
one crystal structure, this phenomenon is
called polymorphism.
If the material is an elemental solid, it is
called allotropy.
An example of allotropy is carbon, which
can exist as diamond (at high pressure)
and graphite (at ambient condition)
44

Polymorphism or Allotropy
Metals exist in more than one crystalline form. This
is caller polymorphism or allotropy.
Temperature and pressure leads to change in
crystalline forms.
Example:- Titanium, Iron, Cobalt
- Iron exists in both BCC and FCC form
Liquid
depending on the temperature.
Iron

9120C

-2730C

Iron
BCC

13940C 15390C

Iron
FCC

Iron
BCC
45

3-33

Tutorial
1. Molybdenum has a BCC crystal structure, an
atomic radius of 0.1363 nm, and an atomic
weight of 95.94 g/mol. Determine its density.
2. Calculate the radius of a palladium atom, given
that Pd has an FCC crystal structure, a density
of 12.0 g/cm3 , and an atomic weight of 106.4
g/mol.
3. Calculate the radius of a tantalum atom, given
that Ta has a BCC crystal structure, a density of
16.6 g/cm3 , and an atomic weight of 180.9
g/mol
46

4.

Below are listed the atomic weight,

density, and atomic radius for three
hypothetical alloy. For each determine
whether its crystal structure is FCC,
BCC or simple cubic. Justify your
determination.
Alloy

Atomic
weight
(g/mol)

Density
(g/cm3)

Atomic
Radius (nm)

43.1

6.40

0.122

184.4

12.30

0.146

91.6

9.60

0.137
47