Learning Outcomes

Chapter 3:
To describe the difference in atomic/molecular structure between crystalline and
noncrystalline materials.
To draw unit cells for face-centered cubic (FCC), body centered cubic (BCC) and
hexagonal close-packed (HCP) crystal structures.
To derive the relationship between unit cell edge length and atomic radius, for FCC and
BCC crystal structures.
To calculate the atomic packing factor for FCC and BCC.
To compute the densities for metals having FCC and BCC crystal structures given their
unit cell dimensions.
To sketch the direction within a cubic unit cell corresponding to the three direction index
integers given (and do the reverse).
To specify the Miller indices for a plane that has been drawn within a cubic unit cell (and
do the reverse).
To calculate the linear density and planar density of crystal structures.
To distinguish between single crystal and polycrystalline materials.
To define isotropy and anisotropy with respect to material properties.
Open

Chapter 3 - 1

Chapter 3: The Structures of Metals

ISSUES TO ADDRESS...
How do atoms assemble into solid structures?
(for now, focus on metals)
How does the density of a material depend on
its structure?
When do material properties vary with the
sample (i.e., part) orientation?
Open

Chapter 3 - 2

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

Open

Dense, ordered packed structures tend to have

lower energies.
Chapter 3 - 3

Materials and Packing

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

crystalline SiO2
Adapted from Fig. 3.22(a),
Callister 7e.

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

Si

Oxygen

noncrystalline SiO2
Adapted from Fig. 3.22(b),
Callister 7e.

Open

Chapter 3 - 4

Section 3.3 Crystal Systems

Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
7 crystal systems

14 crystal lattices

a, b, and c are the lattice constants

Open

Fig. 3.4, Callister 7e.

Chapter 3 - 5

The lattice constant, or lattice

parameter, refers to the physical
dimension of unit cells in a
crystal lattice.Lattices in three
dimensions generally have three
lattice constants, referred to as a,
b, and c.

Open

Chapter 3 - 6

Section 3.4 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

Open

Chapter 3 - 7

Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:
- Typically, only one element is present, so all atomic
radii 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

Have the simplest crystal structures.

We will examine three such structures...

Open

Chapter 3 - 8

When we think of the type of bondings in metals, we

should take into consideration the difficulty in separating
metallic atoms from each other (metals
arehardmaterials), with the possibility of moving them
around (malleabilityandductility). Moreover, the
conductivityof electricity and heat in all directions.
Taking all these facts into consideration, the bonds in
metals have to bestrongand non-directional.
A simple picture that can explainbondingin metals is
the electron sea model that suggests that the atoms are
positively charged (cations) swimming in a sea of
electrons
(Figure)
The
meaning
of direction bonds,

covalent bonds being directional is that atoms bonded

covalently prefer specific orientations in space relative to one
another. As a result, molecules in which atoms are bonded
covalently have definite shapes.

Open

Malleability is the quality of something

that can be shaped into something
else without breaking, like
the malleability of
clay. Malleability also called
plasticity has to do with whether
something can be molded.

Chapter 3 - 9

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)

Coordination No.
the number of atoms or ions
immediately surrounding a
central atom in a complex or
crystal.
Open

(Courtesy P.M. Anderson)

Chapter 3 - 10

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
Open

Adapted from Fig. 3.23,

Callister 7e.

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell
Chapter 3 - 11

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

Adapted from Fig. 3.2,

Callister 7e.

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

Open

(Courtesy P.M. Anderson)

Chapter 3 - 12

Atomic Packing Factor: BCC

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

a
2a

Adapted from
Fig. 3.2(a), Callister 7e.

Open

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 - 13

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

Adapted from Fig. 3.1, Callister 7e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Open

(Courtesy P.M. Anderson)

Chapter 3 - 14

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74
maximum achievable APF

2a

Adapted from
Fig. 3.1(a),
Callister 7e.

Open

Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
atoms
volume
4
3
( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
Chapter 3 - 15

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 Unit Cell

A
B
C

Open

Chapter 3 - 16

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. 3.3(a),

Callister 7e.

Coordination # = 12
APF = 0.74
Open

c/a = 1.633

6 atoms/unit cell
ex: Cd, Mg, Ti, Zn
Chapter 3 - 17

Theoretical Density,
Density = =
=

where

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

nA
VC NA

n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadros number
= 6.023 x 1023 atoms/mol

Open

Chapter 3 - 18

Theoretical Density,
Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2
R
atoms
unit cell

=
volume
unit cell

Open

a
2 52.00

a3 6.023 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

Chapter 3 - 19

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
Open

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

Composites/
fibers

Polymers

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 B1, Callister 7e.
Chapter 3 - 20

Crystals as Building Blocks

Some engineering applications require single crystals:
--diamond single
crystals for abrasives
(Courtesy Martin Deakins,
GE Superabrasives,
Worthington, OH. Used with
permission.)

--turbine blades
Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
of Pratt and Whitney).

Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

Open

Chapter 3 - 21

Polycrystals

Most engineering materials are polycrystals.

1 mm
Nb-Hf-W plate with an electron beam weld.
Each "grain" is a single crystal.
If grains are randomly oriented,

Anisotropic

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)

Isotropic

overall component properties are not directional.

Grain sizes typ. range from 1 nm to 2 cm

Open

(i.e., from a few to millions of atomic layers).

Chapter 3 - 22

Single vs Polycrystals
Single Crystals

E (diagonal) = 273 GPa

Data from Table 3.3,
Callister 7e.
(Source of data is R.W.
Hertzberg, Deformation
and Fracture Mechanics
of Engineering
Materials, 3rd ed., John
Wiley and Sons, 1989.)

-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:

Polycrystals
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.

E (edge) = 125 GPa

200 m

Adapted from Fig.

4.14(b), Callister 7e.
(Fig. 4.14(b) is courtesy
of L.C. Smith and C.
Brady, the National
Bureau of Standards,
Washington, DC [now
the National Institute of
Standards and
Technology,
Gaithersburg, MD].)

Open

Chapter 3 - 23

Section 3.6 Polymorphism

Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
titanium
liquid
, -Ti
1538C
-Fe
BCC
carbon
1394C
diamond, graphite
-Fe
FCC
912C
BCC

-Fe

Open

Chapter 3 - 24

Section 3.8 Point Coordinates

z

Point coordinates for unit cell

center are

111

a/2, b/2, c/2

000

a
x

Point coordinates for unit cell

corner are 111

2c

b
Open

Translation: integer multiple of

lattice constants identical
position in another unit cell

b
Chapter 3 - 25

Crystallographic Directions
Algorithm

1. Vector repositioned (if necessary) to pass

through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas

[uvw]

ex: 1, 0, => 2, 0, 1 => [ 201 ]

-1, 1, 1 => [ 111 ]

where overbar represents a

negative index

families of directions <uvw>

Open

Chapter 3 - 26

Linear Density
Linear Density of Atoms LD =
[110]

Number of atoms
Unit length of direction vector

ex: linear density of Al in [110]

direction
a = 0.405 nm

# atoms

LD
length

2
2a

3.5 nm 1

Open

Chapter 3 - 27

HCP Crystallographic Directions

z

Algorithm
1. Vector repositioned (if necessary) to pass

a2

a3
a1

through origin.
2. Read off projections in terms of unit
cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
4. Enclose in square brackets, no commas
a2
[uvtw]

ex:

, , -1, 0

-a3

a2
2

Adapted from Fig. 3.8(a), Callister 7e.

=>

[ 1120 ]

a3

dashed red lines indicate

projections onto a1 and a2 axes

a1
2

a1

Open

Chapter 3 - 28

HCP Crystallographic Directions

Hexagonal Crystals
4 parameter Miller-Bravais lattice coordinates are
related to the direction indices (i.e., u'v'w') as
follows.
z

[ u 'v 'w ' ] [ uvtw ]

1
(2 u ' - v ')
3
1

v
(2 v ' - u ')
3
t - ( u +v )

u
a2

a3
a1
Fig. 3.8(a), Callister 7e.

w w'

Open

Chapter 3 - 29

Crystallographic Planes

Adapted from Fig. 3.9, Callister 7e.

Open

Chapter 3 - 30

Crystallographic Planes
Miller Indices: Reciprocals of the (three) axial
intercepts for a plane, cleared of fractions &
common multiples. All parallel planes have
same Miller indices.
Algorithm

1. Read off intercepts of plane with axes in

terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl)

Open

Chapter 3 - 31

Crystallographic Planes
z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1/2
1/
2
2

4.

Miller Indices

(100)

b
1
1/1
1
1

1/
0
0

a
x

1/
0
0

1/
0
0

x
Open

Chapter 3 - 32

Crystallographic Planes
z
example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6

b
1
1/1
1
3

(634)

c
c
3/4
1/
4/3

4 a
x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)
Open

Chapter 3 - 33

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example
1. Intercepts
2. Reciprocals
3.

Reduction

a1
1
1
1
1

a2

1/
0
0

a3
-1
-1
-1
-1

c
1
1
1
1

a2

a3

4.

Miller-Bravais Indices

(1011)

a1
Adapted from Fig. 3.8(a), Callister 7e.

Open

Chapter 3 - 34

Crystallographic Planes

We want to examine the atomic packing of

crystallographic planes
Iron foil can be used as a catalyst. The
atomic packing of the exposed planes is
important.
a) Draw (100) and (111) crystallographic planes
for Fe.
b) Calculate the planar density for each of these
planes.

Open

Chapter 3 - 35

Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC structure.
2D repeat unit

(100)

Planar Density =
area
2D repeat unit

Open

1
a2

4 3
R
3

Radius of iron R = 0.1241 nm

Adapted from Fig. 3.2(c), Callister 7e.

atoms
2D repeat unit

1
4 3
3

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2
Chapter 3 - 36

Planar Density of (111) Iron

Solution (cont): (111) plane

1 atom in plane/ unit surface cell

2a

atoms in plane

nit

atoms above plane

r ep

ea

tu

atoms below plane

2D

4 3
area 2 ah 3 a 3
R
3

atoms
2D repeat unit

Planar Density =
Open

area
2D repeat unit

1
16 3
3

atoms =
= 7.0
2
R

3
a
2

nm

16 3 2
R
3

0.70 x 1019

atoms
m2

Chapter 3 - 37

Section 3.16 - X-Ray Diffraction

Open

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.
Chapter 3 - 38

X-Rays to Determine Crystal Structure

Incoming X-rays diffract from crystal
d planes.

tg
u
o

ng
i
o

ys
a
-r

Measurement of
critical angle, c,
allows computation of
planar spacing, d.
Open

or

1
g
in
m
co s
in ray
Xextra
distance
travelled
by wave 2

et
ec
t

reflections must
be in phase for
a detectable signal
Adapted from Fig. 3.19,
Callister 7e.

spacing
between
planes

X-ray
intensity
(from
detector)

n
2 sin c

Chapter 3 - 39

X-Ray Diffraction Pattern

z

Intensity (relative)

c
a
x

y (110)

a
x

c
b

a
x

(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

Adapted from Fig. 3.20, Callister 5e.
Open

Chapter 3 - 40

SUMMARY
Atoms may assemble into crystalline or
amorphous structures.
Common metallic crystal structures are FCC, BCC, and
HCP. Coordination number and atomic packing factor
are the same for both FCC and HCP crystal structures.
We can predict the density of a material, provided we
know the atomic weight, atomic radius, and crystal
geometry (e.g., FCC, BCC, HCP).
Crystallographic points, directions and planes are
specified in terms of indexing schemes.
Crystallographic directions and planes are related
to atomic linear densities and planar densities.
Open

Chapter 3 - 41

SUMMARY
Materials can be single crystals or polycrystalline.
Material properties generally vary with single crystal
orientation (i.e., they are anisotropic), but are generally
non-directional (i.e., they are isotropic) in polycrystals
with randomly oriented grains.
Some materials can have more than one crystal
structure. This is referred to as polymorphism (or
allotropy).
X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Open

Chapter 3 - 42

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:

Open

Chapter 3 - 43