UEME Material Science

Lecture 2

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Previous lecture
Structure of Materials
Structure of atoms, periodic
table
Quantum elementary physics:
Pauli exclusion principle
Types of bonding & materials
classes

Topic 1
Structure of Materials
Structure of atoms, periodic table
Quantum elementary physics: Pauli exclusion
principle
Types of bonding & materials classes
Crystalline and non-crystalline structures
Crystalline point defects and their significance
Use of phase diagrams: unary and binary
phase diagrams

The Structure of
Crystalline Solids (Metal)

How do atoms assemble into solid structure

How does the density of a material depend o

its structure?
When do material properties vary with the
sample (i.e., part) orientation?

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.

Materials and Packing

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

crystalline SiO2

Adapted from Fig. 3.23(a),

Callister & Rethwisch 8e.

Noncrystalline materials...

Si

Oxygen

atoms have no periodic packing

occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline

noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.

Crystal Systems
Unit cell: smallest repetitive volume which contains the
complete
lattice pattern of a crystal.
(lattice means a 3D array of points coinciding with atom
positions).

Metallic Crystal Structures

Tend to be densely packed.
Reasons for dense packing:

- Typically, only one element is present, so all atom

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...

Lattices
Lattices exist in simple cubic
(SC), body-centred cubic (BCC)
face-centred cubic (FCC) forms
and hexagonal close-packed (HCP)
structures.

Simple Cubic Structure (SC)

Rare due to low packing density (only Po has this structu

Close-packed directions are cube edges.
Coordination # = 6
(# nearest neighbors)

Click once on image to start animation

(Courtesy P.M. Anderson)

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

volume
atoms
a

unit cell
R=0.5a

APF =

4
3
a3

close-packed directions
contains 8 x 1/8 =
1atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e.

(0.5a) 3

atom

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
differently only for ease of viewing.

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

Coordination # = 8

Adapted from Fig. 3.2,

Callister & Rethwisch 8e.
(Courtesy P.M. Anderson)

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

BCC

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68

3a

a
2a
Close-packed directions:
Adapted from
Fig. 3.2(a), Callister
& Rethwisch 8e.

atoms
unit cell
APF =

length = 4R =

( 3 a/4 ) 3

3
a3

volume
atom
volume
unit cell

3a

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

Click once on image to start animation

Coordination # = 12

Adapted from Fig. 3.1, Callister &

Rethwisch 8e.

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

(Courtesy P.M. Anderson)

FCC

FCC

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
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 8e.

atoms
unit cell
APF =

4
3

( 2a/4 )3
a3

volume
atom
volume
unit cell

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

Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence
3D Projection

2D Projection
A sites

c
a

Top layer

B sites

Middle layer

A sites

Bottom layer

Adapted from Fig. 3.3(a),

Callister & Rethwisch 8e.

Coordination # = 12
APF = 0.74
c/a = 1.633

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

Our focus
We will focus on SC, BCC and FCC.
HCP is not included in the
assessment.

Theoretical Density,
Density = = Mass of

Total

where

Atoms in Unit Cell

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
= 6.022 x 1023 atoms/mol

Theoretical Density,
Ex: Cr (BCC)

A = 52.00 g/mol
R = 0.125 nm
n = 2 atoms/unit cell
R
Adapted from
Fig. 3.2(a), Callister
& Rethwisch 8e.

atoms

unit cell

=
volume
unit cell

2 52.00

a3 6.022 x 1023

a = 4R/ 3 = 0.2887 nm
g
mol

theoretical

= 7.18 g/cm3

actual

= 7.19 g/cm3

atoms
mol

Densities of Material Classes

In general

metals > ceramics > polymers

30

Why?

20

Metals have...

(g/cm3

close-packing
10
(metallic bonding)
often large atomic masses

Ceramics have...

less dense packing

often lighter elements

Polymers have...

Metals/
Alloys

5
4
3
2

low packing density

1
(often amorphous)
lighter elements (C,H,O)

Composites have...
intermediate values

0.5
0.4
0.3

Graphite/
Composites/
Ceramics/ Polymers
fibers
Semicond

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

ased
B
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, 8e.

Polycrystals
Most engineering materials are polycrystals.

1 mm

Anisotropic

Adapted from Fig. K,

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

Isotropic

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).

Single vs 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)

-If grains are textured,

anisotropic.

E (edge) = 125 GPa

200 m

Data from Table 3.3,

Callister & Rethwisch
8e. (Source of data is
R.W. Hertzberg,
Deformation and
Fracture Mechanics
of Engineering
Materials, 3rd ed.,
John Wiley and Sons,
1989.)

Adapted from Fig.

4.14(b), Callister &
Rethwisch 8e.
(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].)

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

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
b

Translation: integer multiple

of lattice constants
identical position in
another unit cell

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>

Linear Density
Number of atoms

Linear Density of Atoms LD =

Unit length of direction vector
[110]

ex: linear density of Al in [110]

direction
a = 0.405 nm

# atoms
a
Adapted from
Fig. 3.1(a),
Callister &
Rethwisch 8e.

LD
length

2
2a

3.5 nm1

Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.

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)

Crystallographic Planes
z

a
1
1/1
1
1

example
1. Intercepts
2. Reciprocals
3.

Reduction

4.

Miller Indices

example
1. Intercepts
2. Reciprocals
Reduction

4.

Miller Indices

1/
0
0

(110)

a
1/2
1/
2
0
2
0

3.

b
1
1/1
1
1

a
x

1/

1/

0
0

(100)

Crystallographic Planes
z
a
b
c
example
1/2
1
3/4
1. Intercepts
2. Reciprocals 1/ 1/1 1/

4/3

3.

Reduction

4.

Miller Indices

(634)

Family of Planes {hkl}

Ex: {100} = (100),

(010), (001), (100), (010), (001)

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.

Virtual Materials Science &

Engineering
(VMSE)
VMSE is a tool to visualize materials science topics such as
crystallography and polymer structures in three dimensions

Available in Student Companion Site at

www.wiley.com/college/callister

VMSE: Metallic Crystal Structures &

Crystallography Module

VMSE allows you to view crystal structures, directions, planes,

etc. and manipulate them in three dimensions

Unit Cells for Metals

VMSE allows you to view the unit cells and manipulate
them in three dimensions
Below are examples of actual VMSE screen shots

FCC Structure

HCP Structure

VMSE: Crystallographic Planes

Exercises

Additional practice on indexing crystallographic planes

Planar Density of (100) Iron

Solution: At T < 912C iron has the BCC
structure.
2D repeat unit
(100)

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e.

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

a2

4 3
R
3

Radius of iron R = 0.1241 nm

1
4 3
R
3

= 12.1atoms=

nm2

atoms
1.2 x 10
m2
19

Planar Density of (111) Iron

Solution (cont): (111) plane1 atom in plane/ unit surface cell

2a

atoms in plane

ni t

atoms above plane

ep
e

at
u

atoms below plane

2D
r

4 3
area 2 ah 3 a 3
R
3

atoms
2D repeat unit

Planar Density =
area
2D repeat unit

16 3
3

R2

3
a
2

atoms =
7.0
nm2

16 3 2
R
3

0.70 x 1019

atoms
m2

VMSE Planar Atomic Arrangements

VMSE allows you to view planar arrangements and rotate

them in 3 dimensions

BCC (110) Plane

X-Ray Diffraction

Diffraction gratings must have spacings

comparable to the wavelength of diffracted
radiation.
Cant resolve spacings
Spacing is the distance between parallel planes
of atoms.

X-Rays to Determine Crystal

Structure
Incoming X-rays diffract from crystal planes.

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

ut

i
o
g

ng

1
g
2
in
m s
co y
in -ra
X

extra
distance
travelled
by wave 2

de
te
ct
or
s
reflections must
y
a
r
be in phase for
X-

a detectable signal
Adapted from Fig. 3.20,
Callister & Rethwisch
8e.

spacing
d between
planes

X-ray
intensity
(from
detector)

n
2 sinc

X-Ray Diffraction Pattern

z

z
c

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. 3.22, Callister 8e.

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

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

Some materials can have more than one crystal

polycrystals
structure.
This oriented
is referred
to as polymorphism
with randomly
grains.
(or
allotropy).
X-ray diffraction is used for crystal structure and
interplanar spacing determinations.

Adapted from Callister 8e.