AL- FATIHAH

CHAPTER 3:
THE STRUCTURE OF CRYSTALLINE SOLIDS

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 2503 Materials Science & Engineering

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

crystalline SiO2

Si

Oxygen

noncrystalline SiO2

MME 2503 Materials Science & Engineering

CRYSTAL SYSTEMS
4

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

MME 2503 Materials Science & Engineering

Chapter 3 -

CRYSTAL SYSTEMS

MME 2503 Materials Science & Engineering

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.

MME 2503 Materials Science & Engineering

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)

MME 2503 Materials Science & Engineering

ATOMIC PACKING FACTOR (APF)

APF =

Volume of atoms in unit cell*

Volume of unit cell

*assume hard spheres

APF for a simple cubic structure = 0.52
atoms
unit cell

R=0.5a

APF =

volume
atom
4
p (0.5a) 3
1
3

a3
close-packed directions
contains 8 x 1/8 =
1 atom/unit cell
MME 2503 Materials Science & Engineering

volume
unit cell
8

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

MME 2503 Materials Science & Engineering

ATOMIC PACKING FACTOR: BCC

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

a
2a

R
atoms

a
4

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

p ( 3a/4 ) 3
2
unit cell
3
APF =
volume
3
a
unit cell
MME 2503 Materials Science & Engineering

10

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

MME 2501 - Engineering Materials

11

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

a
atoms

4
unit cell
3
APF =

p ( 2a/4 ) 3
a3

volume
atom

volume
unit cell

MME 2501 - Engineering Materials

12

FCC Stacking Sequence

13
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

MME 2501 - Engineering Materials

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
APF = 0.74

6 atoms/unit cell

ex: Cd, Mg, Ti, Zn

c/a = 1.633
MME 2501 - Engineering Materials

14

THEORETICAL DENSIT Y, R
15

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
MME 2501 - Engineering Materials

Chapter 3 -

THEORETICAL DENSIT Y, R
16

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n=2

a = 4R/ 3 = 0.2887 nm

atoms

unit cell

=
volume
unit cell

2 52.00
a3 6.023 x 1023

g
mol

theoretical = 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

MME 2501 - Engineering Materials

Chapter 3 -

DENSITIES OF MATERIAL
CLASSES
Graphite/

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

17

Metals/
Alloys

20

Platinum
Gold, W
Tantalum

10

Silver, Mo
Cu,Ni
Steels
Tin, Zinc

5
4
3
2

Titanium
Aluminum
Magnesium

Composites/
fibers

Ceramics/ Polymers
Semiconductor

*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
G raphite

0.5
0.4
0.3
MME 2501 - Engineering Materials

PTFE
Silicone
PVC
PET
PC
HDPE, PS
PP, LDPE

Glass fibers
GFRE*
Carbon fibers
CFRE *
A ramid fibers
AFRE *

Wood

Chapter 3 -

CRYSTALS AS BUILDING BLOCKS

Some engineering applications require single crystals:
--diamond single
crystals for abrasives

--turbine blades

Properties of crystalline materials

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

MME 2501 - Engineering Materials

18

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,

Isotropic

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).
MME 2501 - Engineering Materials

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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
-Properties may/may not
vary with direction.
-If grains are randomly
oriented: isotropic.

200 mm

(Epoly iron = 210 GPa)

-If grains are textured,

anisotropic.
MME 2501 - Engineering Materials

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POLYMORPHISM
21

Two or more distinct crystal structures for the

same material (allotropy/polymorphism)
iron system
titanium
, -Ti

liquid

carbon
diamond, graphite

BCC

1538C
-Fe

FCC

1394C
-Fe
912C

BCC
MME 2501 - Engineering Materials

-Fe
Chapter 3 -

POINT COORDINATES
z

22

Point coordinates for unit

cell center are
a/2, b/2, c/2

111

c
y

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
MME 2501 - Engineering Materials

Chapter 3 -

CRYSTALLOGRAPHIC DIRECTIONS
z

Algorithm23
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of
unit cell dimensions a, b, and c
y 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

MME 2501 - Engineering Materials

Chapter 3 -

CRYSTALLOGRAPHIC PLANES
26

MME 2501 - Engineering Materials

Chapter 3 -

CRYSTALLOGRAPHIC PLANES
27

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
z
28

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

(200)

b
1
1/1
1
1

1/
0
0

c
y
b

a
x

1/
0
0

1/
0
0

z
c

y
a

x
MME 2501 - Engineering Materials

Chapter 3 -

CRYSTALLOGRAPHIC PLANES
29

example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

a
1/2
1/
2
6
(634)

b
1
1/1
1
3

z
c
c
3/4
1/
4/3

4 a
x

MME 2501 - Engineering Materials

Chapter 3 -

LINEAR DENSIT Y
31

Linear Density of Atoms LD =

Number of atoms

Unit length of direction vector

[110]
ex: linear density of Al in [110]
direction
a = 0.405 nm

# atoms
a

LD =
length

= 3.5 nm -1

2a

MME 2501 - Engineering Materials

Chapter 3 -

CRYSTALLOGRAPHIC PLANES
32

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.

MME 2501 - Engineering Materials

Chapter 3 -

PLANAR DENSIT Y OF (100) IRON

33
Solution: At T < 912C iron
has the BCC
structure.

(100)

Planar Density =
area
2D repeat unit

1
a2

a=

4 3
R
3

Radius of iron R = 0.1241 nm

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

atoms
2D repeat unit

2D repeat unit

4 3
R
3

atoms
atoms
19
= 1.2 x 10
2 = 12.1
2
nm
m2

MME 2501 - Engineering Materials

Chapter 3 -

PLANAR DENSIT Y OF (111) IRON

Solution (cont): (111) plane
34
1 atom in plane/ unit surface cell

2a

atoms in plane
atoms above plane
atoms below plane

h=

3
a
2

atoms
2D repeat unit

4 3 16 3 2
2
area = 2 ah = 3 a = 3
R =
R
3
3

atoms =
= 7.0
2

Planar Density =
area
2D repeat unit

16 3
3

nm

MME 2501 - Engineering Materials

0.70 x 1019

atoms
m2

Chapter 3 -

X-RAY DIFFRACTION
35

Diffraction gratings must have spacings

comparable to the wavelength of diffracted
radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.
MME 2501 - Engineering Materials
Chapter 3 -

X-RAYS TO DETERMINE CRYSTAL

STRUCTURE
36

Incoming X-rays diffract from crystal planes.

extra
distance
travelled
by wave 2

reflections must
be in phase for
a detectable signal

Adapted from Fig. 3.19,

Callister 7e.

spacing
between
planes

Measurement of
critical angle, qc,
allows computation of
planar spacing, d.

X-ray
intensity
(from
detector)

d=

n
2 sin qc

q
qc

MME 2501 - Engineering Materials

Chapter 3 -

X-RAY DIFFRACTION PATTERN

z 37

Intensity (relative)

c
a
x

c
b

y (110)

a
x

c
b

a
x (211)

(200)

Diffraction angle 2q

Diffraction pattern for polycrystalline -iron (BCC)

MME 2501 - Engineering Materials

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.
MME 2501 - Engineering Materials

38

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

39