The Structure

of
Crystalline Solids
Text Book: Chapter 3 / Pages 44-89

57
 Learning Objectives
1. Describe the difference in atomic structure between crystalline and noncrystalline
materials.
2. Draw unit cells for face-centered cubic, bodycentered cubic, and hexagonal
close-packed crystal structures.
3. Derive the relationships between unit cell edge length and atomic radius for face-
centered cubic and body-centered cubic crystal structures.
4. Compute the densities for metals having facecentered cubic and body-centered
cubic crystal structures given their unit cell dimensions.
5. Given three direction index integers, sketch the direction corresponding to these
indices within a unit cell.
6. Specify the Miller indices for a plane that has been drawn within a unit cell.
7. Describe how face-centered cubic and hexagonal close-packed crystal structures
may be generated by the stacking of close-packed planes of atoms.
8. Distinguish between single crystals and polycrystalline materials.
9. Define isotropy and anisotropy with respect to material properties.
58
Levels of atomic
arrangements in materials:
(a) Inert monoatomic gases
have no regular ordering of
atoms:
(b,c) Some materials,
including water vapor,
nitrogen gas, amorphous
silicon and silicate glass
have short-range order.
(d) Metals, alloys, many
ceramics and some
polymers have regular
ordering of atoms/ions that
extends through the
material.
 Fundamental Concepts
Solid materials may be
classified according to the
regularity with which atoms
or ions are arranged with
respect to one another.
A crystalline material is one
in which the atoms are
situated in a repeating or
periodic array over large
atomic distances;
that is, long-range order
exists, such that upon
solidification, the atoms will
position themselves in a
repetitive three-dimensional
pattern, in which each atom
is bonded to its nearest-
neighbor atoms.
60
 Fundamental Concepts, cont.
• Metals, many ceramics, and some polymers have a crystalline
structure in which the atoms are arranged in a regular repeating
structure.
• The atoms form a lattice in the crystalline structure.
• The unit cell is a subdivision of the lattice that still retains the
characteristics of the lattice. In other words, unit cells are small
group of atoms which form a repetitive pattern.

A unit cell defines the crystal structure

by virtue of its geometry and the atom
positions within. By stacking unit cells,
the entire lattice can be constructed.

61
 There are 7 unique arrangements, known as crystal systems, which fill in a 3-dimensional
space.
• Although there are 7
crystal system, there are
14 distinct
arrangements of
lattice points. These
unique arrangements of
lattice points are known
as the Bravais lattices.

• Lattice points are

located at the corners,
the faces, the center or
the base of the unit
cells. In the
orthorhombic system all
four types are
represented.

The length of unit cell

edges and the angles
between
cyristallographic axes
are referred to as lattice
Bravais Lattices 62
parameters.
63
 Metallic Crystal Structures
Most elemental metals (about 90%) have three densely packed crystal structures:

 Face-centered cubic (FCC), (e.g. Cu, Al, Ag, Au, Pb, Ni, etc.)
 Body-centered cubic (BCC), (e.g. Cr, Fe, W, V, Mo, etc.)
 Hexagonal close packed (HCP) (e.g. Zn, Mg, Co, Ti, Cd, etc.)

BCC Structure FCC Structure HCP Structure

• Most metals crystallize in these dense-packed structures because energy
is released as the atoms come closer together and bond more tightly with
each other. Thus, the densely packed structures are in lower and more stable
energy arrangements.

• HCP is denser version of simple hexagonal crystal structure.

64
BCC

Unit cell

FCC

• (a) a hard sphere unit cell representation, (b) a reduced-sphere

unit cell, and (c) an aggregate of many atoms.
65
 Close-Packed Hexagonal

• Figure 3.3 For the hexagonal close-packed crystal structure, (a) a reduced-sphere
unit cell (a and c represent the short and long edge lengths, respectively), and
(b) an aggregate of many atoms.

66
 Coordination Number
• Coordination number is the number of atoms touching particular atoms, or the
number of nearest neighbors. This is one indication of how tightly atoms are packed
together.
• Each atom in the SC lattice has a coordination number of 6.
• Each atom in the BCC lattice has a coordination number of 8.
• Each atom in the FCC lattice has a coordination number of 12.
• Each atom in the HCP lattice has a coordination number of 12.

llustration of coordinations in (a) SC and (b) BCC unit cells. 6 atoms touch each atom in
SC, while the 8 atoms touch each atom in the BCC unit cell.

67
 Models for BCC

• Body-centered cubic (BCC)

In BCC structures, atoms are located at all eight corners and a single atom at
the cube center. Atoms touch along the body diagonal.
 Models for FCC

• Face-centered cubic (FCC)

In FCC structures, atoms are located at each of the corners and centers of all
the cube face . Atoms touch along the face diagonal of the cube. There are four
atomic radii along this length—two radii from the face-centered atom and one
radius from each corner.

69
 Number of Atoms per Unit Cell in Cubic Crystal Systems

A lattice point at a corner of one unit

cell is shared by seven adjacent unit
cell (thus a total of 8 cells); only one-
eighth of each corner belongs to
one particular cell.

In the SC unit cell

 1 lattice po int  corners  lattice po int
  8   1
 8 corner  unit cell  unit cell
or
 1 atom  corners  atom
 
 8 
  1
 8 corner  unit cell  unit cell

70
 Number of atoms in BCC and FCC unit cells
• One complete atom is located at the center of the unit cell, and one-eighth of a sphere
is located at each corner of the cell. Thus there is a total of 2 atoms per BCC unit.

BCC

 1 atom  corners   atom  center  atom

  8   1 1   2
 8 corner  unit cell   center  unit cell  unit cell

• There is one-half atom (i.e., one atom shared between two unit cells) in the center of
each unit cell face and one-eighth atom each unit cell corner, for a total of 4 atoms In
each FCC unit.

FCC
 1 atom  corners   1 atom  face  atom
  8     6   4
 8 corner  unit cell   2 face  unit cell  unit cell
71
Relationship between atomic radius and lattice parameter in
Cubic Crystal Systems

In the SC unit cell: Atoms touch along the edge of the cube, so:

a 0  2r SC

In the BCC: Atoms touch along the body diagonal, which

is 3a o in length. There are two atomic radii from the center
atom and one atomic radius from each of the corner atoms
on the body diagonal.
4r
BCC a0 
3

In the FCC: Atoms touch along the face diagonal of the

cube, which is 2a o in length. There are four atomic radii
along this length-two radii from the face-centered atom
4r
a0   2r 2 and one radius from each corner.
2 FCC
72
 Hexagonal-close packed (HCP) structure
• Metals do not crystallize into the simple hexagonal
crystal structure, because atomic packing factor is
too low. The atoms can attain a lower energy and a
more stable condition by forming the HCP structure.
So, HCP is a special form of the hexagonal
structure.
• In the hexagonal close packed structure, the top
and bottom faces in the unit cell consist of six corner
atoms and a single center atom. Another plane
(midplane) which is situated between the top and Schematic representation of HCP.
a and c represent the short and
bottom planes consist of three atoms. In other long edge lengths, respectively.
words, the six atoms is contained in each unit
cell; one-sixth of each of the 12 top and bottom face
corner atoms, one-half of each of the 2 center face
atoms, and all 3 midplane interior atoms.
 1 atom  corners   atom  center   1 atom  center face  atom
 12    3 1     2   6
 6 corner  unit cell   center  unit cell   2 center face  unit cell  unit cell

Aggregate of many
atoms for HCP 73
 Atomic packing Factor, APF
The APF is the sum of the sphere volumes of all atoms within a a unit
cell (assuming the atomic hard-sphere model) divided by the unit
cell volume - that is,

1. How we can determine the volume of atoms in a unit cell?

2. How we can determine total unit cell volume?

74
75
76
 The APF

 0,74 in the FCC

0,74 in the HCP

0,68 in the BCC

0,52 in the SC

 No common engineering metals have the SC structure.

77
Density Calculations

78
SOLUTION

79
SOLUTION

4(63.5 g / mol )
 23 1 8 3
 8.89 g / cm3
(6.023 x10 mol )(16 2 )(1.28 x10 cm) The computed value is in very close
aggrement with the foregoing result.
Compare to actual : Cu  8.94 g / cm3 80
 Density of BCC Iron
Example:
Determine the density of BCC iron, which has a lattice parameter of 0.2866 nm.

SOLUTION

81
 Density of BCC Iron
Example:
Determine the density of BCC iron, which has a lattice parameter of 0.2866 nm.

SOLUTION
• Atoms/cell = 2, a=0.2866 nm = 2.866  10-8 cm
• Atomic mass = 55.847 g/mol
• Volume of unit cell = (2.866  10-8 cm)3 = 23.54  10-24 cm3/cell
• Avogadro’s number NA = 6.02  1023 atoms/mol

(2)(55.847)
  7.882 g / cm3
(23.54 10  24 )(6.02 10 23 )
82
 Atomic density
Example: Niobium has an atomic radius of 0.1430 nm and a density of 8.57 g/cm3. Determine
whether it has an FCC or BCC crystal structure. Atomic weight of Nb is 92.91 g/mol.

83
 Atomic density
Example: Niobium has an atomic radius of 0.1430 nm and a density of 8.57 g/cm3. Determine
whether it has an FCC or BCC crystal structure. Atomic weight of Nb is 92.91 g/mol.

Solution:
and

For FCC:

For BCC:

84
 Allotropy (polymorphism)
• Many elements or
compounds exist in more
than one crystalline form liquid iron system
under different conditions of
tempereture and pressure. 1539ºC
This phenomenon is termed -Fe
BCC
polymorphism or allotropy.
1400ºC
• Iron exist in both BCC and
FCC -Fe
FCC crystal structures over
the temperature range from 910ºC
room temperature to its BCC
melting point 1538°C. -Fe
• Alpha (α) iron exist from -273
to 912°C and has the BCC
crystal structure.
85
.. 86
 Crystallographic Points, Directions, and Planes
When dealing with crystalline materials, it often becomes necessary to specify a particular
point within a unit cell, crystallographic direction or plane of atoms.
Crystallographic Points (Atom Positions in Cubic Unit Cell)
To locate atom positions in cubic unit cell; x, y, and z axes are used.
 y axis is the direction to the right.
 x axis is the direction coming out of the paper.
 z axis is the direction towards top.

 Negative directions are to the opposite of positive directions.

 Atom positions are located using unit distances along the axes.

x, y, and z axes for locating atom 87

Atom positions in BCC unit cell
positions in cubic unit cell
88
89
90
 Directions in Cubic Unit Cell
• Directions are especially important for metals and alloys. Because the
properties vary with crystallographic orientation.
• In cubic crystals, Direction Indices are vector components of directions
resolved along each axes, resolved to smallest integers.
• To indicate a direction in a cubic unit cell, a direction vector is drawn from an origin,
which is usually a corner of the cubic cell, until it emerges from the cube surface.
• The direction indices are enclosed by square brackets with no separating
commas.
• The letters u, v, w are used in a general sense for the direction indices in the x,
y, and z directions, respectively, and are written as [uvw]
• All parallel direction vectors have the same direction indices.

91
92
.
..

93
94
Some directions in cubic unit cell

95
Example: Draw the following direction vector in cubic unit cell

a ) 112  
b) 1 10  
c) 3 2 1
Solution
b)
a)

c)

96
Example: Draw the following direction vector in cubic unit cell

a ) 112  
b) 1 10  
c) 3 2 1
Solution
b)
a)

c)

97
Family of Directions

98
 Crystallographic Planes
•Miller Indices:
• The orientations of planes for a crystal structure are represented in a similar
manner.
• Again, the unit cell is the basis, with the three-axis coordinate system as
represented in Figure.
• In all but the hexagonal crystal system, crystallographic planes are specified by
three Miller indices as (hkl).
• Any two planes parallel to each other are equivalent and have identical indices.

99
The procedure employed in determination of the h, k, and l index
numbers is as follows:

100
101
Example: Determine the Miller
indices of the cubic crystallographic
plane shown in the figure.

Solution:
1) Transpose the plane parallel to the z axis
¼ unit to the right along the y axis as
shown in the figure so that the plane
intersects the x axis at a unit distance
from the new origin located at the lower-
right back corner of the cube.
2) The new intercepts of the transposed
plane with the coordinate axes are now
(+1, -5/12, ∞).
3) Take the reciprocals of these
intercepts to give (1, -12/5, 0).
4) Clear the 12/5 fraction to obtain

5120
for the Miller indices of this plane.
102
Example:

Solution

103
Example:

Solution

104
Example (continued):

105
106
107
Example:

108
Reversing the directions of all indices specifies another plane parallel to, on the
opposite side of and equidistant from, the origin. Several low-index planes are
below.

109
 Family of Planes {hkl}
A family of planes contains all those planes that are crystallographically
equivalent-that is, having the same atomic packing; and a family is designated
indices that are enclosed in braces-such as 100 . .

Example:

111: 111, 111, 1 11, 111, 11 1 , 111, 1 1 1 , 1 1 1

Also, in the cubic system only, planes having the same indices, irrespective of
order and sign, are equivalent.
For example, both 123 and 3 1 2 belong to the 123 family.

110
One interesting and unique characteristic of cubic crystals is that
planes and directions having the same indices are perpendicular to one
another;

however, for other crystal systems there are no simple geometrical

relationships between planes and directions having the same indices.

In cubic crystals,
[111] direction is perpendicular to (111) plane

111
 Linear and planar densities
Linear and planar densities are important considerations relative to the
process of slip-that is, the mechanism by which metals plastically deform.
Slip occurs on the most densely packed crystallographic planes and, in
those planes, along directions having the greatest atomic packing.

112
Example

113
 Linear and planar densities

Planar Density (PD) =

Example

114
 Close Packed Crystal Structures
• Both face-centered cubic (FCC) and hexagonal
close-packed (HCP) crystal structures have
atomic packing factors of 0.74 which is the most
efficient packing of atoms.

A A sites
B
C c B sites

A sites
a
FCC HCP

115
Hexagonal Close-Packed Structure (HCP)
• ABAB... Stacking Sequence • 2D Projection

• 3D Projection
Top layer

A sites
Middle layer
c B sites
Bottom layer
A sites 6 atoms/unit cell
a ex: Cd, Mg, Ti, Zn

• Coordination number= 12

• APF = 0.74

For HCP, the stacking sequence is

termed AB. This stacking sequence,
ABABAB......, is repeated over and over. 116
 Study questions

1. (a) Drive linear density expressions for FCC [100] and [111] directions in terms of the
atomic radius R.
(b) Compute and compare linear density values for these same two directions for
copper. RCu=0.128 nm
2. (a) Drive linear density expressions for BCC [110] and [111] directions in terms of the
atomic radius R.
(b) Compute and compare linear density values for these same two directions for iron.
RFe=0.124 nm
3. (a) Drive planar density expressions for FCC (100) and (111) planes in terms of the
atomic radius R.
(b) Compute and compare planar density values for these same two planes for
aluminum. RAl=0.143 nm
4. (a) Drive planar density expressions for BCC (100) and (110) planes in terms of the
atomic radius R.
(b) Compute and compare planar density values for these same two planes for
molybdenum. RMo=0.136 nm

117
 Crystalline and Noncrystalline Materials
Single crystal
• The repeated arrengement of
atoms is perfect in single crystal.
• All unit cell have the same
orientation in single crystal.
• They are anisotropic; properties
are dependent of direction.
• Single crystals exist in nature,
but they also be produced
artificially. But, they are ordinarily
difficult to grow.
Polycrystalline materials
• They are composed of collection
of many small grains.
• There exist some atomic
mismatch within the region where
two grains meet; these area
called grain boundary.
• They are anisotropic or isotropic
(properties are independent of
direction). Even though each
grain may be anisotropic, a
specimen composed of the grain
aggregate behaves isotropically.
• Most of the engineering materials
are polycrystalline.
118
Solidification of a crystalline material

119
 ANISOTROPY

 The physical properties of single crystals of some substances depend on

the crystallographic direction in which measurements are taken. For
example, the elastic modulus, the electrical conductivity, and the index of
refraction may have different values in the [100] and [111] directions.

 This directionality of properties is termed anisotropy, and it is associated

with the variance of atomic or ionic spacing with crystallographic direction.

 Substances in which measured properties are independent of the direction

of measurement are isotropic.

120
121