5.

STRUCTURE OF CRYSTALLINE SOLIDS

5.1 Crystal Structures
A crystalline solid has a structure with long range order, ie. the atoms are orderly
arranged in a repeating or periodic array over large atomic distances.

Fig. 5.1: A cubic crystal structure showing: (a) a hard sphere unit cell, (b) a reducedsphere unit cell, and (c) an aggregate of many atoms. [Adapted from W.D. Callister]
The crystal structure of a solid is determined by the manner in which atoms, ions, and
molecules are spatially arranged.

5.2 Units-Cells and Crystal Systems

Units cells are the smallest repeating units within a crystal structure.
The geometry of a unit cell is described in terms of six lattice or cell-parameters:
Cell-lengths: a, b, c
Cell-angles: , ,

Fig. 5.2: A unit cell with x, y, and z coordinates, showing cell-lengths (a, b, and c) and
cell-angles (, , and ). [Adapted from W.D. Callister]
All crystalline solids can be described by one of the seven crystal systems:
Cubic, tetragonal, hexagonal, orthorhombic, rhombohedral, monoclinic, triclinic.

Table 5.1: Characteristics of the seven crystal systems. [Adapted from W.D. Callister]

5.3 Metallic Crystal Structures

Three simple crystal structures are found in most metals:
Face-centred cubic; Body-centred cubic; Hexagonal close-packed

Fig. 5.3: Schematic representations of simple cubic, body-centred cubic, and face-centred
cubic unit cells. [Adapted from D.R. Askeland]
5.3.1 Face-Centred Cubic (FCC)

Fig. 5.4: Face-centred cubic crystal structure showing: (a) a hard sphere unit cell, (b) a
reduced-sphere unit cell, and (c) an aggregate of many atoms. [Adapted from W.D. Callister]

Atoms are located at the corners and the centres of all the cube faces.
The atoms touch one another across a face diagonal.
Each corner atom is shared among eight unit cells, whereas a face-centred atom belongs
to only two.
1
1
Therefore, there are four whole atoms in the unit cell, ie. 6( ) + 8( )
2
8

The cell length a and the atomic radius R are related by

a = 2R 2
Each atom has a coordination number (CN) of 12, ie. there are 12 nearest-neighbour or
touching atoms surrounding it.
CN indicates how tightly and efficiently atoms are packed together.
The packing density of atoms in the unit cell or atomic packing factor (APF) is 0.74
APF = volume of atoms in a unit cell / total unit cell volume
Common metals with the FCC structure are: Cu, Al, Ag, Au, Ni, Pt
Table 5.1: Atomic radii and crystal structures for some common metals. [Adapted from W.D.
Callister]

Example Problem 5.1

Show that in an FCC unit cell, its cell length a is related to the atomic radius R by a =
2R2. Hence calculate the volume of the unit cell.

Fig. 5.5: Illustration of an FCC unit cell. [Adapted from W.D. Callister]
The length of a face-diagonal is 4R; the cell volume is a3.
From the right triangle on the face,
a2 + a2 = (4R)2
a = 2R 2
Hence, the cell volume (Vc) is:
Vc = a3 = (2R 2 )3 = 16R3 2
Example Problem 5.2
Show that the atomic packing factor (APF) for the FCC crystal structure is 0.74.
APF = total volume of spheres in a unit cell / total unit cell volume
V
= s
Vc
4
The volume of each sphere is ( )R3 and there are four atoms per FCC unit cell.
3

4
16
Hence, Vs = (4)( )R3 = ( )R3
3
3

Vc = 16R3 2
Therefore

Vs
16
= ( )R3 / 16R3 2
Vc
3
= 0.74

APF =

5.3.2 Body-Centred Cubic Crystal Structure (BCC)

Fig. 5.6: Body-centred cubic crystal structure showing: (a) a hard sphere unit cell, (b) a
reduced-sphere unit cell, and (c) an aggregate of many atoms. [Adapted from W.D. Callister]
Atoms here are not as densely packed as FCC
Centre and corner atoms touch one another along the cube diagonals.
The cell length a and the atomic radius R are related by:
a=

4R
3

1
There are two whole atoms in each unit cell, ie. 1 + 8( ).
8

The coordination number of each atom is eight, ie. it has 8 surrounding neighbour atoms..
The atomic packing density or APF is 0.68.

Common metals with the FCC structure are: Cr, Fe, W, Mo, Ba, Li
Example Problem 5.3
Show that in an BCC unit cell, its cell length a is related to the atomic radius R by:
4R
.
a=
3

Fig. 5.7: Illustration of an FCC unit cell. [Adapted from W.D. Callister]
The length of the cube diagonal is 4R; the cell volume is a3.
From the right triangle on the bottom face,
a2 + a2 = 2(a2)
From the right triangle on the diagonal face,
a2 + 2a2 = 4R2
3a2 = 4R2
a=

4R
3

5.3.3 Hexagonal Close-Packed Crystal Structure (HCP)

Fig. 5.8: Illustration of an HCP unit cell. [Adapted from W.D. Callister]
Three interior midplane atoms are sandwiched between the top and bottom hexagonal
basal planes.
1
1
There are six whole atoms in the unit cell, ie. 3 + 2[6( ) + 1( )]
6
2

Usually, the

c
ratio is 1.633.
a

The cell length a and the atomic radius R are related by: a = 2R
The coordinator number of each atom is 12.
The atomic packing factor is 0.74.
Common metals with the HCP structure are: Ti, Mg, Cd, Zn

5.4 Stacking Sequences of Closed-Packed Structures

Both FCC and HCP are closed-packed structures but have a very different stacking
sequence of atoms.
FCC has a stacking sequence of ABCABC whereas it is ABABfor HCP.

Fig. 5.9: (a) A portion of a close-packed plane of atoms; A, B, and C positions are
indicated. (b) The AB stacking sequence for close-packed atomic planes [Adapted from W.D.
Callister]

Fig. 5.10: Close-packed plane stacking sequence for HCP. [Adapted from W.D. Callister]

Fig. 5.11: (a) Close-packed plane stacking sequence for FCC. (b) A corner has been
removed to show the relation between the stacking of close-packed planes of atoms and
the FCC structure; the heavy triangle outlines a (111) plane. [Adapted from W.D. Callister]
Both structures have closed-packed planes where the sphere-packing density along these
planes is the maximum.
Presence of closed-packed planes makes a metal easier to deform, ie. more ductile.

5.5 Density Calculations

Knowing the crystal structure of a solid allows its theoretical or true density () to be
calculated as follows:

nA
Vc N A

where n = number of atoms associated with each unit cell

A = atomic weight
Vc = volume of the unit cell
NA = Avogadros number (6.023 1023 atoms/mol)

Example Problem 5.4

Copper has an atomic radius of 0.128 nm (1.28 ), an FCC crystal structure, and an
atomic weight of 63.5 g/mol. Compute its density and compare the answer with its
measured density (8.94 g/cm3).
Known values for Cu:
n = 4; A = 63.5 g/mol; Vc = 16R3 2 ; R = 0.128 nm.

From

nA
nA
=
3
Vc N A (16 R 2 ) N A
=

(4)(63.5)
[16 2 (1.28 10 8 )](6.023 10 23 )

= 8.89 g/cm3

6. Crystallographic Directions and Planes

6.1 Crystallographic Directions [uvw]

Fig. 6.1: Coordinates of selected points in the unit cell. The numbers refer to the distance
from the origin in terms of the numbers of lattice parameters. [Adapted from D.R. Askeland]
Steps for determining the Miller indices [uvw] of directions:
1. Using a right-handed coordinate system, determine the coordinates of two points
that lie on the direction.

2. Subtract the coordinates of the tail point from the coordinates of the head
point.
3. Clear fractions and/or reduce the results obtained from the subtraction to lowest
integers.
4. Enclose the three numbers in square brackets [uvw]. Use a bar over the number if
negative sign.
Example Problem 6.1

Fig. 6.2: Crystallographic directions and coordinates of a unit cell. [Adapted from D.R.
Askeland]

Determine the Miller indices of directions A, B, and C.

Direction A
1.
2.
3.
4.

Two points are 1,0,0 and 0,0,0

1,0,0 0,0,0 = 1,0,0
No fractions to clear or integers to reduce
[100]

Direction B
1.
2.
3.
4.

Two points are 1,1,1 and 0,0,0

1,1,1 0,0,0 = 1,1,1
No fractions to clear or integers to reduce
[111]

Direction C
1. Two points are 0,0,1 and
2. 0,0,1

1
,1,0
2

1
1
,0,0 = ,-1,1
2
2

1
,-1,1) = -1,-2,2
2
4. [ 122 ]

3. 2(

Points to Note:

Because directions are vectors, a direction and its negative are not identical; [100]
and [ 100 ] are in opposite directions.

A direction and its multiple are identical; [100] and [200] are in the same
direction.

Certain groups of directions are equivalent; eg. [100] and [010]

<100> {[100], [ 100 ], [010], [ 010 ], [001], [ 001 ]}

Fig. 6.3: Equivalency of crystallographic directions of a form in cubic systems. [Adapted

from D.R. Askeland]

6.2 Crystallographic Planes [hkl]

Fig. 6.4: A unit-cell showing crystallographic planes and intercepts. [Adapted from D.R.
Askeland]

Steps for determining the Miller indices [hkl] of planes:

1. Identify the points at which the plane intercepts the x,y, and z coordinates in terms
of the number of lattice parameters. If the plane passes through the origin, the
origin of the coordinate system must be moved.
2. Take the reciprocals of these intercepts.
3. Clear fractions but do not reduce to lowest integers.
4. Enclose the three numbers in parentheses brackets (hkl). Use a bar over the
number if negative sign.
Example Problem 6.2

Fig. 6.5: Crystallographic planes and intercepts. [Adapted from D.R. Askeland]
Determine the Miller indices of planes A, B, and C.
Plane A

1. x = 1, y = 1, z = 1
1
1
1
2.
= 1, = 1 , = 1
x
z
y
3. No fractions to clear
4. (111)
Plane B
1. x = 1, y = 2, z =
1
1 1 1
2.
= 1, = , = 0
x
y 2 z
1
1
1
3. Clear fractions:
= 2 , = 1, = 0
x
z
y
4. (210)
Plane C
1. Move origin: x = , y = -1, z =
1
1
1
2.
= 0 , = 1 , = 0
z
x
y
3. No fractions to clear
4. ( 010 )
Points to Note:

Planes and their negatives are identical; (020) and ( 020 ) are the same.

Planes and their multiples are not identical; (010) (020).

Planes of a form are groups of equivalent planes; {110} (110), (101), (011),
( 110 ), ( 101 ), ( 011 )

In cubic systems, a direction that has the same indices as a plane is perpendicular
to that plane.

6.3 Construction of Crystallographic Planes and Directions

To construct a direction or plane in the unit cell, we simply work backwards.
Example Problem 6.3
Draw (a) the direction [ 121 ] and (b) the ( 210 ) plane in a cubic unit-cell.

(a) The coordinates of two points are 0,0,0 and 1, 2 ,1.

(b) Points of intercepts: x =

1
1
1
1
= , y = = 1, z = =
1
0
2
2

Fig. 6.6: Construction of a direction (a) and plane (b) within a unit cell. [Adapted from D.R.
Askeland]

6.4 Close-Packed Planes and Directions

Planes and directions within an unit-cell where atoms are in continuous contact.
Table 6.1: Close-packed planes and directions
Structure
Directions
BCC
<111>
FCC
<110>
HCP
<100>, <110>

Planes
None
{111}
(001), (002)

6.5 Interplanar Spacing (dhkl)

The distance between two adjacent parallel planes of atoms with the same Miller indices.
This distance (dhkl) is related to the lattice parameters ( a, b, c ) as:
a
Cubic:
d hkl =
h2 + k 2 + l 2

Hexagonal:

= 1.33

hkl

h 2 + hk 2 + k 2 l 2
+ 2
a2
c

7. X-Ray Diffraction
Allows information about the crystal structure of material to be obtained.

Fig. 7.1: (a) Destructive and (b) constructive interactions between x-rays and the crystal
structure of a material. Diffraction occurs at angles that satisfy the Bragg equation.
(Adapted from D.R. Askeland)
X-rays that strike certain crystallographic planes at specific angles are reinforced and
diffracted according to the Braggs law:
sin =

2d hkl

where = half the angle between the diffracted beam and the original beam direction,
= wavelength of the x-rays
dhkl = interplanar spacing between the planes that cause Bragg diffraction.

Fig. 7.2: (a) Schematic of an x-ray powder diffractometer showing the incident and
diffracted beam, the sample in powdered form, and the movable x-ray detector. (b) The
diffraction pattern of gold powder. (Adapted from D.R. Askeland)

Analysis of the diffraction pattern allows the identification of the unknown material and
the indexation of the diffracted peaks and their Bragg planes (hkl).
sin 2 =

4a 2

(h 2 + k 2 + l 2 )

sin 2
= (h 2 + k 2 + l 2 )
2
2
4a

BCC:

h 2 + k 2 + l 2 = 2,4,6,8,10,12,......

FCC:

h 2 + k 2 + l 2 = 3,4,8,11,12,16,......

Example Problem 7.1

The results of an X-ray diffraction experiment using x-rays with = 0.07107 nm show
that diffracted peaks occur at the following 2 angles:
Peak
1
2
3
4

Peak
5
6
7
8

2
20.20
28.72
35.36
41.07

2
46.19
50.90
55.28
59.42

Determine the crystal structure, the indices of the plane producing each peak, and the
lattice parameter ( a ) of the material.
Solution:
Peak

sin 2

sin 2

1
2
3
4
5
6
7
8

20.20
28.72
35.36
41.07
46.19
50.90
55.28
59.42

0.0308
0.0615
0.0922
0.1230
0.1539
0.1847
0.2152
0.2456

1
2
3
4
5
6
7
8

0.0308

h2 + k 2 + l 2

(hkl)

2
4
6
8
10
12
14
16

110
200
211
220
310
222
321
400

So, the crystal structure of the material is BCC.

Use any diffracted peal to determine dhkl and a , say peak 8 or (400)
d 400 =

2 sin

0.07107
= 0.071699 nm
2 sin( 29.71)

a = d 400 h 2 + k 2 + l 2 = (0.071699)(4) = 0.2868 nm

So the material is BCC iron.

References:
W.D. Callister, Jr. (2002). Materials Science and Engineering, An Introduction, 6th
Edn. Wiley.
D.R. Askeland (1998). The Science and Engineering of Materials, 3rd Edn. Stanley
Thornes.

Practice Questions (W.D. Callister):

3.3; 3.7; 3.8; 3.10; 3.12; 3.14; 3.15; 3.17; 3.26; 3.27; 3.28; 3.30; 3.33; 3.35; 3.37; 3.38;
3.43; 3.52; 3.53; 3.56; 3.58

Week-2 Tutorial Questions

Chapter 3 (Callister, 6th Edition)
3.6
3.9
3.32
3.36