Chapter 1 - Introduction

1.1. Historical Perspectives

• Materials drives our society

• Early civilizations designated by level of materials development

• Initially natural materials, then

• Develop techniques to produce materials with superior qualities

1
1.2. Materials science and Engineering
• A multidisciplinary subject such as chemistry, physics, and
engineering

What is materials science?

• Involves investigating the relationships that exist between the
structures and properties of materials

• Develop or synthesize new materials

What is materials engineering?

• Involve designing or engineering the structure of a material to produce
a predetermined set of properties
• Create new products or systems using excising materials
2
 Why study materials?
• applied scientists or engineers must make material choices
• materials selection
– in-service performance
– deterioration
– economics

aluminum glass plastic

3
 1.3. Classification of materials
Metals Ceramics & Glasses Polymers
• good conductors • thermally and • very large molecules
of electricity and electrically insulating • Soft, ductile, low
heat • resistant to high strength, low density
• lustrous temperatures and • Thermal & electrical
appearance harsh environments insulators
• susceptible to • hard, but brittle • Optically translucent or
corrosion transparent.
• strong, but
deformable

4
 Classification of Materials: Additional
Categories
Composites Semiconductors Biomaterials
• consist of more than • electrical properties • implanted in human
one material type between conductors body
• designed to display and insulators • compatible with
a combination of • electrical properties body tissues
properties of each can be precisely
component controlled

ex. semiconductor chips

ex. hip replacement
ex. fiberglass surfboards 5
 1.4. Processing  structure  properties  performance
• arrangement of internal
structure components
• subatomic
• atomic
• microscopic
• macroscopic (bulk)

characterization
processing properties
• method of preparing • material characteristic
material • response to external
stimulus
• mechanical,
performance electrical, thermal,
• behavior in a magnetic, optical,
particular deteriorative
application

6
 Structure, Processing, & Properties
• Properties depend on structure
ex: hardness vs structure of steel

(d)
6 00
Hardness (BHN)

30 mm
5 00 (c)
Data obtained from Figs. 10.30(a)
4 00 (b) and 10.32 with 4 wt% C composition,
(a) and from Fig. 11.14 and associated
4 mm discussion, Callister & Rethwisch 8e.
3 00 Micrographs adapted from (a) Fig.
10.19; (b) Fig. 9.30;(c) Fig. 10.33;
30 mm
30 mm and (d) Fig. 10.21, Callister &
2 00 Rethwisch 8e.

100
0.01 0.1 1 10 100 1000
Cooling Rate (ºC/s)
• Processing can change structure
ex: structure vs cooling rate of steel
7
Aluminum oxide (AlO3) may be transparent,
translucent, or opaque depending on the material
structure.

8
 Chapter 2: Atomic Structure &
Interatomic Bonding

ISSUES TO ADDRESS...

• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

9
2.1 Atomic Structure and periodic table
Atomic Structure
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons
}1.67 x 10-27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

• A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.022 x 1023 molecules or atoms

Avagadro‘s number = 6.022 x 10
23 = NA

1 amu/atom = 1g/mol
C 12.011 10

H 1.008 etc.
 Atomic Structure

• Valence electrons determine all of the

following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical

11
 Electronic Structure
• Electrons have wavelike and particulate
properties.
– This means that electrons are in orbitals defined by a
probability.
– Each orbital at discrete energy level is determined by
quantum numbers.

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n -1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

12
 Electron Energy States
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1
13
 SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 8e.
Carbon 6 1s 2 2s 2 2p 2
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

• Valence (outer) shell usually not filled completely.

14
 Electron Configurations
• Valence electrons – those in unfilled shells
• Filled shells more stable
• Valence electrons are most available for
bonding and tend to control the chemical
properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

15
 Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1

16
 The Periodic Table
• Columns: Similar Valence Structure

inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
17
 Electronegativity
• Ranges from 0.7 to 4.0,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

18
 2.2. Atomic Bonding in Solids
Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2
Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6
[Ne] [Ne]

19
 Ionic Bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

20
 Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
-+ -
A +
B
EN = EA + ER =
r rn
Repulsive energy ER

n = 8 for ions
Interatomic separation r

Net energy EN
- +
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.

Attractive energy EA

- + 21
 Examples: Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

22
 Covalent Bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister & Rethwisch 8e.

23
 Primary Bonding
• Metallic Bond -- delocalized as electron cloud

• Ionic-Covalent Mixed Bonding

 (XA -XB) 
2
-
% ionic character = 1 - e 4  x (100%)
 
 

where XA & XB are electronegativities

Ex: MgO XMg = 1.2
XO = 3.5

 ( 3.5-1.2 )2 
 - 
% ionic character  1 - e 4
 x (100%)  73.4% ionic
 
 
24
METALLIC BONDING

25
 SECONDARY BONDING
• Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
Callister & Rethwisch 8e. bonding

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

26
 Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
inter-molecular
27
 Properties From Bonding: Tm
• Bond length, r • Melting Temperature, Tm
Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
―bond energy‖

28
 Properties From Bonding : a
• Coefficient of thermal expansion, a
length, L o coeff. thermal expansion
unheated, T1
DL DL
= a (T2 -T1)
heated, T 2 Lo

• a ~ symmetric at ro
Energy
unstretched length
ro
r a is larger if Eo is smaller.

E
larger a
o
E smaller a
o 29
 Summary: Primary Bonds
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large a

30
 Chapter 3: Crystalline structure and
imperfections in Solids

3.1. The structure of Crystalline Solids

ISSUES TO ADDRESS...
• How do atoms assemble into solid structures?

• How does the density of a material depend on

its structure?

• When do material properties vary with the

sample (i.e., part) orientation?

31
 3.1. Crystal structures
• The atomic arrangement in a crystal is called crystal structure

A crystal structure consists of a lattice and a basis.

• A lattice is a regular, periodic array of points in space.
• The basis may be a single atom (ion) or a group of atoms (ions).
• The unit cell is smallest repetitive volume which contains the
complete lattice pattern of a crystal. It can be chosen from one of
several geometries that contain equivalent information, as indicated
by the dashed regions.
 Two possible choices
of repeating unit are
shown but (b) would
be preferred to (a)
because it is smaller.

Unit cell

The angles (a, β, g) and lengths (a, b, c)

used to define the size and shape of a unit
cell are the unit cell parameters (the
‗lattice parameters‘)

Fig. 3.4, Callister & Rethwisch 8e.

• Crystals are composed of a periodic array of atoms
• The simplest repeating unit in a crystal is called a unit cell
There are a total of seven different lattice systems and 14 different unit cells
(Bravais lattice)
14 Bravais lattice

34
 3.2. Close-packed crystal structures
Energy and Packing
• Non dense, random packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

• Dense, ordered packing Energy

typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have 35

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.

Si Oxygen
Noncrystalline materials...
• atoms have no periodic packing
• occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.23(b),
Callister & Rethwisch 8e.

36
 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

37
 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...

38
 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)

39
 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
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
Adapted from Fig. 3.24,
Callister & Rethwisch 8e. 40
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 (a), Tantalum, Molybdenum

• Coordination # = 8

Adapted from Fig. 3.2,

Callister & Rethwisch 8e.

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

41
 Atomic Packing Factor: BCC
• APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
Adapted from R length = 4R = 3 a
Fig. 3.2(a), Callister &
Rethwisch 8e.
a
atoms volume
4
unit cell 2 p ( 3a/4 ) 3
3 atom
APF =
3 volume
a
unit cell 42
 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 & Rethwisch 8e.

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

43
 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 & atoms volume
Rethwisch 8e. 4
unit cell 4 p ( 2a/4 ) 3
3 atom
APF =
3 volume
a
unit cell
44
 FCC Stacking Sequence
• ABCABC... Stacking Sequence
• 2D Projection
B B
C
A
A sites B B B
C C
B sites B B
C sites

45
 Hexagonal Close-Packed Structure
(HCP)
• ABAB... Stacking Sequence
• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a Adapted from Fig. 3.3(a),
Callister & Rethwisch 8e.

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633 46
 Theoretical Density, r

Mass of Atoms in Unit Cell

Density = r =
Total Volume of Unit Cell

nA
r =
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a3 for cubic
NA = Avogadro‘s number
= 6.022 x 1023 atoms/mol

47
 Theoretical Density, r
• 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 &
a a = 4R/ 3 = 0.2887 nm
Rethwisch 8e.
atoms
g
unit cell 2 52.00 rtheoretical = 7.18 g/cm3
mol
r= ractual = 7.19 g/cm3
a3 6.022 x 1023
volume atoms
unit cell mol 48
 Densities of Material Classes
In general Graphite/
rmetals > rceramics > rpolymers
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
30
Why? Platinum
B ased on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
(metallic bonding) Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia

r (g/cm3 )
5
Ceramics have... 4
Titanium
Al oxide
• less dense packing 3
Diamond
Si nitride
Aluminum Glass -soda
• often lighter elements Concrete
Silicon PTFE
Glass fibers
GFRE*
2 Carbon fibers
Polymers have... Magnesium G raphite
Silicone CFRE *
A ramid fibers
PVC
• low packing density PET
PC
AFRE *
1 HDPE, PS
(often amorphous) PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood

• intermediate values 0.3

Data from Table B.1, Callister & Rethwisch, 8e.
49
 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
- Has single grain
• Polycrystals
-Properties may/may not 200 mm
vary with direction.
-If grains are randomly
oriented: isotropic.
(Epoly iron = 210 GPa)
-If grains are textured,
anisotropic.

• Amorphous solids
-no long range order. ex. glass
50
 Polymorphism
• Two or more distinct crystal structures for the same
material (allotropy/polymorphism)
iron system
ex. titanium
liquid
a, -Ti
1538ºC
BCC -Fe
ex. carbon 1394ºC
diamond, graphite FCC g-Fe
912ºC
BCC a-Fe

51
3.3. Crystallographic Directions and Planes

Point coordinates for unit cell center are

½½½

Point Coordinates

52
 Crystallographic Directions
z Procedure
1. Any line (or vector direction) is specified by two
c points. The first point is, typically, at the origin
(000), if not, subtract.
2. Determine length of vector projection in each of
y three axes in units (or fractions) of a, b, and c.
(000)
a 3. Multiply or divide by a common factor to reduce
b the lengths to the smallest integer values, u v w.
x 4. Enclose in square brackets, no commas: [u v w].
5. Designate negative numbers by a bar.
ex: x(a), y(b), z(c)
=> 2, 0, 1 => [ 201 ]
1, 0, ½

ex: -1, 1, 1 => [ 111 ] where overbar represents a negative index

• families of directions represented by <uvw> 53

 Crystallographic Directions
z pt. 2
Example 2: if point 1 not start from origin
head
pt. 1 x1 = a, y1 = b/2, z1 = 0
pt. 2 x2 = -a, y2 = b, z2 = c

y
pt. 1:
x tail => -2, 1/2, 1

Multiplying by 2 to eliminate the fraction

-4, 1, 2 => [ 412 ] where the overbar represents a

negative index

families of directions <uvw>

54
 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 2
LD   3.5 nm-1
Adapted from
Fig. 3.1(a),
length 2a
Callister &
Rethwisch 8e.

55
 HCP Crystallographic Directions
z
Procedure
1. Vector repositioned (if necessary) to pass
through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no commas
a3
[uvtw] a
a1
2
Adapted from Fig. 3.8(a),
Callister & Rethwisch 8e.
a2 -a3
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate
projections onto a1 and a2 axes a1
56
 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
u  (2 u ' - v ')
3
a2
1
v  (2 v ' - u ')
- 3
a3
t  - (u +v )
w  w'
a1

Fig. 3.8(a), Callister & Rethwisch 8e.

57
 Crystallographic Planes

Adapted from Fig. 3.10,

Callister & Rethwisch 8e.
58
 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.

• Procedure
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)

59
 Crystallographic Planes
z
example a b c
1. Intercepts 1 1  c
2. Reciprocals 1/1 1/1 1/
1 1 0
3. Reduction 1 1 0 y
a b
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (100) a b
x
60
 Crystallographic Planes
z
example a b c c
1. Intercepts 1/2 1 3/4 
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3  y

3. Reduction 6 3 4 a b

4. Miller Indices (634) x

Family of Planes {hkl}

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

61
 Crystallographic Planes (HCP)
• In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1  -1 1
2. Reciprocals 1 1/ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(b),

Callister & Rethwisch 8e.

62
 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.

63
 Planar Density of (100) Iron
Solution: At T < 912ºC iron has the BCC structure.
2D repeat unit

(100) 4 3
a R
3

Adapted from Fig. 3.2(c), Callister & Rethwisch 8e. Radius of iron R = 0.1241 nm
atoms
2D repeat unit 1
1 atoms atoms
19
Planar Density = = 2 = 12.1 = 1.2 x 10
area a2 4 3 nm 2 m2
R
2D repeat unit 3
64
 Planar Density of (111) Iron
Solution (cont): (111) plane 1 atom in plane/ unit surface cell

2a atoms in plane
atoms above plane
atoms below plane

3
h a
2
2
 4 3  16 3 2
area  2 ah  3 a  3 
2
R   R
atoms  3  3
2D repeat unit 1
atoms = atoms
Planar Density = = 7.0 0.70 x 1019
nm 2 m2
area 16 3 2
R
2D repeat unit 3
65
 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.

66
 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).

67
 3.4. Imperfections in Solids
ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable?

68
 Solidification

• Solidification- a result of casting of molten material

– 2 steps
• Nuclei form
• Nuclei grow to form crystals – grain structure
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig.4.14 (b), Callister 7e.

• Crystals grow until they meet each other

69
 Polycrystalline Materials

Grain Boundaries
• regions between crystals
• transition from lattice of
one region to that of the
other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
– high chemical reactivity
Adapted from Fig. 4.7, Callister 7e.

70
Types of defects based on dimensionality
0D 1D 2D
(Point defect) (Line defect) (surface defect)
• vacancy • edge dislocation • grain boundary
• interstitial • screw dislocation • twin boundary
• substitutional • mixed dislocation • stacking faults

3D
(volume defect)
• cracks/voids/pores
• inclusion- foreign particles

71
 Point Defects
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

72
 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

 -Q 
 exp 
Nv v
No. of potential
N  kT 
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
73
 Measuring Activation Energy

• We can get Qv from  -Q 

Nv
= exp 
 v
an experiment. N  kT 
• Measure this... • Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T 1/ T
defect concentration
74
 Estimating Vacancy Concentration
• Find the equil. # of vacancies in 1 m3 of Cu at 1000C.
• Given:
r = 8.4 g /cm 3 A Cu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
 -Q 
exp 
Nv  v -4
 kT  = 2.7 x 10
N
1273K
8.62 x 10-5 eV/atom-K
NA
For 1 m3 , N= r x x 1 m3 = 8.0 x 1028 sites
A Cu
• Answer:
Nv = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies
75
 Point Defects in Alloys
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)

Second phase particle

--different composition
--often different structure.

76
Conditions for substitutional solid solution (S.S.)
• W. Hume – Rothery rule
– 1. Dr (atomic radius) < 15%
– 2. Proximity in periodic table
• i.e., similar electronegativities
– 3. Same crystal structure for pure metals
– 4. Valency
• All else being equal, a metal will have a greater tendency to
dissolve a metal of higher valency than one of lower valency

77
Application of Hume–Rothery rules – Solid
Solutions
Element Atomic Crystal Electro- Valence
Radius Structure nega-
1. Would you predict (nm) tivity

more Al or Ag Cu
C
0.1278
0.071
FCC 1.9 +2

to dissolve in Zn? H 0.046

O 0.060
Ag 0.1445 FCC 1.9 +1
Al 0.1431 FCC 1.5 +3
2. More Zn or Al Co 0.1253 HCP 1.8 +2
Cr 0.1249 BCC 1.6 +3
in Cu? Fe
Ni
0.1241
0.1246
BCC
FCC
1.8
1.8
+2
+2
Pd 0.1376 FCC 2.2 +2
Zn 0.1332 HCP 1.6 +2

Table on p. 106, Callister 7e.

78
 Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

Adapted from Fig. 7.8, Callister 7e.

79
Dislocations
• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b  to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b  to dislocation line
Burger‘s vector, b: measure of lattice distortion

80
 Screw Dislocation

Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister 7e.

81
 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

82
 Imperfections in Solids
Dislocations are visible in electron micrographs

Adapted from Fig. 4.6, Callister 7e.

83
 Dislocations & Crystal Structures
• Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

• Comparison among crystal structures:

FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;
BCC: none

• Specimens that Mg (HCP)

were tensile
tested. tensile direction
Al (FCC)
84
 Planar Defects in Solids
• twin boundary (plane)
– Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 4.9,

Callister 7e.

• Stacking faults
– For FCC metals an error in ABCABC packing sequence
– Ex: ABCABABC
• Grain boundary
- Polycrystalline material comprised
of small crystals or grains

Grain Boundary 85
 Summary
• Point, Line, planar, bulk defects exist in solids.

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• Defects affect material properties (e.g., grain

boundaries control crystal slip).
• Defects may be desirable or undesirable
(e.g., dislocations may be good or bad, depending
on whether plastic deformation is desirable or not.)

86
 Chapter 4 Diffusion

ISSUES TO ADDRESS...
• How does diffusion occur?

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for

some simple cases?

• How does diffusion depend on structure

and temperature?

87
 4.1. Diffusion
Diffusion - Mass transport by atomic motion
Mechanisms:
Gases & Liquids – random (Brownian) motion
Solids – vacancy diffusion or interstitial diffusion

• Interdiffusion: In an alloy, atoms tend to migrate

from regions of high conc. to regions of low conc.
Initially Adapted from After some time
Figs. 5.1 and
5.2, Callister &
Rethwisch 8e.

88
 Diffusion
• Self-diffusion: In an elemental solid, atoms also migrate.
Label some atoms After some time
C
C
A D
A
D
B
B

There is no net mass transport, but atoms migrate in a random

manner throughout the crystal.

89
 Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- activation energy to exchange.

increasing elapsed time

90
 Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can diffuse
between atoms.

Adapted from Fig. 5.3(b), Callister & Rethwisch 8e.

Interstitial diffusion is more rapid than vacancy diffusion

91
 4.2. Fick‘s Law of Diffusion
• How do we quantify the amount or rate of diffusion?

moles (or mass) diffusing mol kg

J  Flux   or
surface area time  cm s m2s
2

• Measured empirically
– Make thin film (membrane) of known surface area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
M l dM mass J  slope
J  diffused
At A dt
time

92
Fick‘s First Law (Steady-State Diffusion)
Rate of diffusion independent of time
dC
Flux proportional to concentration gradient =
dx

C1 C1 Fick‘s first law of diffusion

dC
C2 C2 J  -D
dx
x1 x2
x
D  diffusion coefficient
dC DC C2 - C1
if linear  
dx Dx x2 - x1

93
Example: Chemical Protective Clothing
(CPC)

• Methylene chloride is a common ingredient of paint

removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves should be worn.
• If butyl rubber gloves (0.04 cm thick) are used, what
is the diffusive flux of methylene chloride through the
glove?
• Data:
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s C1 = 0.44 g/cm3
– surface concentrations: C2 = 0.02 g/cm3
94
 Example (cont).
• Solution – assuming linear conc. gradient
glove
C1 dC C2 - C1
tb 
2 J -D  -D
paint
6D dx x2 - x1
skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

-8 (0.02 g/cm3 - 0.44 g/cm3 )

2 -5 g
J  - (110 x 10 cm /s)  1.16 x 10
(0.04 cm) cm2s

95
 Diffusion and Temperature

• Diffusion coefficient increases with increasing T.

 Qd 
D  Do exp- 
 R T 

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

96
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in a-Fe Al in Al
10-14 C in g-Fe Fe in a-Fe
Fe in g-Fe

10-20
0.5 1.0 1.5 1000 K/T

Adapted from Fig. 5.7, Callister & Rethwisch 8e. (Date for Fig. 5.7
taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

97
Example: At 300ºC the diffusion coefficient and
activation energy for Cu in Si are
D(300ºC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350ºC?

D transform ln D
data

Temp = T 1/T

Qd 1 Qd  1
lnD2  lnD0 -   and lnD1  lnD0 -  
R  T2  R  T1 
D Q  1 1
 lnD2 - lnD1  ln 2  - d  - 
D1 R  T2 T1 
98
 Example (cont.)
 Qd  1 1 
D2  D1 exp-  - 
 R  T2 T1 

T1 = 273 + 300 = 573 K

T2 = 273 + 350 = 623 K

-11 2  - 41,500 J/mol  1 1 

D2  (7.8 x 10 m /s) exp  - 
 8.314 J/mol - K  623 K 573 K 

D2 = 15.7 x 10-11 m2/s

99
 Fick‘s Second Law (Non-steady State Diffusion)
• The concentration of diffusing species is a function of both
time and position C = C(x,t)

C  2C
Fick‘s Second Law D 2
t x

C x , t  - Co  x 
Solution:  1 - erf  
Cs - Co  2 Dt 

C(x,t) = Conc. at point x at

CS
time t
erf (z) = error function

2 z C(x,t)

-y 2
 e dy
p 0
Co
erf(z) values are given in 100
Table 5.1 Adapted from Fig. 5.5,
Callister & Rethwisch 8e.
 Processing Using Diffusion
• Case Hardening:
Adapted from
-- Diffuse carbon atoms chapter-opening
into the host iron atoms photograph,
Chapter 5,
at the surface. Callister &
Rethwisch 8e.
-- Example of interstitial (Courtesy of
Surface Division,
diffusion is a case Midland-Ross.)

hardened gear.

• Result: The presence of C

atoms makes iron (steel) harder.

101
 Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
Adapted from Figure 18.27, Callister &
Rethwisch 8e. 102
 Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials with secondary • materials with covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

103
 Chapter 5: Mechanical Properties
and Failure of Materials
Mechanical Properties
ISSUES TO ADDRESS...
• Stress and strain: What are they and why are
they used instead of load and deformation?
• Elastic behavior: When loads are small, how much
deformation occurs? What materials deform least?
• Plastic behavior: At what point does permanent
deformation occur? What materials are most
resistant to permanent deformation?
• Toughness and ductility: What are they and how
do we measure them?
104
5.1. Concepts of Stress and Strain
Types of Loading

105
 Concepts of Stress and Strain
(tension and compression)

To compare specimens of different sizes, the load is calculated per unit area.
•Engineering stress: σ = F / Ao
F is load applied perpendicular to specimen cross-section; A0 is cross-sectional area
(perpendicular to the force) before application of the load.
•Engineering strain: ε = Δl / lo (× 100 %)
Δl is change in length, lo is the original length.

•These definitions of stress and strain allow one to compare test results for specimens of
different cross-sectional area Ao and of different length lo.
•Stress and strain are positive for tensile loads, negative for compressive loads

106
• Shear stress: τ = F / Ao
F is load applied parallel to the upper and lower faces each of which has an area Ao.
• Shear strain: γ = tanθ (× 100 %)
θ is strain angle
• Torsion is variation of pure shear. The shear stress in this case is a function of applied
torque T, shear strain is related to the angle of twist, υ.

107
 Engineering Strain
• Tensile strain: • Lateral strain:
/2
-L
e   eL 
Lo Lo wo
wo

L /2
• Shear strain:
q
Dx g = Dx/y = tan q

y 90º - q
Strain is always
90º dimensionless.
Adapted from Fig. 6.1(a) and (c), Callister & Rethwisch 8e. 108
 Stress-Strain Testing
• Typical tensile test • Typical tensile
machine specimen

Adapted from
extensometer specimen Fig. 6.2,
Callister &
Rethwisch 8e.

gauge
length

Adapted from Fig. 6.3, Callister & Rethwisch 8e. (Fig. 6.3 is taken from H.W.
Hayden, W.G. Moffatt, and J. Wulff, The Structure and Properties of Materials,
Vol. III, Mechanical Behavior, p. 2, John Wiley and Sons, New York, 1965.)
109
 5.2 Elastic and plastic deformations
Elastic Deformation

elastic deformation is time

independent

• Elastic deformation: stress and strain are proportional

• Elasticity can be linear or Non linear
• Metals and ceramics usually show linear elastic behavior 110

• Some materials (e.g., gray cast iron, concrete, and many polymers) exhibit
non linear elasticity
 Plastic Deformation (Metals)
1. Initial 2. Small load 3. Unload
bonds
stretch planes
& planes still
shear sheared

plastic
elastic + plastic

F
F
Plastic means permanent! linear linear
elastic elastic

plastic
111
 Linear Elastic Properties
• Modulus of Elasticity, E:
(also known as Young's modulus)

• Hooke's Law: This modulus may be thought of as stiffness, or a

material’s resistance to elastic deformation.
s=Ee
s F
E

e
Linear-
elastic F
simple
tension
test

112
 Poisson's ratio, n
• Poisson's ratio, n:
eL
The ratio of lateral strain to
n > 0.50 density increases
linear strains.
eL n < 0.50 density decreases
n- e
(voids form)
e
metals: n ~ 0.33 -n Units:
ceramics: n ~ 0.25 E: [GPa] or [psi]
polymers: n ~ 0.40 n: dimensionless

• Materials subject to tension shrink laterally, those

subject to compression, bulge.
• Theoretical value for isotropic material: 0.25
Maximum value: 0.50, Typical value: 0.24 - 0.30
113
Other Elastic Properties: shear modulus
• Elastic Shear t
modulus, G: G
g
t=Gg

Relationship of shear stress to shear strain:

τ = G γ, where: γ = tanθ = Δy / zo
G is Shear Modulus (Units: N/m2 or Pa)

For isotropic material:

E = 2G(1+υ) → G ~ 0.4E
114
 Young‘s Moduli: Comparison
Graphite
Metals Composites
Ceramics Polymers
Alloys /fibers
Semicond
1200
10 00 Diamond
800
600
Si carbide
400 Tungsten Al oxide Carbon fibers only
Molybdenum Si nitride
E(GPa) 200
Steel, Ni
Tantalum <111>
C FRE(|| fibers)*
Platinum Si crystal
Cu alloys <100> Aramid fibers only
10 0 Zinc, Ti
80 Silver, Gold
Glass -soda A FRE(|| fibers)* Based on data in Table B.2,
Aluminum Glass fibers only
60
40
Magnesium,
Tin G FRE(|| fibers)* Callister & Rethwisch 8e.
Concrete Composite data based on
109 Pa 20 GFRE*
CFRE *
reinforced epoxy with 60 vol%
of aligned
G raphite G FRE( fibers)*
10 carbon (CFRE),
8 C FRE( fibers) *
6 AFRE( fibers) *
aramid (AFRE), or
Polyester glass (GFRE)
4 PET
PS fibers.
PC Epoxy only
2
PP
1 HDP E
0.8
0.6 Wood( grain)
PTF E
0.4

0.2 LDPE 115

 Plastic (Permanent) Deformation
(at lower temperatures, i.e. T < Tmelt/3)

• Simple tension test:

Elastic+Plastic
engineering stress, s at larger stress

Elastic
initially
permanent (plastic)
after load is removed

ep engineering strain, e

plastic strain Adapted from Fig. 6.10(a),

Callister & Rethwisch 8e.

116
 Yield Strength, sy
• Stress at which noticeable plastic deformation has
occurred.
when ep = 0.002
tensile stress, s
sy = yield strength
sy

Note: for 2 inch sample

e = 0.002 = Dz/z
 Dz = 0.004 in

engineering strain, e
ep = 0.002 Adapted from Fig. 6.10(a),
Callister & Rethwisch 8e.
117
Stress- Strain Curve for Mild Steel (Ductile Material)

Yield stress Ultimate stress

Point point
Breaking stress
point

Plastic state
Of material
Stress
Elastic State
Of material

E = modulus of
elasticity
Strain
 Yield Strength : Comparison
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
2000
Steel (4140) qt

1000
Yield strength, sy (MPa)

Ti (5Al-2.5Sn) a

in ceramic matrix and epoxy matrix composites, since

700 W (pure)

since in tension, fracture usually occurs before yield.

in tension, fracture usually occurs before yield.

600 Cu (71500) cw
500 Mo (pure)
400 Steel (4140) a
Steel (1020) cd Room temperature
300
values
Hard to measure ,

Hard to measure,
Al (6061) ag
200 Steel (1020) hr
¨
Ti (pure) a
Ta (pure)
Cu (71500) hr Based on data in Table B.4,
Callister & Rethwisch 8e.
100
a = annealed
dry
70 PC
hr = hot rolled
60 Nylon 6,6 ag = aged
50 Al (6061) a PET
cd = cold drawn
40 PVC humid
cw = cold worked
PP
30 HDPE qt = quenched & tempered
20

LDPE
Tin (pure) 119
10
 Tensile Strength, TS
• Maximum stress on engineering stress-strain curve.
Adapted from Fig. 6.11,
Callister & Rethwisch 8e.
TS
F = fracture or
sy
ultimate
engineering

strength
stress

Typical response of a metal

Neck – acts
as stress
concentrator
strain
engineering strain
• Metals: occurs when noticeable necking starts.
• Polymers: occurs when polymer backbone chains are
aligned and about to break.
120
 Tensile Strength: Comparison
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
5000 C fibers
Aramid fib
3000 E-glass fib
Tensile strength, TS (MPa)

2000 Steel (4140) qt

A FRE(|| fiber)
1000 W (pure) Diamond GFRE(|| fiber)
Ti (5Al-2.5Sn)aa CFRE(|| fiber)
Steel (4140)
Cu (71500) cw Si nitride
Cu (71500) hr Al oxide
300
Steel (1020)
Al (6061) ag
Ti (pure) a
Room temperature
200 Ta (pure)
values
Al (6061) a
100 Si crystal wood(|| fiber) Based on data in Table B.4,
<100> Nylon 6,6
Glass-soda PC PET Callister & Rethwisch 8e.
40 PVC GFRE( fiber) a = annealed
Concrete PP
30 CFRE( fiber) hr = hot rolled
A FRE( fiber)
HDPE ag = aged
20 Graphite
LDPE cd = cold drawn
cw = cold worked
10 qt = quenched & tempered
AFRE, GFRE, & CFRE =
aramid, glass, & carbon
fiber-reinforced epoxy
wood ( fiber)
composites, with 60 vol%
fibers.
1 121
 Ductility
Lf - Lo
• Plastic tensile strain at failure: %EL  x 100
Lo
smaller %EL
Engineering
tensile
stress, s larger %EL Ao
Lo Af Lf
Adapted from Fig. 6.13,
Callister & Rethwisch 8e.

Engineering tensile strain, e

• Another ductility measure: Ao - Af

%RA = x 100
Ao

122
 Toughness
• Energy to break a unit volume of material
• Approximate by the area under the stress-strain curve.

Engineering small toughness (ceramics)

tensile large toughness (metals)
stress, s
Adapted from Fig. 6.13, very small toughness
Callister & Rethwisch 8e. (unreinforced polymers)

Engineering tensile strain, e

Brittle fracture: elastic energy

Ductile fracture: elastic + plastic energy
123
 Resilience, Ur
• Ability of a material to store energy
– Energy stored best in elastic region

ey
Ur   sde
0
If we assume a linear
stress-strain curve this
simplifies to

1
Ur  sy e y
2
Adapted from Fig. 6.15,
Callister & Rethwisch 8e.
124
 Elastic Strain Recovery

syi D

syo
2. Unload
Stress

1. Load 3. Reapply
load
Strain

Adapted from Fig. 6.17, Elastic strain

Callister & Rethwisch 8e. recovery
125
 Hardness
• Resistance to permanently indenting the surface.
• Large hardness means:
-- resistance to plastic deformation or cracking in
compression.
-- better wear properties.
apply known force measure size
e.g., of indent after
10 mm sphere removing load

Smaller indents
D d mean larger
hardness.

most brasses easy to machine cutting nitrided

plastics Al alloys steels file hard tools steels diamond

increasing hardness
126
 Hardness: Measurement

• Rockwell
– No major sample damage
– Each scale runs to 130 but only useful in range
20-100.
– Minor load 10 kg
– Major load 60 (A), 100 (B) & 150 (C) kg
• A = diamond, B = 1/16 in. ball, C = diamond

• HB = Brinell Hardness
– TS (psia) = 500 x HB
– TS (MPa) = 3.45 x HB 127
 Hardness: Measurement
Table 6.5

128
 True Stress & Strain
Note: S.A. changes when sample
stretched
sT  F Ai sT  s1 + e 
• True stress eT  ln i  o  eT  ln1 + e 

• True strain

Adapted from Fig. 6.16,

Callister & Rethwisch 8e.

129
 Hardening
• An increase in sy due to plastic deformation.
s
large hardening
sy
1
sy small hardening
0

e
• Curve fit to the stress-strain response:
hardening exponent:
sT  K eT  n n = 0.15 (some steels)
to n = 0.5 (some coppers)
―true‖ stress (F/A) ―true‖ strain: ln(L/Lo)
130
 Summary
• Stress and strain: These are size-independent
measures of load and displacement, respectively.
• Elastic behavior: This reversible behavior often
shows a linear relation between stress and strain.
To minimize deformation, select a material with a
large elastic modulus (E or G).
• Plastic behavior: This permanent deformation
behavior occurs when the tensile (or compressive)
uniaxial stress reaches sy.
• Toughness: The energy needed to break a unit
volume of material.
• Ductility: The plastic strain at failure.

131
 5.3. Failure in Materials
ISSUES TO ADDRESS...
• How do cracks that lead to failure form?
• How is fracture resistance quantified? How do the fracture
resistances of the different material classes compare?
• How do we estimate the stress to fracture?
• How do loading rate, loading history, and temperature
affect the failure behavior of materials?

Ship-cyclic loading Computer chip-cyclic Hip implant-cyclic

from waves. thermal loading. loading from walking.
Adapted from chapter-opening photograph, Adapted from Fig. 22.30(b), Callister 7e. Adapted from Fig. 22.26(b),
Chapter 8, Callister & Rethwisch 8e. (by (Fig. 22.30(b) is courtesy of National Callister 7e.
Neil Boenzi, The New York Times.) Semiconductor Corporation.)
132
 Fracture mechanisms
• Ductile fracture
– Accompanied by significant plastic
deformation
• Brittle fracture
– Little or no plastic deformation
– Catastrophic

133
 Ductile vs Brittle Failure
• Classification:
Fracture Very Moderately
Brittle
behavior: Ductile Ductile

Adapted from Fig. 8.1,

Callister & Rethwisch 8e.

%AR or %EL Large Moderate Small

• Ductile fracture is Ductile: Brittle:
usually more desirable Warning before No
than brittle fracture! fracture warning

134
 Example: Pipe Failures
• Ductile failure:
-- one piece
-- large deformation

• Brittle failure:
-- many pieces
-- small deformations

Figures from V.J. Colangelo and F.A.

Heiser, Analysis of Metallurgical Failures
(2nd ed.), Fig. 4.1(a) and (b), p. 66 John
Wiley and Sons, Inc., 1987. Used with
permission.

135
 Moderately Ductile Failure
• Failure Stages:
void void growth shearing
necking fracture
nucleation and coalescence at surface
s

• Resulting 50
50mm
mm
fracture
surfaces
(steel)
100 mm
particles From V.J. Colangelo and F.A. Heiser, Fracture surface of tire cord wire
serve as void Analysis of Metallurgical Failures (2nd loaded in tension. Courtesy of F.
ed.), Fig. 11.28, p. 294, John Wiley and Roehrig, CC Technologies, Dublin,
nucleation Sons, Inc., 1987. (Orig. source: P. OH. Used with permission.
sites. Thornton, J. Mater. Sci., Vol. 6, 1971, pp.
347-56.) 136
Moderately Ductile vs. Brittle Failure

cup-and-cone fracture brittle fracture

Adapted from Fig. 8.3, Callister & Rethwisch 8e.

137
 Brittle Failure
Arrows indicate point at which failure originated

Adapted from Fig. 8.5(a), Callister & Rethwisch 8e.

138
 Brittle Fracture Surfaces
• Intergranular 304 S. Steel • Transgranular
(between grains) (metal) (through grains)

316 S. Steel
(metal)

160 mm
4 mm

3 mm
1 mm
Al Oxide (ceramic)
Polypropylene (polymer) 139
 Fracture Toughness Ranges
Graphite/
Metals/ Composites/
Ceramics/ Polymers
Alloys fibers
Semicond
100
C-C (|| fibers) 1
70 Steels
60 Ti alloys
50
40
Al alloys
30 Mg alloys Based on data in Table B.5,
K Ic (MPa · m0.5 )

Callister & Rethwisch 8e.

20 Composite reinforcement geometry is: f
Al/Al oxide(sf) 2 = fibers; sf = short fibers; w = whiskers;
Y2 O 3 /ZrO 2 (p) 4 p = particles. Addition data as noted
10 C/C( fibers) 1 (vol. fraction of reinforcement):
Al oxid/SiC(w) 3 1. (55vol%) ASM Handbook, Vol. 21, ASM Int.,
Diamond Si nitr/SiC(w) 5 Materials Park, OH (2001) p. 606.
7 Al oxid/ZrO 2 (p) 4 2. (55 vol%) Courtesy J. Cornie, MMC, Inc.,
6 Si carbide Glass/SiC(w) 6 Waltham, MA.
5 Al oxide PET 3. (30 vol%) P.F. Becher et al., Fracture
4 Si nitride Mechanics of Ceramics, Vol. 7, Plenum Press
PP (1986). pp. 61-73.
3 PVC 4. Courtesy CoorsTek, Golden, CO.
5. (30 vol%) S.T. Buljan et al., "Development of
2 PC Ceramic Matrix Composites for Application in
Technology for Advanced Engines Program",
ORNL/Sub/85-22011/2, ORNL, 1992.
6. (20vol%) F.D. Gace et al., Ceram. Eng. Sci.
Proc., Vol. 7 (1986) pp. 978-82.
1 <100>
Si crystal PS Glass 6
<111>
0.7 Glass -soda
0.6 Polyester
Concrete 140
0.5
 Influence of Temperature on
Impact Energy
• Ductile-to-Brittle Transition Temperature (DBTT)...
Low strength (FCC and HCP) metals e.g., Cu, Ni
Impact Energy

Low strength steels (BCC) e.g., iron at T < 914ºC

polymers
Brittle More Ductile
High strength materials

Temperature Adapted from Fig. 8.15,

Callister & Rethwisch 8e.
Ductile-to-brittle
transition temperature

141
 Fatigue
• Fatigue = failure under applied cyclic stress (e.g., bridges,
aircraft, and machine components).

specimen compression on top Adapted from Fig. 8.18,

Callister & Rethwisch 8e.
motor (Fig. 8.18 is from Materials
bearing bearing counter
Science in Engineering, 4/E
by Carl. A. Keyser, Pearson
flex coupling Education, Inc., Upper
tension on bottom Saddle River, NJ.)

• Stress varies with time. s

smax
-- key parameters are S, sm, and
S
cycling frequency sm
smin time

• Key points: Fatigue...

--can cause part failure, even though smax < sy.
--responsible for ~ 90% of mechanical engineering failures.
142
 Types of Fatigue Behavior

S = stress amplitude
• Fatigue limit, Sfat: case for
--no fatigue if S < Sfat unsafe steel (typ.)
Sfat

safe Adapted from Fig.

8.19(a), Callister &
Rethwisch 8e.

10 3 10 5 10 7 10 9
N = Cycles to failure

S = stress amplitude
• For some materials, case for
there is no fatigue unsafe Al (typ.)
limit!
safe Adapted from Fig.
8.19(b), Callister &
Rethwisch 8e.
10 3 10 5 10 7 10 9
N = Cycles to failure
143
 Improving Fatigue Life

S = stress amplitude
1. Impose compressive Adapted from
surface stresses Fig. 8.24, Callister &
Rethwisch 8e.
(to suppress surface near zero or compressive sm
cracks from growing) moderate tensile sm
Larger tensile sm

N = Cycles to failure

--Method 1: shot peening --Method 2: carburizing

shot
C-rich gas
put
surface
into
compression

2. Remove stress bad better

concentrators. Adapted from
Fig. 8.25, Callister &
bad better Rethwisch 8e.

144
 Creep
Sample deformation at a constant stress (s) vs. time
s
s,e

0 t

Primary Creep: slope (creep rate)

decreases with time.
Secondary Creep: steady-state
i.e., constant slope De/Dt).
Adapted from
Fig. 8.28, Callister &
Tertiary Creep: slope (creep rate) Rethwisch 8e.

increases with time, i.e. acceleration of rate. 145

 Creep: Temperature Dependence
• Occurs at elevated temperature, T > 0.4 Tm (in K)

tertiary

primary
secondary

elastic

Adapted from Fig. 8.29,

Callister & Rethwisch 8e.

146
 Creep Failure
• Failure: along grain boundaries.

g.b. cavities

applied
stress

From V.J. Colangelo and F.A. Heiser, Analysis of

Metallurgical Failures (2nd ed.), Fig. 4.32, p. 87, John
Wiley and Sons, Inc., 1987. (Orig. source: Pergamon
Press, Inc.)

147
 Prediction of Creep Rupture Lifetime
• Estimate rupture time
S-590 Iron, T = 800ºC, s = 20,000 psi

100 Time to rupture, tr

T (20 + log t r )  L

Stress (103 psi)

20 function of
temperature
10 applied stress
time to failure (rupture)

data for
S-590 Iron

12 16 20 24 28
1
(1073 K )(20 + logtr )  24x103
103 L (K-h)
Adapted from Fig. 8.32, Callister & Rethwisch
8e. (Fig. 8.32 is from F.R. Larson and J. Ans: tr = 233 hr
Miller, Trans. ASME, 74, 765 (1952).)
148
 Estimate the rupture time for
S-590 Iron, T = 750ºC, s = 20,000 psi
• Solution:
Time to rupture, tr 100

Stress (103 psi)

T (20 + log t r )  L
20
temperature function of
applied stress 10
time to failure (rupture)
data for

(1023 K)(20 + logtr )  24x103 S-590 Iron

1
12 16 20 24 28
103 L (K-h)
Ans: tr = 2890 hr Adapted from Fig. 8.32, Callister & Rethwisch
8e. (Fig. 8.32 is from F.R. Larson and J.
Miller, Trans. ASME, 74, 765 (1952).)
149
 SUMMARY
• Engineering materials not as strong as predicted by theory
• Flaws act as stress concentrators that cause failure at
stresses lower than theoretical values.
• Sharp corners produce large stress concentrations
and premature failure.
• Failure type depends on T and s :
-For simple fracture (noncyclic s and T < 0.4Tm), failure stress
decreases with:
- increased maximum flaw size,
- decreased T,
- increased rate of loading.
- For fatigue (cyclic s:
- cycles to fail decreases as Ds increases.
- For creep (T > 0.4Tm):
- time to rupture decreases as s or T increases. 150
 Chapter 6:
Dislocations & Strengthening
Mechanisms
ISSUES TO ADDRESS...
• Why are the number of dislocations present
greatest in metals?

• How are strength and dislocation motion related?

• Why does heating alter strength and other properties?

151
 6.1. Dislocations & Plastic Deformations
Dislocations and Materials Classes

• Metals (Cu, Al):

+ + + + + + + +
Dislocation motion easiest + + + + + + + +
- non-directional bonding + + + + + + + +
- close-packed directions ion cores
electron cloud
for slip
• Covalent Ceramics
(Si, diamond): Motion difficult
- directional (angular) bonding

• Ionic Ceramics (NaCl):

+ - + - + - +
Motion difficult
- + - + - + -
- need to avoid nearest
neighbors of like sign (- and +) + - + - + - +
152
 Dislocation Motion
Dislocation motion & plastic deformation
• Metals - plastic deformation occurs by slip – an edge
dislocation (extra half-plane of atoms) slides over
adjacent plane half-planes of atoms.

• If dislocations can't move,

Adapted from Fig. 7.1,
Callister & Rethwisch 8e.

plastic deformation doesn't occur! 153

 Dislocation Motion
• A dislocation moves along a slip plane in a slip direction
perpendicular to the dislocation line
• The slip direction is the same as the Burgers vector direction

Edge dislocation

Adapted from Fig. 7.2,

Callister & Rethwisch 8e.

Screw dislocation

154
 Deformation Mechanisms
Slip System
– Slip plane - plane on which easiest slippage occurs
• Highest planar densities (and large interplanar spacings)
– Slip directions - directions of movement
• Highest linear densities

Adapted from Fig.

7.6, Callister &
Rethwisch 8e.

– FCC Slip occurs on {111} planes (close-packed) in <110>

directions (close-packed)
=> total of 12 slip systems in FCC
– For BCC & HCP there are other slip systems.
155
 Stress and Dislocation Motion
• Resolved shear stress, tR
– results from applied tensile stresses
Applied tensile Resolved shear Relation between
stress: s = F/A stress: tR =Fs /A s s and tR

A
F slip plane
tR tR = FS /AS
normal, ns
AS Fcos l A /cos f
FS
F nS f
l A
tR FS AS
F

tR  s cos l cos f
156
 Critical Resolved Shear Stress
• Condition for dislocation motion: tR  tCRSS
• Ease of dislocation motion depends typically
on crystallographic orientation
10-4 GPa to 10-2 GPa
tR  s cos l cos f
s s s

tR = 0 tR = s/2 tR = 0
l = 90° l = 45° f = 90°
f = 45°

t maximum at l = f = 45º 157

Single Crystal Slip

Adapted from Fig.

7.9, Callister &
Rethwisch 8e.

Adapted from Fig. 7.8,

Callister & Rethwisch 8e.
158
 Ex: Deformation of single crystal
a) Will the single crystal yield?
b) If not, what stress is needed?
f = 60°
tcrss = 20.7 MPa
l = 35°
t  s cosl cosf
s  45 MPa

Adapted from t  ( 45 MPa) (cos 35 )(cos 60 )

Fig. 7.7,
Callister &
Rethwisch 8e.   ( 45 MPa) (0.41)
t  18.4 MPa  tcrss  20.7 MPa
s = 45 MPa
So the applied stress of 45 MPa will not cause the
crystal to yield.
159
 Ex: Deformation of single crystal
What stress is necessary (i.e., what is the
yield stress, sy)?

tcrss  20.7 MPa  s y cos l cos f  s y (0.41)

tcrss 20.7 MPa

 sy    50.5 MPa
cos l cos f 0.41

So for deformation to occur the applied stress must

be greater than or equal to the yield stress

s  s y  50.5 MPa
160
 Slip Motion in Polycrystals
• Polycrystals stronger than s
single crystals – grain
boundaries are barriers
to dislocation motion.
Adapted from Fig.
• Slip planes & directions 7.10, Callister &
Rethwisch 8e.
(l, f) change from one (Fig. 7.10 is
courtesy of C.
grain to another. Brady, National
Bureau of
• tR will vary from one Standards [now the
National Institute of
grain to another. Standards and
Technology,
Gaithersburg, MD].)
• The grain with the
largest tR yields first.

• Other (less favorably

oriented) grains 300 mm
yield later.
161
 Anisotropy in sy
• Can be induced by rolling a polycrystalline metal
- before rolling - after rolling
Adapted from Fig. 7.11,
Callister & Rethwisch 8e.
(Fig. 7.11 is from W.G. Moffatt,
G.W. Pearsall, and J. Wulff,
The Structure and Properties
of Materials, Vol. I, Structure,
p. 140, John Wiley and Sons,
New York, 1964.)

rolling direction
235 mm
- isotropic - anisotropic
since grains are since rolling affects grain
equiaxed & orientation and shape.
randomly oriented.

162
 6.2. Strengthening Mechanisms
There are four strategies for strengthening: Reduce Grain
Size, Form Solid Solutions, Precipitation Strengthening, and
Cold Work (Strain Hardening).

1: Reduce Grain Size

• Grain boundaries are
barriers to slip.
• Barrier "strength"
increases with
Increasing angle of
misorientation. Adapted from Fig. 7.14, Callister & Rethwisch
8e. (Fig. 7.14 is from A Textbook of Materials
• Smaller grain size: Technology, by Van Vlack, Pearson Education,
Inc., Upper Saddle River, NJ.)
more barriers to slip.

• Hall-Petch Equation: s yield  so + k y d -1 / 2

163
 2: Form Solid Solutions

• Impurity atoms distort the lattice & generate lattice strains.

• These strains can act as barriers to dislocation motion.
• Smaller substitutional • Larger substitutional
impurity impurity

A C

B D

Impurity generates local stress at A Impurity generates local stress at C

and B that opposes dislocation and D that opposes dislocation
motion to the right. motion to the right.

164
Lattice Strains Around Dislocations

Adapted from Fig. 7.4,

Callister & Rethwisch 8e.

165
 Strengthening by Solid
Solution Alloying
• Small impurities tend to concentrate at dislocations
(regions of compressive strains) - partial cancellation of
dislocation compressive strains and impurity atom tensile strains
• Reduce mobility of dislocations and increase strength

Adapted from Fig. 7.17,

Callister & Rethwisch 8e.
166
 Strengthening by Solid
Solution Alloying
• Large impurities tend to concentrate at
dislocations (regions of tensile strains)

Adapted from Fig. 7.18,

Callister & Rethwisch 8e.

167
 Ex: Solid Solution
Strengthening in Copper
• Tensile strength & yield strength increase with wt% Ni.
Tensile strength (MPa)

180

Yield strength (MPa)

Adapted from Fig.
400 7.16(a) and (b),
Callister &
120 Rethwisch 8e.
300

200 60
0 10 20 30 40 50 0 10 20 30 40 50
wt.% Ni, (Concentration C) wt.%Ni, (Concentration C)

• Empirical relation: s y ~ C1/ 2

• Alloying increases sy and TS.

168
 3: Precipitation Strengthening

• Hard precipitates are difficult to shear.

Ex: Ceramics in metals (SiC in Iron or Aluminum).
precipitate
Large shear stress needed
Side View to move dislocation toward
precipitate and shear it.

Unslipped part of slip plane Dislocation

Top View
―advances‖ but
precipitates act as
S ―pinning‖ sites with
spacing S.
Slipped part of slip plane

1
• Result: sy ~
S
169
 Application:
Precipitation Strengthening
• Internal wing structure on Boeing 767
Adapted from chapter-
opening photograph,
Chapter 11, Callister &
Rethwisch 3e. (courtesy of
G.H. Narayanan and A.G.
Miller, Boeing Commercial
Airplane Company.)

• Aluminum is strengthened with precipitates formed

by alloying.
Adapted from Fig. 11.26,
Callister & Rethwisch 8e.
(Fig. 11.26 is courtesy of
G.H. Narayanan and A.G.
Miller, Boeing Commercial
Airplane Company.)

1.5mm
170
 4: Cold Work (Strain Hardening)

• Deformation at room temperature (for most metals).

• Common forming operations reduce the cross-sectional
area:
-Forging force -Rolling
roll
die Ad
A o blank Ad Ao
Adapted from Fig.
11.8, Callister & roll
Rethwisch 8e.
-Drawing force -Extrusion
Ao
die Ad container die holder
Ao tensile force
force ram billet extrusion Ad
die container die
Ao - Ad
%CW  x 100
Ao 171
 Dislocation Structures Change During
Cold Working
• Dislocation structure in Ti after cold working.
• Dislocations entangle
with one another
during cold work.
• Dislocation motion
becomes more difficult.

Fig. 4.6, Callister &

Rethwisch 8e.
(Fig. 4.6 is courtesy
of M.R. Plichta,
Michigan
Technological
University.)

172
 Dislocation Density Increases During
Cold Working
total dislocation length
Dislocation density =
unit volume
– Carefully grown single crystals
 ca. 103 mm-2
– Deforming sample increases density
 109-1010 mm-2
– Heat treatment reduces density
 105-106 mm-2

• Yield stress increases as rd increases:

173
 Lattice Strain Interactions Between
Dislocations

Adapted from Fig.

7.5, Callister &
Rethwisch 8e.

174
 Impact of Cold Work
As cold work is increased
• Yield strength (sy) increases.
• Tensile strength (TS) increases.
• Ductility (%EL or %AR) decreases.

Adapted from Fig. 7.20,

Callister & Rethwisch 8e.

low carbon steel

175
 Mechanical Property Alterations
Due to Cold Working
• What are the values of yield strength, tensile strength &
ductility after cold working Cu? 2 2
pDo pDd
-
Copper %CW  4 4 x 100
Cold pDo2
Work
4
Do2 - Dd2
 x 100
Do = 15.2 mm Dd = 12.2 mm Do2

(15.2 mm)2 - (12.2 mm)2

%CW  x 100  35.6%
2
(15.2 mm)
176
 Mechanical Property Alterations
Due to Cold Working
• What are the values of yield strength, tensile strength &
ductility for Cu for %CW = 35.6%?

60

tensile strength (MPa)

yield strength (MPa)

700 800

ductility (%EL)
40
500 600
300 MPa Cu
300 Cu 400 340 MPa 20
Cu 7%
100 200 00
0 20 40 60 0 20 40 60 20 40 60
% Cold Work % Cold Work % Cold Work

sy = 300 MPa TS = 340 MPa %EL = 7%

Adapted from Fig. 7.19, Callister & Rethwisch 8e. (Fig. 7.19 is adapted from Metals Handbook: Properties
and Selection: Iron and Steels, Vol. 1, 9th ed., B. Bardes (Ed.), American Society for Metals, 1978, p. 226;
and Metals Handbook: Properties and Selection: Nonferrous Alloys and Pure Metals, Vol. 2, 9th ed., H.
Baker (Managing Ed.), American Society for Metals, 1979, p. 276 and 327.) 177
6.3. Effect of Heat Treating After Cold Working
• 1 hour treatment at Tanneal...
decreases TS and increases %EL.
• Effects of cold work are nullified!
annealing temperature (ºC)
100 200 300 400 500 600 700 • Three Annealing stages:
tensile strength (MPa)

600 60
tensile strength 1. Recovery

ductility (%EL)
50 2. Recrystallization
500
40 3. Grain Growth

400 30
Adapted from Fig. 7.22, Callister & Rethwisch
ductility 20 8e. (Fig. 7.22 is adapted from G. Sachs and
300 K.R. van Horn, Practical Metallurgy, Applied
Metallurgy, and the Industrial Processing of
Ferrous and Nonferrous Metals and Alloys,
American Society for Metals, 1940, p. 139.)

178
 Three Stages During Heat Treatment:
1. Recovery
Reduction of dislocation density by annihilation.
• Scenario 1 extra half-plane
of atoms Dislocations
Results from annihilate
diffusion atoms
and form
diffuse
a perfect
to regions
atomic
of tension
extra half-plane plane.
of atoms
• Scenario 2
3 . ―Climbed‖ disl. can now tR
move on new slip plane
2 . grey atoms leave by
4. opposite dislocations
vacancy diffusion
meet and annihilate
allowing disl. to ―climb‖
1. dislocation blocked; Obstacle dislocation
can‘t move to the right

179
 Three Stages During Heat Treatment:
2. Recrystallization
• New grains are formed that:
-- have low dislocation densities
-- are small in size
-- consume and replace parent cold-worked grains.
0.6 mm 0.6 mm

Adapted from
Fig. 7.21(a),(b),
Callister &
Rethwisch 8e.
(Fig. 7.21(a),(b)
are courtesy of
J.E. Burke,
General Electric
Company.)

33% cold New crystals

worked nucleate after
brass 3 sec. at 580C.
180
 As Recrystallization Continues…
• All cold-worked grains are eventually consumed/replaced.

0.6 mm 0.6 mm

Adapted from
Fig. 7.21(c),(d),
Callister &
Rethwisch 8e.
(Fig. 7.21(c),(d)
are courtesy of
J.E. Burke,
General Electric
Company.)

After 4 After 8
seconds seconds

181
 Three Stages During Heat Treatment:
3. Grain Growth
• At longer times, average grain size increases.
-- Small grains shrink (and ultimately disappear)
-- Large grains continue to grow
0.6 mm 0.6 mm
Adapted from
Fig. 7.21(d),(e),
Callister &
Rethwisch 8e.
(Fig. 7.21(d),(e)
are courtesy of
J.E. Burke,
General Electric
Company.)

After 8 s, After 15 min,

580ºC 580ºC
coefficient dependent
• Empirical Relation:
on material and T.
exponent typ. ~ 2
grain diam. elapsed time
at time t. d n
- don  Kt
182
 TR = recrystallization
temperature

TR

Adapted from Fig. 7.22,

Callister & Rethwisch 8e.

º
183
 Recrystallization Temperature
TR = recrystallization temperature = temperature
at which recrystallization just reaches
completion in 1 h.
0.3Tm < TR < 0.6Tm

For a specific metal/alloy, TR depends on:

• %CW -- TR decreases with increasing %CW
• Purity of metal -- TR decreases with
increasing purity

184
 Cold Working vs. Hot Working
• Hot working  deformation above TR
• Cold working  deformation below TR

Grain Size Influences Properties

• Metals having small grains – relatively strong and
tough at low temperatures
• Metals having large grains – good creep resistance
at relatively high temperatures
 Summary
• Dislocations are observed primarily in metals
and alloys.
• Strength is increased by making dislocation
motion difficult.
• Strength of metals may be increased by:
-- decreasing grain size
-- solid solution strengthening
-- precipitate hardening
-- cold working
• A cold-worked metal that is heat treated may experience
recovery, recrystallization, and grain growth – its properties
will be altered.

186
 Chapter 7: Phase Diagrams
ISSUES TO ADDRESS...
• When we combine two elements...
what equilibrium state do we get?
• In particular, if we specify...
--a composition (e.g., wt% Cu - wt% Ni), and
--a temperature (T )
then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?

Phase A Phase B

Nickel atom
Copper atom
187
 7.1 Introduction
Definitions
– Solutions – solid solutions, single phase
– Mixtures – more than one phase Adapted from Fig. 9.1,
Callister 7e.

Sucrose/Water Phase Diagram

• Solubility Limit: 10 0
Max concentration for

Temperature (°C)
Solubility
which only a single phase 80 Limit L
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup 0 20 40 6065 80 100
If Co > 65 wt% sugar: syrup + sugar.

Sugar
Water

Co =Composition (wt% sugar)

Pure
Pure

188
 Components and Phases
• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g., a and ).

Aluminum-  (lighter
Copper
phase)
Alloy

a (darker
phase)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.

189
 Effect of T & Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B (100°C,70) D (100°C,90)
1 phase 2 phases
100
L
Temperature (°C)

80
(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20°C,70)
2 phases
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 7e.
Co =Composition (wt% sugar)
190
 Phase Equilibria
Simple solution system (e.g., Ni-Cu solution)

Crystal electroneg r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.
• Ni and Cu are totally miscible in all proportions.

191
 7.2. Phase Diagrams
• Phase diagram is a graphical representation of all the equilibrium
phases as a function of temperature, pressure, and composition.
• For one component systems, the equilibrium state of the system is
defined by two independent parameters (P and T)

Phase diagrams for binary

systems
In two component system the
equilibrium state is defined by P, T
and composition. But we held P phase diagram for H2O
constant, and the phase diagram is
a function of temperature and
composition. 192
 Binary Isomorphous Systems
• Isomorphous system - complete solid solubility of the two
components (both in the liquid and solid phases).
• Indicate phases as function of T, Co, and P.
• For this course:
-binary systems: just 2 components.
-independent variables: T and Co (P = 1 atm is almost always used).

Three phase region can be identified on the phase

diagram:
Liquid (L) , solid + liquid (α +L), solid (α )
Liquidus line separates liquid from liquid + solid
Solidus line separates solid from liquid + solid

193
 Phase Diagram for Cu-Ni system
T(°C)
1600
Interpretation of a binary phase
1500 diagrams
L (liquid)
1400 We can use phase diagram to determine:
1) The number & type of phases that
1300 are present
2) Compositions of the phases
1200 a 3) The relative fractions of the phases
1100
(FCC solid
solution)
1000
0 20 40 60 80 100
wt% Ni

194
 The Lever Rule
• Tie line – connects the phases in equilibrium with
each other - essentially an isotherm
T(°C) How much of each phase?
tie line
Think of it as a lever (teeter-totter)
1300 L (liquid)
ML Ma
B
TB
a
1200 (solid)
R S R S
20 3 0C C
L o
40 C
a
50
M a S  M L R
wt% Ni Adapted from Fig. 9.3(b),
Callister 7e.

ML S C - C0 R C - CL
WL    a Wa   0
ML + Ma R + S Ca - CL R + S Ca - CL
195
 The number and types of phases present
• Rule 1: If we know T and Co, then we know:
--the number and types of phases present.

T(°C)
• Examples: 1600
L (liquid)
A(1100°C, 60):

B (1250°C,35)
1 phase: a 1500
Cu-Ni
B (1250°C, 35): 1400 phase
2 phases: L + a diagram
1300 a
(FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100 A(1100°C,60)
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH, 1991). 1000
0 20 40 60 80 100 wt% Ni
196
 Composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase. Cu-Ni
T(°C) system
• Examples:
TA A
Co = 35 wt% Ni tie line
At T A = 1320°C: 1300 L (liquid)

Only Liquid (L) B

CL = Co ( = 35 wt% Ni) TB
a
At T D = 1190°C:
1200 D (solid)
Only Solid ( a) TD
Ca = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250°C: CLCo Ca wt% Ni
Both a and L Adapted from Fig. 9.3(b), Callister 7e.
CL = C liquidus ( = 32 wt% Ni here) (Fig. 9.3(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
Ca = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
197
 Weight fractions of phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%). Cu-Ni
• Examples: T(°C) system
Co = 35 wt% Ni TA A
tie line
At T A : Only Liquid (L) 1300 L (liquid)
W L = 100 wt%, W a = 0 B
At T D: Only Solid ( a) TB R S
a
W L = 0, Wa = 100 wt%
1200 D (solid)
At T B : Both a and L TD
S  43 - 35  73 wt %
WL 
20 3 032 35 4 0 43 50
R + S 43 - 32 CLCo Ca wt% Ni
Adapted from Fig. 9.3(b), Callister 7e.
R
Wa 
(Fig. 9.3(b) is adapted from Phase Diagrams of
= 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)

198
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(°C) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, ) 1000
• Limited solubility: a L + a 779°C L + 
800
a: mostly Cu TE 8.0 71.9 91.2
: mostly Ag 600
• TE : No liquid below TE a+
• CE : Min. melting TE 400

composition 200
0 20 40 60 CE 80 100
• Eutectic transition Co , wt% Ag
L(CE) a(CaE) + (CE) Adapted from Fig. 9.7,
Callister 7e.

199
 EX: Pb-Sn Eutectic System (1)
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present: a +  Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 11 wt% Sn 300
L (liquid)
C = 99 wt% Sn
--the relative amount a L+ a
200 183°C L + 
of each phase: 18.3 61.9 97.8
S C - CO 150
Wa = =  R S
R+S C - Ca 100
a+
99 - 40 59
= = = 67 wt%
99 - 11 88
C - Ca 0 11 20 40 60 80 99100
W = R = O Ca Co C
R+S C - C a C, wt% Sn
Adapted from Fig. 9.8,
40 - 11 29 Callister 7e.
= = = 33 wt%
99 - 11 88 200
 EX: Pb-Sn Eutectic System (2)
• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...
--the phases present: a + L Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Ca = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+ a
--the relative amount 220
200
a R S L + 
of each phase: 183°C
CL - CO 46 - 40
Wa = = 100
CL - Ca 46 - 17 a+
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
Ca Co CL
CO - Ca 23 C, wt% Sn
WL = = = 79 wt% Adapted from Fig. 9.8,
CL - Ca 29 Callister 7e.

201
 Summary
• Phase diagrams are useful tools to determine:
--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.
• Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.
• Binary eutectics and binary eutectoids allow for
a range of microstructures.

202
 Chapter 8: Electrical Properties

ISSUES TO ADDRESS...
• How are electrical conductance and resistance
characterized?
• What are the physical phenomena that distinguish
conductors, semiconductors, and insulators?
• For metals, how is conductivity affected by
imperfections, temperature, and deformation?
• For semiconductors, how is conductivity affected
by impurities (doping) and temperature?

203
 8.1. Electrical Conduction
• Ohm's Law: V=IR
voltage drop (volts = J/C) resistance (Ohms)
C = Coulomb current (amps = C/s)

• Resistivity, r:
-- a material property that is independent of sample size and
geometry surface area
RA
r of current flow
l
current flow
path length
• Conductivity, s 1
s
 r

 204
 Electrical Properties
• Which will have the greater resistance?
2 2r 8r
D R1  
 D 2 pD 2
p 
 2

2D
 r r R1
R2   
 2D 2 pD2 8
 p 
  2 

• Analogous to flow of water in a pipe

• Resistance depends on sample geometry and
size.

205
 Definitions
Further definitions

J=se <= another way to state Ohm‘s law

current I
J  current density   like a flux
surface area A
e  electric field potential = V/

J = s (V/ )

Electron flux conductivity voltage gradient

206
 Conductivity: Comparison
• Room temperature values (Ohm-m)-1 = ( - m)-1
METALS conductors CERAMICS
-10
Silver 6.8 x 10 7 Soda-lime glass 10 -10-11
Copper 6.0 x 10 7 Concrete 10 -9
Iron 1.0 x 10 7 Aluminum oxide <10-13

SEMICONDUCTORS POLYMERS
-14
Silicon 4 x 10 -4 Polystyrene <10
Germanium 2 x 10 0 Polyethylene 10 -15-10-17
GaAs 10 -6
semiconductors insulators
Selected values from Tables 18.1, 18.3, and 18.4, Callister & Rethwisch 8e.

207
 Example: Conductivity Problem
What is the minimum diameter (D) of the wire so that V < 1.5 V?

 100 m
Cu wire - I = 2.5 A +

 V

100 m
< 1.5 V
 V
R 
pD 2 As I 2.5 A

4 6.07 x 107 (Ohm-m)-1

Solve to get D > 1.87 mm

208
 Electron Energy Band Structures

Adapted from Fig. 18.2, Callister & Rethwisch 8e.

209
 Band Structure Representation

Adapted from Fig. 18.3,

Callister & Rethwisch 8e.

210
 Conduction & Electron Transport
• Metals (Conductors):
-- for metals empty energy states are adjacent to filled states.
-- thermal energy Partially filled band Overlapping bands
excites electrons
Energy Energy
into empty higher
empty
energy states. band
-- two types of band GAP empty
structures for metals band
- partially filled band partly
- empty band that filled filled

filled states
band

filled states
overlaps filled band band

filled filled
band band

211
 Energy Band Structures: Insulators &
Semiconductors
• Insulators: • Semiconductors:
-- wide band gap (> 2 eV) -- narrow band gap (< 2 eV)
-- few electrons excited -- more electrons excited
across band gap across band gap
Energy empty Energy empty
conduction conduction
band band
GAP ?
GAP

filled filled

filled states
filled states

valence valence
band band

filled filled
band band
212
 Drift Speed
When a current flows through a conductor
the electric field causes the charges to move
with a constant drift speed vd . This drift speed
is superimposed on the random motion of the
charges.

J  nvd e J  nevd
Consider the conductor of cross-sectional area A shown in the figure. We assume
that the current in the conductor consists of positive charges. The total charge
q within a length L is given by q   nAL  e. This charge moves through area A
L q nALe
in a time t  . The current is i    nAvd e.
vd t L / vd
i nAvd e
The current density is J    nvd e.
A A
In vector form: J  nevd .
Electron Mobility

J  nevd

J sE
Metals: Influence of Temperature and Impurities on
Resistivity
• Presence of imperfections increases resistivity
-- grain boundaries
These act to scatter
-- dislocations
electrons so that they
-- impurity atoms take a less direct path.
-- vacancies
6
• Resistivity
Resistivity, r
(10 -8 Ohm-m)

5
increases with:
4 -- temperature
3 rd -- wt% impurity
-- %CW
2 ri
1
rt
r = rthermal
0 -200 -100 0 T (ºC) + rimpurity
Adapted from Fig. 18.8, Callister & Rethwisch 8e. (Fig. 18.8
adapted from J.O. Linde, Ann. Physik 5, p. 219 (1932); and C.A.
+ rdeformation
Wert and R.M. Thomson, Physics of Solids, 2nd ed., McGraw-Hill
Book Company, New York, 1970.) 215
 Estimating Conductivity
• Question:
-- Estimate the electrical conductivity s of a Cu-Ni alloy Adapted from Fig.
18.9, Callister &
that has a yield strength of 125 MPa. Rethwisch 8e.
180
Yield strength (MPa)

(10 -8 Ohm-m)
50

Resistivity, r
160
140 40
125 30
120
100 20
21 wt% Ni 10
80
60 0
0 10 20 30 40 50 0 10 20 30 40 50
wt% Ni, (Concentration C) wt% Ni, (Concentration C)
Adapted from Fig. 7.16(b), Callister & Rethwisch 8e. -8
r  30 x 10 Ohm - m
From step 1:
1
s   3.3 x 106(Ohm - m)-1
CNi = 21 wt% Ni r
216
 Charge Carriers in Insulators and
Semiconductors
Adapted from Fig. 18.6(b),
Callister & Rethwisch 8e.
Two types of electronic charge
carriers:
Free Electron
– negative charge
– in conduction band

Hole
– positive charge
– vacant electron state in
the valence band

Move at different speeds - drift velocities

217
 Intrinsic Semiconductors
• Pure material semiconductors: e.g., silicon &
germanium
– Group IVA materials
• Compound semiconductors
– III-V compounds
• Ex: GaAs & InSb
– II-VI compounds
• Ex: CdS & ZnTe
– The wider the electronegativity difference between
the elements the wider the energy gap.

218
Intrinsic Semiconduction in Terms of Electron
and Hole Migration
• Concept of electrons and holes:
valence electron hole electron hole
electron Si atom
pair creation pair migration

- + - +

no applied applied applied

electric field electric field electric field
• Electrical Conductivity given by:
Adapted from Fig. 18.11,
Callister & Rethwisch 8e.
# holes/m3
s  n e me + p e mh
hole mobility
# electrons/m3 electron mobility
219
 Number of Charge Carriers
Intrinsic Conductivity
s  n e me + p e mh

• for intrinsic semiconductor n = p = ni

 s = ni|e|(me + mh)

• Ex: GaAs
s 10-6 (  m)-1
ni  
e m e + m h  (1.6 x10-19 C)(0.85 + 0.45 m2 /V  s)

For GaAs ni = 4.8 x 1024 m-3

For Si ni = 1.3 x 1016 m-3
220
 Intrinsic Semiconductors:
Conductivity vs T
• Data for Pure Silicon:
-- s increases with T
s  ni e me + mh 
-- opposite to metals

-E gap / kT
ni  e


material band gap (eV)

Si 1.11
 Ge
GaP
0.67
2.25
CdS 2.40
Selected values from Table 18.3,
Callister & Rethwisch 8e.

Adapted from Fig. 18.16,

Callister & Rethwisch 8e. 221
 Chapter 9:
Thermal Properties

ISSUES TO ADDRESS...
• How do materials respond to the application of heat?
• How do we define and measure...
-- heat capacity?
-- thermal expansion?
-- thermal conductivity?
-- thermal shock resistance?

• How do the thermal properties of ceramics, metals,

and polymers differ?

222
 9.1. Heat Capacity
The ability of a material to absorb heat
• Quantitatively: The energy required to produce a unit rise in
temperature for one mole of a material.
energy input (J/mol)
heat capacity dQ
(J/mol-K) C
dT temperature change (K)

• Two ways to measure heat capacity:

Cp : Heat capacity at constant pressure.
Cv : Heat capacity at constant volume.
Cp usually > Cv
J  Btu 
• Heat capacity has units of  
mol  K  lb - mol  F 
223
 Dependence of Heat Capacity on
Temperature
• Heat capacity...
-- increases with temperature
-- for solids it reaches a limiting value of 3R

R = gas constant 3R Cv = constant

= 8.31 J/mol-K

Adapted from Fig. 19.2,

Callister & Rethwisch 8e.
0 T (K)
0 qD
Debye temperature
(usually less than T room )
• From atomic perspective:
-- Energy is stored as atomic vibrations.
-- As temperature increases, the average energy of
atomic vibrations increases. 224
 Atomic Vibrations
Atomic vibrations are in the form of lattice waves or phonons

Adapted from Fig. 19.1,

Callister & Rethwisch 8e.
225
 Specific Heat: Comparison
Material cp (J/kg-K)
• Polymers at room T
Polypropylene 1925 cp (specific heat): (J/kg-K)
Polyethylene 1850 Cp (heat capacity): (J/mol-K)
Polystyrene 1170
Teflon 1050
• Why is cp significantly
increasing cp

• Ceramics larger for polymers?

Magnesia (MgO) 940
Alumina (Al2O3) 775
Glass 840
• Metals
Aluminum 900
Steel 486 Selected values from Table 19.1,
Tungsten 138 Callister & Rethwisch 8e.

Gold 128
226
 Thermal Expansion
Materials change size when temperature
is changed
Tinitial
 initial
Tfinal > Tinitial
Tfinal
 final

l -l
final initial
 a l (Tfinal -Tinitial )
l initial
linear coefficient of
thermal expansion (1/K or 1/ºC)

 227
Atomic Perspective: Thermal Expansion

Asymmetric curve: Symmetric curve:

-- increase temperature, -- increase temperature,
-- increase in interatomic -- no increase in interatomic
separation separation
-- thermal expansion -- no thermal expansion
Adapted from Fig. 19.3, Callister & Rethwisch 8e. 228
 Coefficient of Thermal Expansion:
Comparison
Material a (10-6/C)
at room T
• Polymers
Polypropylene 145-180 Polymers have larger
Polyethylene 106-198 a values because of
Polystyrene 90-150 weak secondary bonds
Teflon 126-216
• Metals • Q: Why does a
increasing a

Aluminum 23.6 generally decrease

Steel 12 with increasing
Tungsten 4.5 bond energy?
Gold 14.2
• Ceramics
Magnesia (MgO) 13.5 Selected values from Table 19.1,
Alumina (Al2O3) 7.6 Callister & Rethwisch 8e.

Soda-lime glass 9
Silica (cryst. SiO2) 0.4
229
 Thermal Expansion: Example
Ex: A copper wire 15 m long is cooled from
40 to -9ºC. How much change in length will it
experience?
• Answer: For Cu a  16.5 x 10-6 ( C)-1

rearranging Equation 19.3b

D  a   0 DT  [
16.5 x 10-6 (1/ C)](15 m)[40C - ( -9C)]

D  0.012 m  12 mm

230
 9.2. Thermal Conductivity
The ability of a material to transport heat.
Fourier’s Law
temperature
dT
q  -k gradient
heat flux dx
(J/m2-s) thermal conductivity (J/m-K-s)

T1 T2
T2 > T1
x1 heat flux x2

• Atomic perspective: Atomic vibrations and free electrons in

hotter regions transport energy to cooler regions.

231
 Thermal Conductivity: Comparison
Energy Transfer
Material k (W/m-K) Mechanism
• Metals
Aluminum 247 atomic vibrations
Steel 52 and motion of free
Tungsten 178
electrons
Gold 315
• Ceramics
increasing k

Magnesia (MgO) 38
Alumina (Al2O3) 39 atomic vibrations
Soda-lime glass 1.7
Silica (cryst. SiO2) 1.4
• Polymers
Polypropylene 0.12
Polyethylene 0.46-0.50 vibration/rotation of
Polystyrene 0.13 chain molecules
Teflon 0.25
Selected values from Table 19.1, Callister & Rethwisch 8e. 232
 Thermal Stresses
• Occur due to:
-- restrained thermal expansion/contraction
-- temperature gradients that lead to differential
dimensional changes

Thermal stress  s
 Ea (T0 -Tf )  Ea DT

E -Young's modulus

233
 Example Problem
-- A brass rod is stress-free at room temperature (20ºC).
-- It is heated up, but prevented from lengthening.
-- At what temperature does the stress reach -172 MPa?
Solution:
T0 Original conditions
0
Step 1: Assume unconstrained thermal expansion
0 D D
 ethermal  a (Tf -T0 )
Tf room

Step 2: Compress specimen back to original length

0 D
 -D
s s ecompress   -ethermal
room
234
 Example Problem (cont.)
0 The thermal stress can be directly
calculated as
s s
s  E(ecompress )

Noting that ecompress = -ethermal and substituting gives

s  -E(ethermal )  -Ea
 (Tf -T0 )  Ea (T0 -Tf )

Rearranging and solving for Tf gives

 20ºC
-172 MPa (since in compression)
s
Tf  T0 -
Ea

Answer: 106ºC 100 GPa 20 x 10-6/ºC

 235
 Thermal Shock Resistance
• Occurs due to: nonuniform heating/cooling
• Ex: Assume top thin layer is rapidly cooled from T1 to T2
rapid quench
s
tries to contract during cooling T2 Tension develops at surface
resists contraction T1 s  -Ea (T1 -T2 )
Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set s = sf)
quench rate sf
(T1 - T2 )   (T1 -T2 ) fracture 
k Ea
set equal
sf k
• (quench rate) for  Thermal Shock Resistance (
T SR) 
fracture  Ea
sf k
• Large TSR when is large
Ea
236
 Summary
The thermal properties of materials include:
• Heat capacity:
-- energy required to increase a mole of material by a unit T
-- energy is stored as atomic vibrations
• Coefficient of thermal expansion:
-- the size of a material changes with a change in temperature
-- polymers have the largest values
• Thermal conductivity:
-- the ability of a material to transport heat
-- metals have the largest values
• Thermal shock resistance:
-- the ability of a material to be rapidly cooled and not fracture
sf k
-- is proportional to
Ea

237
Chap 10: Magnetic Properties
a) Transmission electron micrograph
showing the microstructure of the
perpendicular magnetic recording
medium used in hard-disk drives.

b) Magnetic storage hard disks used

in laptop (left) and desktop (right)
computers.

c) Inside of a hard disk drive.

d) Laptop computer
 Generation of a Magnetic Field -- Vacuum
• Created by current through a coil:
B N = total number of turns
 = length of each turn (m)
I = current (ampere)

B = magnetic field (tesla)

I

239
 Generation of a Magnetic Field --
within a Solid Material
• A magnetic field is induced in the material
B
B = Magnetic field (tesla)
inside the material

current I

m
• Relative permeability (dimensionless) mr 
m0

240
 Origins of Magnetic Moments
• Magnetic moments arise from electron motions and the
spins on electrons.

magnetic moments
electron electron

nucleus spin
Adapted from Fig. 20.4,
Callister & Rethwisch 8e.

electron orbital electron

motion spin
• Net atomic magnetic moment:
-- sum of moments from all electrons.

• Four types of response...

241
 Types of Magnetism

(3) ferromagnetic e.g. Fe3O4, NiFe2O4

(4) ferrimagnetic e.g. ferrite(a), Co, Ni, Gd
( cm as large as 106 !)
B (tesla)

(2) paramagnetic ( cm ~ 10-4)

e.g., Al, Cr, Mo, Na, Ti, Zr
vacuum (cm = 0)
(1) diamagnetic (cm ~ -10-5)
e.g., Al2O3, Cu, Au, Si, Ag, Zn

H (ampere-turns/m)

Plot adapted from Fig. 20.6, Callister & Rethwisch 8e.

Values and materials from Table 20.2 and discussion in
Section 20.4, Callister & Rethwisch 8e.

242
 Magnetic Responses for 4 Types
No Applied Applied
Magnetic Field (H = 0) Magnetic Field (H)

opposing
None
(1) diamagnetic Adapted from Fig.
20.5(a), Callister &
No magnetic moment Rethwisch 8e.
before magnetization,
not attracted by a magnet

random

aligned
(2) paramagnetic Adapted from Fig.
20.5(b), Callister &
aligned Rethwisch 8e.

aligned
(3) ferromagnetic Adapted from Fig.
20.7, Callister &
(4) ferrimagnetic Rethwisch 8e.

243
 Influence of Temperature on
Magnetic Behavior

With increasing temperature, the saturation magnetization

diminishes gradually and then abruptly drops to zero at Curie
244
Temperature, Tc.
Magnetic Domains

245
 Domains in Ferromagnetic & Ferrimagnetic
Materials
• As the applied field (H) increases the magnetic domains
change shape and size by movement of domain boundaries.
B sat
H
H Adapted from Fig. 20.13,
induction (B)

Callister & Rethwisch

H • ―Domains‖ with 8e. (Fig. 20.13 adapted

Magnetic

from O.H. Wyatt and D.

aligned magnetic Dew-Hughes, Metals,
Ceramics, and
H moment grow at Polymers, Cambridge
University Press, 1974.)
expense of poorly
aligned ones!
H
0 Applied Magnetic Field (H)

H=0
246
 Hysteresis and Permanent
Magnetization
• The magnetic hysteresis phenomenon

B
Stage 2. Apply H,
Stage 3. Remove H, alignment align domains
remains! => permanent magnet!
Adapted from Fig. 20.14,
Callister & Rethwisch 8e.
H
Stage 4. Coercivity, HC
Negative H needed to Stage 1. Initial (unmagnetized state)
demagnitize!

Stage 6. Close the

Stage 5. Apply -H, hysteresis loop
align domains

247
 Hard and Soft Magnetic Materials

Hard magnetic materials: B

-- large coercivities
-- used for permanent magnets
-- add particles/voids to
inhibit domain wall motion

Soft
-- example: tungsten steel --
Hc = 5900 amp-turn/m) H

Soft magnetic materials:

-- small coercivities
-- used for electric motors
-- example: commercial iron 99.95 Fe

Adapted from Fig. 20.19, Callister & Rethwisch

8e. (Fig. 20.19 from K.M. Ralls, T.H. Courtney,
and J. Wulff, Introduction to Materials Science
and Engineering, John Wiley and Sons, Inc.,
1976.)
248
 Magnetic Storage
• Digitized data in the form of electrical signals are transferred to
and recorded digitally on a magnetic medium (tape or disk)
• This transference is accomplished by a recording system that
consists of a read/write head
-- ―write‖ or record data by applying a
magnetic field that aligns domains
in small regions of the recording
medium
-- ―read‖ or retrieve data from
medium by sensing changes
in magnetization

249
 Magnetic Storage Media Types
• Hard disk drives (granular/perpendicular media):
-- CoCr alloy grains (darker regions)
separated by oxide grain boundary Fig. 20.25, Callister
segregant layer (lighter regions)

80 nm
& Rethwisch 8e.
(Fig. 20.25 from
-- Magnetization direction of each Seagate Recording
grain is perpendicular to plane of Media)
disk

• Recording tape (particulate media):

Fig. 20.24, Callister

~ 500 nm

~ 500 nm
& Rethwisch 8e.
(Fig. 20.24
courtesy Fuji Film
Inc., Recording
Media Division)

-- Acicular (needle-shaped) -- Tabular (plate-shaped)

ferromagnetic metal alloy ferrimagnetic barium-ferrite
particles particles 250
 Summary
• A magnetic field is produced when a current flows
through a wire coil.
• Magnetic induction (B):
-- an internal magnetic field is induced in a material that is
situated within an external magnetic field (H).
-- magnetic moments result from electron interactions with
the applied magnetic field
• Types of material responses to magnetic fields are:
-- ferrimagnetic and ferromagnetic (large magnetic susceptibilities)
-- paramagnetic (small and positive magnetic susceptibilities)
-- diamagnetic (small and negative magnetic susceptibilities)
• Types of ferrimagnetic and ferromagnetic materials:
-- Hard: large coercivities
-- Soft: small coercivities
• Magnetic storage media:
-- particulate barium-ferrite in polymeric film (tape)
-- thin film Co-Cr alloy (hard drive) 251
 Chapter 11: Optical Properties

ISSUES TO ADDRESS...
• What phenomena occur when light is shined on a material?
• What determines the characteristic colors of materials?
• Why are some materials transparent and others are
translucent or opaque?
• How does a laser operate?

252
11.1. Electromagnetic Radiation and Light
Interactions
Light has both particulate and wavelike characteristics
– Photon - a quantum unit of light

hc
E  hn 
l

E  energy of a photon
 l  wavelength of radiation
n  frequency of radiation
h  Planck‘ s constant (6.62 x 10-34 J  s)
c  speed of light in a vacuum (3.00 x 108 m/s)

253
The spectrum of electromagnetic radiation

254
 Refraction
• Transmitted light distorts electron clouds.
electron
no cloud
transmitted transmitted
+ + distorts
light light

• The velocity of light in a material is lower than in a vacuum.

c (velocity of light in vacuum)
n = index of refraction 
v (velocity of light in medium)

-- Adding large ions (e.g., lead) to glass Material n

decreases the speed of light in the glass.
-- Light can be ―bent‖ as it passes through a
Typical glasses ca. 1.5 -1.7
transparent prism Plastics 1.3 -1.6
PbO (Litharge) 2.67
Diamond 2.41
Selected values from Table 21.1,
Callister & Rethwisch 8e.

255
 Total Internal Reflectance
n1 sin f2
n2 < n1 
f2 n2 sin f1
n2 f1 = incident angle
n1 f2 = refracted angle
  fc = critical angle
fc fc exists when f2 = 90°
f1 For f1 > fc light is internally
reflected
• Fiber optic cables are clad in low n material so that light will
experience total internal reflectance and not escape from the optical
fiber.  256
 Example: Diamond in air
• What is the critical angle fc for light passing from diamond
(n1 = 2.41) into air (n2 = 1)?
• Solution: At the critical angle, f1  fc
and f2  90
n1 sin f2
Rearranging the equation 
 n2 sin f1
 n n2
sin f1  sin fc  sin(90) 
2
n1 n1

Substitution gives
1
 sin fc  fc  24.5
2.41
257
 Light Interactions with Solids
• Incident light is reflected, absorbed, scattered, and/or
transmitted: I0  IT + IA + IR + IS

Reflected: IR Absorbed: IA
Transmitted: IT
 Incident: I0
Scattered: IS
• Optical classification of materials:
Transparent Adapted from Fig. 21.10, Callister
Translucent 6e. (Fig. 21.10 is by J. Telford,
with specimen preparation by P.A.
Opaque Lessing.)

single polycrystalline polycrystalline

crystal dense porous
258
11.2. Optical Properties of Metals: Absorption

• Absorption of photons by electron transitions:

Energy of electron
unfilled states

DE = hn required!

filled states
Planck‘s constant freq.
of
(6.63 x 10-34 J/s) incident
Adapted from Fig. 21.4(a),
Callister & Rethwisch 8e.
light
• Unfilled electron states are adjacent to filled states
• Near-surface electrons absorb visible light.
259
 Light Absorption
The amount of light absorbed by a material is
calculated using Beer‘s Law

 = absorption coefficient, cm-1

 = sample thickness, cm
IT I 0 e - I 0 = incident light intensity
IT = transmitted light intensity

Rearranging and taking the natural log of both sides

of the equation leads to

 IT 
ln   - 
 I 0 
260
 Reflection of Light for Metals
• Electron transition from an excited state produces a photon.

Energy of electron
IR unfilled states
―conducting‖ electron
photon emitted Electron transition
from metal
surface
filled states

Adapted from Fig. 21.4(b),

Callister & Rethwisch 8e.

261
 Reflection of Light for Metals (cont.)
• Reflectivity = IR /I0 is between 0.90 and 0.95.
• Metal surfaces appear shiny
• Most of absorbed light is reflected at the same wavelength
• Small fraction of light may be absorbed
• Color of reflected light depends on wavelength distribution
– Example: The metals copper and gold absorb light in
blue and green => reflected light has gold color

262
 Reflectivity of Nonmetals
• For normal incidence and light passing into a solid
having an index of refraction n:
 n -12

R  reflectivity   
 n + 1
• Example: For Diamond n = 2.41
2
 2.41- 1
 R    0.17
 2.41+ 1
 17% of light is reflected

263
 Scattering of Light in Polymers
• For highly amorphous and pore-free polymers
– Little or no scattering
– These materials are transparent
• Semicrystalline polymers
– Different indices of refraction for amorphous and
crystalline regions
– Scattering of light at boundaries
– Highly crystalline polymers may be opaque
• Examples:
– Polystyrene (amorphous) – clear and transparent
– Low-density polyethylene milk cartons – opaque

264
Selected Light Absorption in Semiconductors
Absorption of light of frequency n by by electron transition
occurs if hn > Egap Energy of electron
Examples of photon energies:
unfilled states
blue light: hn = 3.1 eV
red light: hn = 1.8 eV

Egap
incident photon
energy hn
filled states Adapted from Fig. 21.5(a),
Callister & Rethwisch 8e.

• If Egap < 1.8 eV, all light absorbed; material is opaque (e.g., Si, GaAs)
• If Egap > 3.1 eV, no light absorption; material is transparent and
colorless (e.g., diamond)
• If 1.8 eV < Egap < 3.1 eV, partial light absorption; material is colored
265
Computations of Minimum Wavelength
Absorbed
(a) What is the minimum wavelength absorbed by
Ge, for which Eg = 0.67 eV?

Solution:
hc (6.63 x 10-34 J s)(3 x 108 m/s)
lGe (min)  
E g (Ge) (0.67 eV)(1.60 x 10-19 J/eV)

l Ge (min)  1.86 x 10 -6 m  1.86 mm


(b) Redoing this computation for Si which has a band gap
of
1.1 eV
lSi (min)  1.13 mm

Note: the presence of donor and/or acceptor states allows for light
absorption at other wavelengths.

266
 Color of Nonmetals
• Color determined by the distribution of wavelengths:
-- transmitted light
-- re-emitted light from electron transitions
• Example 1: Cadmium Sulfide (CdS), Eg = 2.4 eV
-- absorbs higher energy visible light (blue, violet)
-- color results from red/orange/yellow light that is transmitted
• Example 2: Ruby = Sapphire (Al2O3) + (0.5 to 2) at% Cr2O3
-- Sapphire is transparent and
80

Transmittance (%)
colorless (Eg > 3.1 eV) sapphire
70
-- adding Cr2O3 : ruby
• alters the band gap 60
• blue and orange/yellow/green 50
wavelength, l (= c/n)(mm)
light is absorbed 40
0.3 0.5 0.7 0.9
• red light is transmitted Adapted from Fig. 21.9, Callister & Rethwisch 8e.
• Result: Ruby is deep (Fig. 21.9 adapted from "The Optical Properties of
Materials" by A. Javan, Scientific American, 1967.)
red in color
267
 Luminescence
• Luminescence – reemission of light by a material
– Material absorbs light at one frequency and reemits it at
another (lower) frequency.
– Trapped (donor/acceptor) states introduced by
impurities/defects
Conduction band • If residence time in trapped state is
relatively long (> 10-8 s)
-- phosphorescence

• For short residence times (< 10-8 s)

trapped Eemission -- fluorescence
Eg states
Example: Toys that glow in the dark.
activator
level Charge toys by exposing them to
light. Reemission of light over time—
phosphorescence
Valence band
268
 Photoluminescence
Hg atom

UV light

electrode electrode
• Arc between electrodes excites electrons in mercury atoms in
the lamp to higher energy levels.
• As electron falls back into their ground states, UV light is emitted
(e.g., suntan lamp).
• Inside surface of tube lined with material that absorbs UV and
reemits visible light
- For example, Ca10F2P6O24 with 20% of F - replaced by Cl -
• Adjust color by doping with metal cations
Sb3+ blue
Mn2+ orange-red 269
 Cathodoluminescence
• Used in cathode-ray tube devices (e.g., TVs, computer monitors)
• Inside of tube is coated with a phosphor material
– Phosphor material bombarded with electrons
– Electrons in phosphor atoms excited to higher state
– Photon (visible light) emitted as electrons drop back into
ground states
– Color of emitted light (i.e., photon wavelength) depends on
composition of phosphor
ZnS (Ag+ & Cl-) blue
(Zn, Cd) S + (Cu++Al3+) green
Y2O2S + 3% Eu red

• Note: light emitted is random in phase & direction

– i.e., is noncoherent

270
 Other Applications of Optical
Phenomena
• New materials must be developed to make new &
improved optical devices.
– Organic Light Emitting Diodes (OLEDs)
• More than one color available from a single diode
• Also sources of white light (multicolor)

Fig. 21.12, Callister & Rethwisch 8e.

(Reproduced by arrangement with
Silicon Chip magazine.)

271
 Other Applications - Solar Cells
• p-n junction: • Operation:
-- incident photon of light produces elec.-hole pair.
P-doped Si -- typical potential of 0.5 V produced across junction
conductance Si -- current increases w/light intensity.
electron creation of
Si P Si hole-electron
light pair
Si - - -
n-type Si
p-n junction -
n-type Si p-type Si +
p-n junction + + +
p-type Si
• Solar powered weather station:
hole Si
Si B Si

Si
B-doped Si polycrystalline Si
Los Alamos High School weather
station (photo courtesy
P.M. Anderson)

272
 SUMMARY
• Light radiation impinging on a material may be reflected
from, absorbed within, and/or transmitted through
• Light transmission characteristics:
-- transparent, translucent, opaque
• Optical properties of metals:
-- opaque and highly reflective due to electron energy band
structure.
• Optical properties of non-Metals:
-- for Egap < 1.8 eV, absorption of all wavelengths of light radiation
-- for Egap > 3.1 eV, no absorption of visible light radiation
-- for 1.8 eV < Egap < 3.1 eV, absorption of some range of light
radiation wavelengths
-- color determined by wavelength distribution of transmitted light
• Other important optical applications/devices:
-- luminescence, photoconductivity, light-emitting diodes, solar
cells, lasers, and optical fibers
273