Chapter 3:

The Structure of Crystalline Solids

1

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?
MME 2501 - Engineering Materials

Materials and Packing

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

Noncrystalline materials...
atoms have no periodic packing
occurs for:
-complex structures
-rapid cooling
"Amorphous" = Noncrystalline
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crystalline SiO2

Si

Oxygen

noncrystalline SiO2

Crystal Systems
3

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

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Chapter 3 -

Crystal Systems
4

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Chapter 3 -

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.

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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)

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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

APF =

close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
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volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
--Note: All atoms are identical; the center atom is shaded

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

Coordination # = 8

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

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Atomic Packing Factor: BCC

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

a
2a

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

atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell
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9

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded

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

Coordination # = 12

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

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10

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 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
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11

FCC Stacking Sequence

ABCABC... Stacking Sequence
12
2D Projection
BB
BB
C
A
BB
BB
BB
A sites
C
C
BB sites
sites
BB
BB
C sites
FCC Unit Cell

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A
B
C

Chapter 3 -

Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence
3D Projection

2D Projection
A sites

Top layer

B sites

Middle layer

A sites

Bottom layer

Coordination # = 12

6 atoms/unit cell

APF = 0.74

ex: Cd, Mg, Ti, Zn

c/a = 1.633
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13

Theoretical Density,
14

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

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Chapter 3 -

Theoretical Density,
15

Ex: Cr (BCC)

A = 52.00 g/mol
R = 0.125 nm
n=2
R
atoms
unit cell

=
volume
unit cell

a
2 52.00

a3 6.023 x 1023

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a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol
Chapter 3 -

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
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16 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/ Polymers
Semiconductor

Composites/
fibers

*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

Chapter 3 -

Crystals as Building Blocks

Some engineering applications require single crystals:
--turbine blades

--diamond single
crystals for abrasives

Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.

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17

Polycrystals
Most engineering materials are polycrystals.

Anisotropic

1 mm
Nb-Hf-W plate with an electron beam weld.
Each "grain" is a single crystal.
If grains are randomly oriented,
overall component properties are not directional.

Grain sizes typically range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).
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18

Isotropic

Single vs Polycrystals
Single Crystals

E (diagonal) = 273 GPa

-Properties vary with

direction: anisotropic.
-Example: the modulus
of elasticity (E) in BCC iron:
E (edge) = 125 GPa

Polycrystals

200 m

-Properties may/may not

vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.
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19

Polymorphism
20

Two or more distinct crystal structures for the same

material (allotropy/polymorphism)
iron system
titanium
, -Ti
carbon
diamond, graphite

liquid
BCC

1538C
-Fe

FCC

1394C
-Fe
912C

BCC

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-Fe
Chapter 3 -

Point Coordinates
z

21

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

Translation: integer multiple of

lattice constants identical
position in another unit cell

b
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Chapter 3 -

Crystallographic Directions
22
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 ]

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where overbar represents a

negative index
Chapter 3 -

Crystallographic Planes
25

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Chapter 3 -

Crystallographic Planes
26

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)
MME 2501 - Engineering Materials

Chapter 3 -

Crystallographic Planes
example
1. Intercepts
2. Reciprocals
3.

Reduction

a
1
1/1
1
1

4.

Miller Indices

(110)

example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
0
2
0

27

b
1
1/1
1
1

z
c

1/
0
0

a
x

b
c

1/ 1/
0
0

(200)

x
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Chapter 3 -

Crystallographic Planes
28

example
1. Intercepts
2. Reciprocals
3.
4.

a
b
c
c
1/2
1
3/4
1/ 1/1 1/
2 1
4/3

a
Reduction
6 3
4
x
Miller Indices
(634)

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Chapter 3 -

Linear Density
Number of atoms

30

Linear Density of Atoms LD =

[110]

ex: linear density of Al in [110]

direction
a = 0.405 nm

# atoms

LD
length

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Unit length of direction vector

2
2a

3.5 nm 1

Chapter 3 -

Crystallographic Planes
31

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.

Draw (100) and (111) crystallographic planes

for Fe.
b) Calculate the planar density for each of these
planes.
a)

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Chapter 3 -

Planar Density of (100) Iron

32
Solution: At T < 912C iron
has the BCC structure.

2D repeat unit

(100)

Planar Density =
area
2D repeat unit

1
a2

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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
R
3

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

Planar Density of (111) Iron

Solution (cont): (111) plane33 1 atom in plane/ unit surface cell

2a

atoms in plane

nit

atoms above plane

r ep

ea

tu

atoms below plane

2D

3
a
2

4 3
16 3 2

area 2 ah 3 a 3
R
R

3
3

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
16 3

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atoms =
= 7.0
2
R

nm

0.70 x 1019

atoms
m2

Chapter 3 -

X-Ray Diffraction
34

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.

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

X-Rays to Determine Crystal Structure

35

Incoming X-rays diffract from crystal

planes.
d

tg
u
o

ng
i
o

ys
a
-r

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

1
g

in
2
m
co ys
i n -ra
X

extra
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 -

X-Ray Diffraction Pattern

z
c

Intensity (relative)

c
a
x

y (110)

a
x

z36

z
c
b

a
x

(211)

(200)

Diffraction angle 2

Diffraction pattern for polycrystalline -iron (BCC)

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Chapter 3 -

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.
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37

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.

MME 2501 - Engineering Materials

38