Lecture 3: The Structure of Crystalline Solids

ISSUES TO ADDRESS...
What is the difference in atomic arrangement
between crystalline and noncrystalline solids?
What features of a materials atomic
structure determine its density?
Under what circumstances does a material
property vary with the measurement direction?
Crystalline structures of metals and alloys
Chapter 3 - 1

Energy and Packing

Non dense, random packing

Energy
Typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packing

r
Energy
typical neighbor
bond length

typical neighbor
bond energy

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 2

Materials and Packing

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

crystalline SiO2
Adapted from Fig. 3.25(a),
Callister & Rethwisch 9e.

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

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.25(b),
Callister & Rethwisch 9e.
Chapter 3 - 3

The Cubic
System

b=4r
b2=2a2
S=a2
V=a3

FCC

Lattice Parameter (a)

and Atomic Radius (r)

One Atom

Two Atoms

Four Atoms

Chapter 3 -

Chapter 3 -

Metallic Crystal Structures

How can we stack metal atoms to minimize
empty space?
2-dimensions

vs.

Now stack these 2-D layers to make 3-D structures

Chapter 3 - 6

Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:
- Typically, only one element is present, so all atomic
______ are the same.
- Metallic bonding is not directional.
- Nearest neighbor distances tend to be small in
order to lower bond energy.
- Electron cloud shields cores from each other.

Metals have the simplest crystal structures.

We will examine three such structures...

Chapter 3 - 7

Simple Cubic Structure (SC)

Rare due to low packing density (only Po has this structure)
Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)

Click once on image to start animation

(Courtesy P.M. Anderson)

Chapter 3 - 8

Atomic Packing Factor (APF)

Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
APF for a simple cubic structure = 0.52
atoms
unit cell

a
R = 0.5a
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.3 (a),
Callister & Rethwisch 9e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell

Chapter 3 - 9

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

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

Coordination # = 8

Click once on image to start animation

(Courtesy P.M. Anderson)

Adapted from Fig. 3.2,

Callister & Rethwisch 9e.

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

Chapter 3 - 10

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 9e.

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

atoms
volume
4
( 3a/4 ) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell

Chapter 3 - 11

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12

Click once on image to start animation

(Courtesy P.M. Anderson)

Adapted from Fig. 3.1, Callister & Rethwisch

9e.

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

Chapter 3 - 12

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF
Close-packed directions:
length = 4R = 2 a

2a

Unit cell contains:

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

Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 9e.

atoms
unit cell
APF =

4
3

( 2a/4 ) 3

a^3

volume
atom
volume
unit cell
Chapter 3 - 13

FCC Stacking Sequence

ABCABC... Stacking Sequence
2D Projection
B
B
C
A
B
B
B
A sites
C
C
B sites
B
B
C sites
FCC _____ Cell

A
B
C

Chapter 3 - 14

Hexagonal Close-Packed Structure

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

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Adapted from Fig. 3.4(a),

Callister & Rethwisch 9e.

Coordination # = __
APF = ______

__ atoms/unit cell
ex: Cd, Mg, Ti, Zn

c/a = _______
Chapter 3 - 15

Three Crystalline
Structures for Most
of Metals
BCC
FCC
HCP

Chapter 3 -

Common Metallic Crystal Structures

Chapter 3 -

PACKING FRACTION /EFFICIENCY

Relation between atomic radius (r) and

lattice parameter (a)

SC*

BCC*

FCC

HCP

a = 2r

Sqrt3*a
= 4r

Sqrt2*a =
4r

a = 2r
c 4r

Atoms / cell

Lattice points / cell

No. of nearest neighbours

12

12

Packing fraction

3
8

2
6

3
6

3
6

= 0.68

= 0.74

Crystal formed by monoatomic decoration of the lattice

DCDiamond Cubic
Chapter 3 -

2
3

METALLICMetals

Positive ions in a free electron cloud

Metallic bonds are non-directional

Each atoms tends to surround itself with as many neighbors as possible!
Usually high temperature(FCC) Low Temp. (BCCOpen
structure)

FCC Al, Fe (910 - 1410C), Cu, Ag, Au, Ni, Pd, Pt

BCC Li, Na, K , Ti, Zr, Hf, Nb, Ta, Cr, Mo, W, Fe (below 910C)
HCP Be, Mg, Ti, Zr, Hf, Zn, Cd
Others La, Sm-Po, -Mn, Pu

Have the simplest crystal structures

Chapter 3 -

Chapter 3 -

Periodic Table of The Elements

Chapter 3 -

Periodic Table of Metal Structures

Chapter 3 -

Theoretical Density,
Density = =

where

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = # of atoms/unit cell
A = atomic weight
VC = volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.022 x 1023 atoms/mol
Chapter 3 - 23

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
Adapted from
Fig. 3.2(a), Callister &
Rethwisch 9e.

atoms
unit cell
=

volume
unit cell

a
2 52.00

a 3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol
Chapter 3 - 24

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 B.1, Callister & Rethwisch, 9e.
Chapter 3 - 25