Chapter 3: The Structure of Crystalline Solids

ISSUES TO ADDRESS...
How do atoms assemble (arrange) into solid structures?
(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?
Structure Levels: Subatomic now: Atomic
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 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
Chapter 3 - 3

Crystal Systems
Unit cell: smallest repetitive volume which
contains the complete lattice pattern of a crystal.
There are 6 lattice parameters
Their different combinations lead to:
7 crystal systems (shapes)
14 crystal lattices
In metals: Cubic and Hexagonal
a, b, and c are the lattice constants
Fig. 3.4, Callister 7e.
Chapter 3 - 4

Table 3.2
Lattice Parameter Relationships and Figures Showing
Unit Cell Geometries for the Seven Crystal Systems

See other shapes

Chapter 3 - 5

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
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...

Chapter 3 - 7

Parameters in Studying Crystal Structures

Number and Position of Atoms in unit cell

Coordination No.
No. of touching-neighbor atoms
Cube edge (length)
Atomic Packing Factor (APF):
Fraction of volume occupied by atoms
Fraction of empty space = 1 APF
APF = Total volume of atoms in the unit cell
Volume of the unit cell

Chapter 3 - 8

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)

* Po: Polonium

Chapter 3 - 9

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

APF =

volume
atom
4
(0.5a) 3
1
3
a3

volume
unit cell
Chapter 3 - 10

Body Centered Cubic Structure (BCC)

Atoms touch each other along cube diagonals.
examples: Cr, Fe(), W, Ta, Mo*
Coordination # = 8

No of Atoms per unit cell = 1 center + 8 corners x 1/8 =2 atoms

--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.
* Cr: Chromium, W: Tungsten, Ta: Tantalum, Mo: Molybdenum
Chapter 3 - 11

Atomic Packing Factor: BCC

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

a
2a

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

No. atoms
volume
4
( 3a/4) 3
2
unit cell
atom
3
APF =
volume
a3
unit cell

Chapter 3 - 12

Face Centered Cubic Structure (FCC)

Atoms touch each other along face diagonals.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag
Coordination # = 12

No of atoms per unit cell = 6 face x 1/2 + 8 corners x 1/8 = 4 atoms

--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.
Chapter 3 - 13

Atomic Packing Factor: FCC

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

2a

Close-packed directions:
length = 4R = 2 a

a
atoms
volume
4
3
( 2a/4)
4
unit cell
atom
3
APF =
volume
3
a
unit cell
Chapter 3 - 14

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

Chapter 3 - 15

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
c/a = 1.633

No. of atoms/unit cell = 6

ex: Cd, Mg, Ti, Zn

Cd: Cadmium, Mg: Magnesium, Ti: Titanium, Zn: Zinc

Chapter 3 - 16

Polymorphism
Polymorphous Material:
Same Material with two or more distinct crystal structures
iron system
Crystal Structure is a Property:
It may vary with temperature
liquid
Allotropy /polymorphism
Examples
Titanium: , -Ti

BCC

1538C
-Fe

Carbon: diamond, graphite

FCC

1394C
-Fe

BCC

912C
-Fe

Heating
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
Chapter 3 - 18

Theoretical Density,
Example: For Cr
Known: A = 52.00 g/mol and R = 0.125 nm
Crystal Structure: BCC
For BCC: n = 2 and a = 4R/ 3 = 0.2887 nm
Calculate:

atoms
unit cell

=
volume
unit cell
Compare

2 52.00

g
mol

a3 6.023 x 1023
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?

20

Metals have...

close-packing (metallic bonding)

10

Ceramics have...
less dense packing
often lighter elements

Polymers have...

(g/cm3 )

often large atomic masses

low packing density

(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

5
4
3
2
1

0.5
0.4
0.3

Metals/
Alloys
Platinum
Gold, W
Tantalum
Silver, Mo
Cu,Ni
Steels
Tin, Zinc
Titanium
Aluminum
Magnesium

Water

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

Chapter 3 - 20

Structure-Properties

Materials-Structures
Amorphous: Random atomic orientation
Crystalline:
Single Crystal Structure:
One Crystal
Perfectly repeated unit cells.
Polycrystalline
Many crystals
Properties
Anisotropy: depend on direction
Isotropy: does not depend on direction

Chapter 3 - 21

Single Crystals
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.

Chapter 3 - 22

Properties for Single and Polycrystals

Single Crystals

E (diagonal) = 273 GPa

-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)

E (edge) = 125 GPa

200 m

-If grains are textured, anisotropic.

Chapter 3 - 23

Polycrystals
Most engineering materials are polycrystals.

Anisotropic

1 mm
Isotropic
Each "grain" is a single crystal (composed of many unit cells).
If grains are randomly oriented,
overall component properties are not directional.
Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).

Chapter 3 - 24

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

Translation:
integer multiple of lattice constants
identical position in another unit cell

b
Chapter 3 - 25

Crystallographic Directions
Vectors or lines between two points
Described by indices
Algorithm (for obtaining indices)
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 (multiply by a factor)
4. Enclose in square brackets, no commas
[uvw]
(note: If the value is ve put the sign over the number) x
Instead of 1 and 2: you can
1. Determine coordinates of head (H) and tail (T)
2. Subtract:
head tail
Then as before (steps 3 and 4)

Ex 2: -1, 1, 1 => [ 111 ]

y
Ex 1: 1, 0,

2, 0, 1

[ 201 ]

(overbar represents a negative index)

families of directions <uvw>

Chapter 3 - 26

Linear Density
Linear Density of Atoms LD =

Number of atoms
Unit length of direction vector

ex: linear density of Al in [110] direction

[110]

a = 0.405 nm
# atoms

LD
length

2
2a

3.5 nm 1
a

Chapter 3 - 27

HCP Crystallographic Directions

Algorithm

1. Vector repositioned (if necessary) to pass

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]

a3

a2

a1

ex:

, , -1, 0

-a3

a2
2

=>

[ 1120 ]

a3

dashed red lines indicate

projections onto a1 and a2 axes

a1
2

a1
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'
Chapter 3 - 29

Crystallographic Planes

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 (for obtaining Miller Indices)
If the plane passes through the origin, choose another origin
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)

Chapter 3 - 31

Crystallographic Planes
z

Example 1
1. Intercepts
2. Reciprocals
3.

Integers

a
1
1/1
1
1

4.

Miller Indices

(110)

Example 2
1. Intercepts
2. Reciprocals
3.

Integers

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
Chapter 3 - 32

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

4.

Integers
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)
Chapter 3 - 33

Crystallographic Planes (HCP)

In hexagonal unit cells the same idea is used
z

example
1. Intercepts
2. Reciprocals
3.

Integers

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

Chapter 3 - 34

Planar Density
Concept
The atomic packing of crystallographic planes
No. of atoms per area of a plane
Importance
Iron foil can be used as a catalyst.
The atomic packing of the exposed planes is important.
Example
a) Draw (100) and (111) crystallographic planes
for Fe (BCC).
b) Calculate the planar density for each of these planes.

Chapter 3 - 35

Planar Density of (100) Iron

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

(100)

4 3
R
3

Radius of iron R = 0.1241 nm

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

1
a2

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

it

atoms above plane

rep
ea
t

un

atoms below plane

2D

4 3
area 2 ah 3 a 3
R
3

atoms
2D repeat unit

Planar Density =
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

Determination of Crystal Structure

Wave: has an amplitude and wave length ()
Diffraction: phase relationship between two (or more) waves that
have been scattered.
Scattering:

In-phase
Out-of-phase

Constructive
Destructive

Detecting scattered waves after encountering an object:

Identify positions of atoms

Diffraction occurs when a wave encounters a series of regularly
spaced atoms IF:
1)
The obstacles are capable of scattering the wave
2)
Spacing between them nearly = wave length
Wave length depend on the source (i.e. material of the anode).
Chapter 3 - 38

X-Ray Diffraction

Diffraction gratings must have spacings comparable to

the wavelength of diffracted radiation.
Cant resolve spacings
Chapter 3 - 39

Constructive versus Destructive Diffraction

Chapter 3 - 40

Constructive X-Ray Diffraction

Chapter 3 - 41

X-Ray Experiment

Chapter 3 - 42

X-Rays to Determine Crystal Structure

extra distance traveled by wave 2

ys
a
-r

reflections must be in phase for

a detectable signal

d Interplaner spacing
spacing between planes

Constructive diffraction occurs when

the second wave travels a distance = n
From Geometry
extra traveled distance = 2 d sin
Then

n
d
2 sin c

or

In-phase
X-ray intensity

tg
u
o

ng
i
o

de
te
ct

1
g
in
m
co s
in ray
X-

Incoming X-rays diffract from crystal planes.

Constructive

c
Chapter 3 - 43

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

n
d
2 sin c
d=

a
(h2+k2+l2)0.5

Braggs Law, n: order of reflection

for plane (h k l)

Atoms in other planes cause extra scattering

For validity of Braggs law
For BCC
h+k+l = even
For FCC
h, k, l all even or odd
Sample calculations
Given the plane indices and
Crystal structure,
get
a (from C.S. and R) and d (from indices)
Then with wavelength get angle or wavelength
Chapter 3 - 44

Solved Problem
3.58 Determine the expected diffraction angle for the first-order reflection
from the (310) set of planes for BCC chromium
when monochromatic radiation of wavelength 0.0711 nm is used.

BCC
d=

a
(h2+k2+l2)0.5

for plane (h k l)

For (310)

Brags Law

Chapter 3 - 45

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)

Chapter 3 - 46

SUMMARY
Atoms may assemble into crystalline or amorphous
structures.
Common metallic crystal structures are FCC, BCC, and
HCP.
Coordination number and atomic packing factor
arecan
thepredict
same for
FCCofand
HCP crystal
structures.
We
theboth
density
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.
Chapter 3 - 47

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.

Chapter 3 - 48