Module 3

Structure of Crystalline Solids

 Intended Learning Outcomes
1. Illustrate the different structures of crystalline
solids.
2. Derive the relationships between unit cell edge
length and atomic radius for face-centered cubic
and body-centered cubic crystal structures.
3. Compute the densities for metals having face-
centered cubic and body-centered cubic crystal
structures given their unit cell dimensions.
 Fundamental Concepts
• Crystalline Structure
➢ 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.
• Non Crystalline Structures
➢ do not crystallize and the long-range
atomic order is absent.
 METALLIC CRYSTALS
• tend to be densely packed.
• have several reasons for dense packing:
-Typically, made of heavy element.
-Metallic bonding is not directional; i.e., no
restrictions as to the number and position of
nearest-neighbor atoms
-Nearest neighbor distances tend to be small in
order to lower bond energy.

• have the simplest crystal structures.

We will look at four such structures...
Unit Cell
• Unit cells for most crystal structures are
parallelepipeds or prisms having three
sets of parallel face
• A unit cell is the basic structural unit or
building block of the crystal structure
SIMPLE CUBIC STRUCTURE (SC)
• Cubic unit cell is 3D repeat unit
• Rare (only Po has this structure)
• Close-packed directions (directions along which atoms touch each other)
are cube edges.
• Coordination # = 6
(# nearest neighbors)

(Courtesy P.M. Anderson)

[Link]
 ATOMIC PACKING FACTOR
• In crystalline materials:
➢ It is the fraction of volume in a crystal
structure that is occupied by atoms
(assuming atoms are hard spheres). It tells
us how efficiently atoms are packed
together in a crystal.
ATOMIC PACKING FACTOR
contains 8 x 1/8 =
a 1 atom/unit cell

R=0.5a

close-packed directions
Adapted from Fig. 3.19,
Callister 6e.

• APF for a simple cubic structure = 0.52

 BODY CENTERED CUBIC
STRUCTURE (BCC)
• Coordination # = 8

Adapted from Fig. 3.2,

(Courtesy P.M. Anderson) Callister 6e.

• Close packed directions are cube diagonals.

--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.
ATOMIC PACKING FACTOR: BCC

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from a
Fig. 3.2,
Callister 6e.

• APF for a body-centered cubic structure = p3/8 = 0.68

 FACE CENTERED CUBIC
STRUCTURE (FCC)
• Coordination # = 12

Adapted from Fig. 3.1(a),

(Courtesy P.M. Anderson) Callister 6e.

• Close packed directions are face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.
ATOMIC PACKING FACTOR: FCC

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e.

• APF for a face-centered cubic structure = p/(32) = 0.74

(best possible packing of identical spheres)
 FCC STACKING SEQUENCE
• FCC Unit Cell

• ABCABC... Stacking Sequence

• 2D Projection

A
B B
C
A
A sites B B B
C C
B sites B B
C sites
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)

Ideally, c/a = 1.633 for close packing

However, in most metals, c/a ratio deviates from this value
 HEXAGONAL CLOSE-PACKED
STRUCTURE (HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites

B sites

A sites
Adapted from Fig. 3.3,
Callister 6e.

• Coordination # = 12
• APF = 0.74, for ideal c/a ratio of 1.633
 COMPARISON OF CRYSTAL
STRUCTURES

Crystal structure coordination # packing factor close packed directions

• Simple Cubic (SC) 6 0.52 cube edges

• Body Centered Cubic (BCC) 8 0.68 body diagonal

• Face Centered Cubic (FCC) 12 0.74 face diagonal

• Hexagonal Close Pack (HCP) 12 0.74 hexagonal side

 THEORETICAL DENSITY, r
Density = mass/volume

mass = number of atoms per unit cell * mass of each atom

mass of each atom = atomic weight/avogadro’s number

Characteristics of Selected Elements at 20C
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ teristics of
Cadmium Cd 112.41 8.65 0.149 Selected
Elements",
Calcium Ca 40.08 1.55 0.197 inside front
Carbon C 12.011 2.25 0.071 cover,
Cesium Cs 132.91 1.87 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------
 THEORETICAL DENSITY, r

Example: Copper
Data from Table
• crystal structure = FCC: 4 atoms/unit cell
• atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
• atomic radius R = 0.128 nm (1 nm = 10 -7cm)

Result: theoretical rCu = 8.89 g/cm3

Compare to actual: rCu = 8.94 g/cm3
 DENSITIES OF MATERIAL CLASSES
rmetals> rceramics> rpolymers
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.
 The atomic weight, density, and atomic
radius for three hypothetical alloys are listed
in the following table. For each, determine
whether
The atomic its crystal
weight, density, structure
and atomic radius is FCC,
for three hypothetical alloysBCC, orthe
are listed in
simple
following cubic
table. For each, and
determine whether then
its crystal
cubic and then justify your determination. (15 Points)
structurejustify
is FCC, BCC, your
or simple

determination.