Chapter 3

The Structure of Crystalline Solids

(Callister p47-50; p65-68; p73-80;p97-100)

Study theme outcomes: At the end of this chapter a student will be able to:
- formulate the definitions and the terms listed at the end of the chapter
- sketch BCC, FCC, BCT and HCP unit cells and indicate the location of
the atoms
- define the shape and size of the above unit cells in terms of their axial
lengths and inter-axial angles
- determine the coordination number and the number of atoms per unit cell
of the BCC, FCC, BCT and HCP unit cells
- calculate the lattice constants (a, c) of the BCC, FCC and HCP unit cells
if the size of the atoms or ions involved is given, and vice versa
- calculate the atomic packing factor (APF) of the BCC, FCC, and HCP
crystals
- distinguish between close-packed and non-close-packed directions and
planes within unit cells
- explain the difference in stacking sequence of close-packed planes in
FCC and HCP crystal types
- calculate the density of a material if the atomic mass, atomic radius, and
crystal type are given
- solve the problems referred to in the on clickUp

3.1 The Space Lattice and Unit Cells.

 Crystal Structure. A solid material has a crystal structure if the atoms

or ions are arranged in a regular pattern that repeats itself in three
dimensions (3-D).

 Space Lattice. This is represented by the points of intersection of a

network of lines in 3-D. These points represent the center of the atoms
or ions in the crystal.
Each point in the space lattice has identical surroundings.

 Unit Cell. This is the smallest portion (building block) of the space
lattice which is fully representative of the entire space lattice.

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 Fig 3.1 Space Lattice Unit Cell

The lattice constants (axial lengths a, b, c; inter-axial angles ,,) fully

define the size and the shape of the unit cell.

3.2 Principal Metallic Crystal Structures.

Most metals have simple and dense-packed crystal structures. This is due
to fact that all the atoms have the same size and due to the electropositive
nature of metals.

The more important crystal structures are:

(a) (FCC)
(b) (BCC)
(c) (HCP)
(d) (BCT)

Example:
If the cube size of the unit cell of iron is 0,287 nanometers (nm), how many
unit cells can be fitted into a length of 1 mm?

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 The FCC Crystal Structure

Fig. 3.2

Refer to the figure: Black dots represent the centers of the metal atoms.
The four spheres (atoms) at the corners of a face are in contact with the
sphere (atom) in the center of the face.

 Coordination Number (CN):

The number of nearest neighbors to each atom in the crystal lattice.
For FCC: CN = 12
 Number of atoms per unit cell:
For FCC: Atoms per unit cell =6x½+8x⅛=4
 The Atomic Packing Factor (APF)

APF = Volume of atoms per unit cell

The volume of the unit cell

The APF is an indication of the packing density of atoms for each specific
crystal type.

The FCC structure has the densest packed atoms, thus:

APF = 4 x 4/3 x  x R3 / a3 but a = 22*R or 4R/√2

FCC: APF = 0,74

See examples: Callister 4.1 & 4.2

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 Examples of FCC metals: Al, Cu, Pb, Ni, Au

The BCC crystal structure.

Fig 3.3: BCC structure

 Coordination Number (CN):

for BCC: CN = 8

 Number of atoms per unit cell:

for BCC: Atoms per unit cell =1+8x⅛=2

 The relationship between cube side (lattice constant) and atomic

radius:
R = atomic radius
a = lattice constant (cube side)

Fig 3.4: Length of the cube diagonal

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Example 3.1: Iron is BCC and has an atomic radius of 0,124 nm. Calculate
its lattice constant.

 The Atomic Packing Factor (APF)

Example 3.2:

Calculate the APF for BCC.

atoms per unit cell =

volume per atom =
volume of unit cell =

APF = but for BCC a =

Thus APF for BCC = 0,68

Examples of BCC metals: Fe, Cr, Mo, V, W.

(Refer also diamond (covalent) structures

The HCP Crystal Structure

Fig 3.5: Hexagonal closed packed structure (reduced, hard

sphere model and an aggregate of atoms)
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The HCP crystal structure also has an APF of 0,74 but the mode of
packing of the atoms is different from that of FCC. (See Example problem
4.3)

Examples of HCP metals: Cd, Zn, Mg, Co

Assignment:
1) Make a free-hand sketch of the HCP unit cell and indicate
the positions of the atoms.

2) Determine the Coordination Number for HCP:

CN = 6 + 3 + 3 = 12
(central (plane ( plane
plane) below) above)

3) Number of atoms per unit cell

4) Geometrical relationships:

a = 2R and c/a = 1,633 (for ideal HCP)

Examples: Zn, Mg, Co

3.3 Polymorphism or Allotropy.

It is a phenomenon occurring in some materials, by which it transforms

from one crystal type to another, due to the change in temperature and/or
pressure.
Examples:
(1) Iron (Fe) (A metallic bond):

912C 1394C
-iron -iron -iron
(BCC) (FCC) (BCC)

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(2) Carbon (C): (A covalent bond)

High T
graphite diamond
(hexagonal flakes) High P (diamond-cubic)

Table with an allotropic form for some metals (Ref. Smith Table 3.5)

Metal Structure Transformation Structure

below temp. temp. oC above temp.
Ca FCC 447 BCC
Co HCP 427 FCC
Hf HCP 1742 BCC
Li HCP -193 BCC
Na HCP -233 BCC
Tl HCP 234 BCC
Ti HCP 883 BCC
Y HCP 1481 BCC
Zr HCP 872 BCC

3.4 Crystal Systems and Bravais unit cells.

Bravais lattices or unit cells. (Callister Table 3.1)

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 Fig 3.6: The 14 Bravais lattices

These are the only 14 different ways in which atoms can be geometrically
arranged in space, in order that all the atoms within each space lattice will
have identical surroundings.

There are therefore 14 standard unit cells (Bravais) which describe all the
possible crystal structures of materials.

The type of crystal structure of each material has an important effect on its
properties and behavior.

Unit cells are divided into 7 crystal systems

The 14 unit cells could be subdivided into 4 types namely:

# simple
# body-centered
# face-centered
# base-centered

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3.5 Closed-packed Crystal Structures.
The FCC and the HCP crystal structures are both closed-packed structures
(APF =0,74). There are however two major differences:

1) In the FCC structure, successive closed-packed planes have a stacking

sequence of ABC ABC ABC, etc..
In the HCP structure, successive closed-packed planes have a
stacking sequence of AB AB AB, etc..

2) More than one set of closed-packed planes are present in the FCC
structure, each with a different orientation. Various sets of closed
packed planes are therefore intersecting each other in this structure.
The HCP structure has only one set of closed-packed planes. The
closed-packed planes have therefore only one orientation within the
crystal structure.

These differences in the stacking of closed-packed planes are the major

factors responsible for the difference in mechanical properties of FCC and
HCP metals.

The BCC crystal is not a closed-packed structure and hence has no

closed-packed planes. The most densely-packed planes in BCC are the
diagonal planes. There are a number of these planes intersecting each
other in the BCC structure.

Assignment: Sketch the BCC unit cell and indicate the position of the
atoms.
a) Sketch one diagonal plane within the BCC unit cell.
b) Make a separate sketch of the plane to show the
atomic arrangement within this plane. (Use circles to
represent the atoms.)
c) Sketch the BCC unit cell and draw two possible intersecting
diagonal planes within this unit cell.

Please refer to problems in Chapter 3 and 4 of Callister of the relevant

sections.

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