Lecture 9 Materials - Merged

Phase Diagrams
Recall a previous example (solid solubility)
Phase A Phase B
Zinc atom
Copper atom
• When we combine two elements...
what equilibrium state do we get? To ?
• In particular, if we specify...
- a composition (Co), and
- a temperature (To)
then...
How many phases do we get?
Co
What is the composition of each phase?
How much of each phase do we get?
1
Definitions and Basic Concepts
•Component: chemically recognizable species (e.g. Fe and C in
carbon steel, H2O and NaCl in salted water).
- A binary alloy contains two components, a ternary alloy – three, etc.
•Phase: a chemically homogeneous portion of a microstructure; a

region of uniform composition and crystal structure.
-Do not confuse phase with grain. A single phase material usually contains
many grains. Each phase in a multiphase material usually contains many
grains
- A phase may contain one or more components.
•System: a series (family) of possible alloys, compounds, and

mixtures resulting from the same components.
- Examples: the Fe-C system (yields tens of different steels), the water-
sugar system, the alumina-silica system.
•Solvent: host or major component in solution, Solute: minor
component. 2
Solubility Limit of a component in a phase is the maximum amount of the
component that can be dissolved in it yielding a single phase mixture.
-e.g. alcohol has unlimited solubility in water (from 0 to 100% alcohol, the
mixture is single-phased), sugar has a limited solubility, oil is insoluble.
- The same concepts apply to solid phases: Cu and Ni are mutually soluble in
any amount (unlimited solid solubility), while C has a limited solubility in Fe.
Equilibrium: The stable configuration of a system, when a sufficient amount of time

has elapsed that no further changes occur.
-Equilibrium may take place rapidly (on the order of microseconds), or may require
a geological time frame.
-We will be dealing with equilibrium phase diagrams, that is, the nature of a system
at any given temperature after a “sufficiently” long period of time.
3
•Microstructure: The properties of an alloy depend not only on proportions of the
phases but also on how they are arranged structurally at the microscopic level.
Thus, the microstructure is specified by:
(1) the number of phases, (2) their proportions, and (3) their arrangement in space.
➢ This is an alloy of Fe with 4 wt.% C.

➢ There are several phases.
-The long grey regions are flakes of
graphite.
- The matrix is a fine mixture of BCC
Fe and Fe3C compound.
Phase diagrams will help us to understand and predict

the microstructures like the one shown above
4
Binary Phase Diagrams
Phase diagrams show what phases exist at equilibrium and what phase
transformations we can expect when we change one of the parameters of the system.
Example: the sugar – water phase diagram
P
P’’
Temperature is
plotted on y axis,
composition on x axis
weight % or atomic %
P’
The region to the left of the red line is a single phase region (syrup)
The region to the right of the red line is a two phase region (syrup + sugar)
a single phase syrup mixture is established at 70°C with 64 % of sugar (point P)
- decreasing the temperature (cte sugar concentration), sugar will precipitate and we have two phases (point P’)
- increasing the sugar concentration (cte temperature), sugar will precipitate and we have two phases (point P’’)
5
Binary Isomorphous Systems (I)
Isomorphous system - complete solid solubility of the two
components (both in the liquid and solid phases).
L
100% of B,
+L no A
In one-component systems (as pure A or B in the figure)

melting occurs at a well-defined melting temperature

0 % of B,
only A
6
Binary Isomorphous Systems (I)
Isomorphous system - complete solid solubility of the
two components (both in the liquid and solid phases).
In this multi-component system (A + B)
three phase-regions can be identified on the phase diagram:
Liquid (L) , solid + liquid ( +L), solid ( )
Liquidus line separates liquid from liquid + solid
T2 (above the liquidus line, all is liquid)
Solidus line separates solid from liquid + solid
(below the solidus line, all is solid)
T1 In multi-component systems melting occurs over a range of temperatures,

between the solidus and liquidus lines, which means that
solid and liquid phases are in equilibrium in this temperature range
a 60%A – 40%B solid alloy will melt

between T1 and T2 in the picture
Phase diagrams are maps of the equilibrium phases associated with composition, temperature and pressure.
(Since most materials engineering work involves atmospheric pressure,we are usually
most interested in composition – temperature diagrams)
Binary phase diagrams are two component maps widely used by engineers.
They are helpful in predicting phase transformations and the resulting microstructures7
Binary Isomorphous Systems (II)
Example of isomorphous system: Cu-Ni
the complete solubility occurs because both Cu and Ni have
the same crystal structure, FCC, similar radii and electronegativity
Pure copper along this axis
Pure nickel along this axis


What 1085°C and 1453°C stand for?

Melting points for pure copper and pure nickel, respectively
8
A first glance at the overall system behavior
Liquidus
L
Temperature
liquid solution
+L
Solidus
liquid solution
 +
crystallites of
solid solution
A 20 40 60 80 B
polycrystal
solid solution Composition, wt %
9
Interpretation of a binary phase diagrams
For a given temperature and composition we can use phase diagram to determine:
1) The phases that are present
2) Compositions of the phases
3) The relative fractions of the phases
Finding the composition in a two phase region:
To understand how to read and interpret phase diagrams,
let us first consider the system water-sugar at 70° C. The
Solubility limit is 70% (wt%) of sugar.
this must be understood as the maximum concentration
of sugar the liquid may contain at 70° C.
Solving…
10
2 let us first consider the system water-sugar at 70° C. The
1
● ● 3● 4● 5● Solubility limit is 70% (wt%) of sugar.
So what are the concentrations of sugar in the liquid at
points 1 – 5 in the figure?
11
1
1 = 20% ; 2 = 40% ; 3 = 70 %
12
1
1 = 20% ; 2 = 40% ; 3 = 70 % 4 = 70% ; 5 = 70%
Indeed, any extra amount of sugar beyond 70% (at 70° C )

one tries to add to the system will be expelled by the liquid
and precipitate as pure sugar.
13
1
1 = 20% ; 2 = 40% ; 3 = 70 % 4 = 70% ; 5 = 70%

The system at point 4 contains 80% of sugar split in some amount of liquid syrup, L,
(with 70% of sugar) and some amount of precipitated solid crystals, S, (100% of sugar)
14
1
1 = 20% ; 2 = 40% ; 3 = 70 % 4 = 70% ; 5 = 70%

We can then write: Total concentration of sugar at point 4, C4 = 0.7 L + 1S = 0.8
As well as: L + S = 1 Which reflects the fact that the material can only be L or S
Solving… L = 2 / 3 (or 66.7%) ; S = 1 / 3 (or 33.3%)
15
1
1 = 20% ; 2 = 40% ; 3 = 70 % 4 = 70% ; 5 = 70%

We can then write: Total concentration of sugar at point 4, C4 = 0.7 L + 1S = 0.8
Answering the questions at the top of the slide…
Solving… L = 2 / 3 (or 66.7%) ; S = 1 / 3 (or 33.3%)
phases that are present : Liquid syrup and solid sugar
compositions of the phases: (L = 30% water, 70% sugar) ; (S = 100%) sugar
relative fractions of the phases: 66.7% L ; 33.3% S 16
What we did before was the theoretical development of what is called…
The lever rule
Finding the amounts of phases in a two phase region:
1. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Fraction of a phase is determined by taking the length
of the tie line to the phase boundary for the other
phase, and dividing by the total length of tie line
 +

W W
The lever rule is a mechanical analogy to the mass balance

calculation. The tie line in the two-phase region is
analogous to a lever balanced on a fulcrum:
W must be higher than W to equilibrate the lever
17
What we did before was the theoretical development of what is called…
The lever rule
Finding the amounts of phases in a two phase region:
1. Locate composition and temperature in diagram
2. In two phase region draw the tie line or isotherm
3. Fraction of a phase is determined by taking the length
of the tie line to the phase boundary for the other
phase, and dividing by the total length of tie line
 +

W W
The lever rule is a mechanical analogy to the mass balance

calculation. The tie line in the two-phase region is
analogous to a lever balanced on a fulcrum:
W must be higher than W to equilibrate the lever
The point for which we want to calculate the composition is closer to
, which means there will be more  than .
18
Derivation of the lever rule
1) All material must be in one phase or the other:

W + W = 1
2) Mass of a component that is present in both phases

equal to the mass of the component in one phase +
mass of the component in the second phase:
WC + W  C  = Co
3) Solution of these equations gives us the lever rule.
W  = (C - Co) / (C - C )
W = (Co - C ) / (C - C )
19

W + W  = 1

WC + W  C  = Co
W  = (C - Co) / (C - C )
W = (Co - C ) / (C - C )
This is what we did in our previous example (water + sugar)
Total concentration of sugar at point 4, C4 = 0.7 L + 1S = 0.8
20

W + W  = 1

WC + W  C  = Co
W  = (C - Co) / (C - C )
W = (Co - C ) / (C - C )
This is what we did in our previous example (water + sugar)
Total concentration of sugar at point 4, C4 = 0.7 L + 1S = 0.8
21
Phase compositions and amounts
Determine phase compositions and proportions at [T = 1250° C, 45% Ni]
22
CL = 0.36 Ni C = 0.53 Ni
23
CL = 0.36 Ni C = 0.53 Ni
0.36 L + 0.53 = 0.45 with  + L = 1
0.36 (1 −  ) + 0.53 = 0.45

0.09
=  53% ; L = 47%
0.17
24
Phase compositions and amounts. Example with the lever rule
25
Phase compositions and amounts. Example with the lever rule
Co = 35 wt. %, CL = 31.5 wt. %, C = 42.5 wt. %
Mass fractions:
WL = S / (R+S) = (C - Co) / (C - CL) = 0.68
W = R / (R+S) = (Co - CL) / (C - CL) = 0.32
26
Development of microstructure in isomorphous alloys
Equilibrium (very slow) cooling from a liquid with 35%
wt of Ni from point a to point e
27
28
29
30
31
How much sugar (in g) can you dissolve in 2 L of water at 50 C?
32
68%
33
68%
Answer =
34
68%
Answer = 4250 g !!!
35
A question I bet you’ll get false
68%
Answer = 4250 g !!!

68% is the concentration of sugar
36
68%
Answer = 4250 g !!!

68% is the concentration of sugar in the syrup (water + sugar), not in water
37
68%
Answer = 4250 g !!!

68% is the concentration of sugar in the syrup (water + sugar), not in water
msugar msugar
0.68 = =
msugar + mwater msugar + 2000 g
0.32msugar = 2000  0.68  msugar = 4250 g
38
Till now we just saw isomorphous alloys with a single solid phase.
Let us see the case of a binary system with two or more solid phases
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, α, β) 1000
• Limited solubility: α
α: mostly Cu TE 800 β
β: mostly Ag 600
400
200
0 20 40 60 80 100
C, wt% Ag
Chapter 9 - 39
Cu-Ag
T(°C) system
(L, α, β) 1000
α: mostly Cu TE 800 8.0
779°C β
71.9 91.2
β: mostly Ag 600
• TE : No liquid below TE
• CE : Composition at 400
temperature TE 200
0 20 40 60 CE 80 100
C, wt% Ag
Chapter 9 - 40
Cu-Ag
T(°C) system
(L, α, β) 1000
α: mostly Cu TE 800 8.0
779°C β
71.9 91.2
β: mostly Ag 600
• TE : No liquid below TE
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) (CE) + (CE)
cooling
L(71.9 wt% Ag)  (8.0 wt% Ag) +  (91.2 wt% Ag) Chapter 9 - 41
heating
Cu-Ag
T(°C) system
(L, α, β) 1000
• Limited solubility: α L + α 779°C L+β β
T 800
α: mostly Cu E 8.0 71.9 91.2
β: mostly Ag 600
• TE : No liquid below TE α+β
temperature TE 200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) (CE) + (CE)
cooling
L(71.9 wt% Ag)  (8.0 wt% Ag) +  (91.2 wt% Ag) Chapter 9 - 42
heating
In eutectic diagrams we apply the Lever Rule just as we did before
EX 1: Pb-Sn Eutectic System

• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
Answer: T(°C) system
300
L (liquid)
α L+ α
200 183°C L+β β
18.3 61.9 97.8
150
100
α +β
0 20 60 80 100
C, wt% Sn
Chapter 9 - 43

Answer: α + β T(°C) system
-- the phase compositions
300
Answer: L (liquid)
α L+ α
200 183°C L+β β
18.3 61.9 97.8
150
100
α +β
0 20 40 60 80 100
C0
C, wt% Sn
Chapter 9 - 44

300
Answer: Cα = 11 wt% Sn L (liquid)
Cβ = 99 wt% Sn
-- the relative amount α L+ α
200 183°C L+β β
of each phase 18.3 61.9 97.8
Answer: 150
100
α +β
0 11 20 40 60 80 99100
Cα C0 Cβ
C, wt% Sn
Chapter 9 - 45

300
Cβ = 99 wt% Sn
-- the relative amount α L+ α
200 183°C L+β β
of each phase 18.3 61.9 97.8
Answer: 150
S Cβ - C0 R S
Wα = = 100
R+S Cβ - Cα α +β
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - Cα Cα C0 Cβ
Wβ = R = C, wt% Sn
R+S Cβ - Cα
40 - 11 29
= = = 0.33
99 - 11 88 Chapter 9 - 46
-- the phases present: Pb-Sn
Answer: T(°C) system
300
L (liquid)
L+ α
220
200 α L+ β β
183°C
100
α +β
0 20 60 80 100
C, wt% Sn
Chapter 9 - 47
Answer: α + L T(°C) system
300
Answer: L (liquid)
L+ α
220
200 α L+ β β
183°C
100
α +β
0 20 40 60 80 100
C0
C, wt% Sn
Chapter 9 - 48
300
CL = 46 wt% Sn L+ α
220
-- the relative amount 200 α L+ β β
of each phase 183°C
Answer:
100
α +β
0 17 20 40 46 60 80 100
Cα C0 CL
C, wt% Sn
Chapter 9 - 49
300
CL = 46 wt% Sn L+ α
220
-- the relative amount 200 α R S L+ β β
of each phase 183°C
Answer:
100
Wα =
CL - C0
=
46 - 40 α +β
CL - Cα 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Cα C0 CL
29 C, wt% Sn
C0 - Cα 23
WL = = = 0.79
CL - Cα 29
Chapter 9 - 50
Microstructural Developments
in Eutectic Systems I
• For alloys for which C0 < 2 wt% Sn T(°C) L: C0 wt% Sn
400
• Result: at room temperature L
-- polycrystalline with grains of α
α phase having composition C0 300 L
L+ α
200
α
α: C0 % Sn (Pb-Sn
TE
System)
100
α+β
0 10 20 30
C0 C, wt% Sn
2%
(room T solubility limit)
Chapter 9 - 51
in Eutectic Systems II
L: C0 wt% Sn
• For alloys for which 400
T(°C)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
at temperatures in α + β range 300 α
L +α
-- α: C0 wt% Sn
α
200
TE
100
α+ β Pb-Sn
system
0 10 20 30
2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
Chapter 9 - 52
L: C0 wt% Sn
T(°C)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
L +α
-- polycrystalline with α grains α: C0 wt% Sn
and small β-phase particles 200 α
TE
α
β
100
α+ β Pb-Sn
system
0 10 20 30
2 C0 C, wt% Sn
(sol. limit at TE)
Chapter 9 - 53
L: C0 wt% Sn
T(°C)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
L +α
TE
α
Why  particles in a  matrix β
and not the inverse? 100
α+ β Pb-Sn
system
0 10 20 30
2 C0 C, wt% Sn
(sol. limit at TE)
Chapter 9 - 54
L: C0 wt% Sn
T(°C)
2 wt% Sn < C0 < 18.3 wt% Sn L
• Result: L
L +α
TE
α
Why  particles in a  matrix β
and not the inverse? 100
α+ β Pb-Sn
Because as we cool down,
system
 precipitates from  phase
(as sugar would have precipitated from the syrup) 0 10 20 30
2 C0 C, wt% Sn
(sol. limit at TE)
Chapter 9 - 55
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of α and β phases.
Micrograph of Pb-Sn
T(°C) eutectic
L: C0 wt% Sn microstructure
300 L
Pb-Sn
system
L+ α
200
α 183°C L+β β
TE
100 160 μm
α+β β: 97.8 wt% Sn
α: 18.3 wt%Sn
0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn
Chapter 9 - 56
Lamellar Eutectic Structure
The lamellar − layered structure grows as indicated by the arrow.

It grows into and replace the liquid phase.
Chapter 9 - 57
The lamellar − layered structure grows as indicated by the arrow.

It grows into and replace the liquid phase.
But why do Pb and Sn segregate themselves and redistribute along the solid phases?
Chapter 9 - 58
Sn-poor,
Sn-rich Pb-rich
Sn-rich,
Pb-rich Pb-poor
Sn-rich
As the lamella grow, they pump their main component from the liquid ahead of them
Chapter 9 - 59
Sn-rich
Pb-rich
Sn-rich
This local exhaustion of the liquid in Pb (ahead of ) and Sn (ahead of ) creates

a concentration gradient that triggers diffusion of Pb towards  and Sn towards 
Chapter 9 - 60
in Eutectic Systems IV
• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: α phase particles and a eutectic microconstituent
T(°C) L: C0 wt% Sn
300 L
Pb-Sn
L+ α
system
200
α L+β β
TE
100 α+ β
0 20 40 60 80 100
C, wt% Sn
Chapter 9 - 61
T(°C) L: C0 wt% Sn
L
300 L α
Pb-Sn
L+ α
system
200
α L+β β
TE
100 α+ β
0 20 40 60 80 100
C, wt% Sn
Chapter 9 - 62
• Just above TE :
T(°C) L: C0 wt% Sn αL
L
Cα = 18.3 wt% Sn
300 L α CL = 61.9 wt% Sn
Pb-Sn S
L+ α Wα = = 0.50
system R+S
200
α R S L+β β WL = (1- Wα ) = 0.50
TE
100 α+ β
0 20 40 60 80 100
18.3 61.9
C, wt% Sn
Chapter 9 - 63
• Just above TE :
L
Cα = 18.3 wt% Sn
300 L α CL = 61.9 wt% Sn
Pb-Sn S
L+ α Wα = = 0.50
system R+S
200
α R S L+β β WL = (1- Wα ) = 0.50
TE R S
• Just below TE :
100 α+ β Cα = 18.3 wt% Sn
Cβ = 97.8 wt% Sn
Wα = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wβ = 0.27
C, wt% Sn
Chapter 9 - 64
• Just above TE :
L
Cα = 18.3 wt% Sn
300 L α CL = 61.9 wt% Sn
Pb-Sn S
L+ α Wα = = 0.50
system R+S
200
α R S L+β β WL = (1- Wα ) = 0.50
Primary 
TE R S
• Just below TE :
100 α+ β Cα = 18.3 wt% Sn
Eutectic  Cβ = 97.8 wt% Sn
Eutectic 
Wα = S = 0.73
0 20 40 60 80 100 R+S
18.3 61.9 97.8 Wβ = 0.27
C, wt% Sn
Chapter 9 - 65
Hypoeutectic & Hypereutectic
“under” “over”
300
L
T(°C)
α L+ α
200 L+β β (Pb-Sn
TE
α+β System)
100
0 20 40 60 80 100 C, wt% Sn
eutectic
61.9
Chapter 9 - 66
300
L
T(°C)
α L+ α
200 L+β β (Pb-Sn
TE
α+β System)
100
0 20 40 60 80 100 C, wt% Sn
eutectic
61.9
eutectic: C0 = 61.9 wt% Sn
160 μm
eutectic micro-constituent
Chapter 9 - 67
300
L
T(°C)
α L+ α
200 L+β β (Pb-Sn
TE
α+β System)
100
0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
eutectic: C0 = 61.9 wt% Sn

α β
α β
α α β β
α β
α β
175 μm 160 μm
eutectic micro-constituent
Chapter 9 - 68
Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
cool
L heat
α + β (For Pb-Sn, 183°C, 61.9 wt% Sn, see previous slide)
Chapter 9 - 69
cool
L heat
• Eutectoid – one solid phase transforms to two other solid phases

S2 S1+S3 intermetallic compound - cementite
cool
γ heat
α + Fe3C (For Fe-C, 727°C, 0.76 wt% C)
Chapter 9 - 70
cool
L heat
• Eutectoid – one solid phase transforms to two other solid phases

S2 S1+S3 intermetallic compound - cementite
cool
γ heat
α + Fe3C (For Fe-C, 727°C, 0.76 wt% C)
• Peritectic - liquid and one solid phase transform to a second solid phase
S1 + L S2
δ +L cool γ (For Fe-C, 1493°C, 0.16 wt% C)
heat
Chapter 9 - 71
Eutectoid & Peritectic
Cu-Zn Phase diagram
e e
e
Chapter 9 - 72
Peritectic transformation γ + L δ
Cu-Zn Phase diagram
e e
e
Chapter 9 - 73
Peritectic transformation γ + L δ
Cu-Zn Phase diagram
e e
e
Eutectoid transformation δ γ+e
Chapter 9 - 74
Iron-Carbon (Fe-C) Phase Diagram
T(°C)
Note that a C concentration range 1600
up to 6.7% only triggers a complex δ
behavior 4 solid phases: L
1400
, g, d and Fe3C
γ γ +L
1200 1148°C L+Fe3C
(austenite)
Fe3C (cementite)
1000
γ +Fe3C
800
Ferrite, α
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) C, wt% C
Chapter 9 - 75
• 2 important T(°C)
1600
points δ
- Eutectic (A): 1400 L
L  γ + Fe3C γ +L
1200
γ A
1148°C L+Fe3C
(austenite)
Fe3C (cementite)
1000
γ +Fe3C
800
α
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 4.30 C, wt% C
Chapter 9 - 76
1600
points δ
1200
γ A
- Eutectoid (B): (austenite)
1148°C L+Fe3C
Fe3C (cementite)
γ  α + Fe3C
1000
γ +Fe3C
800 727°C = Teutectoid
α
B
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
Chapter 9 - 77
1600
points δ
1200
γ A
1148°C L+Fe3C
Fe3C (cementite)
γ  α + Fe3C
1000 γ γ
γ γ γ +Fe3C
727°C = Teutectoid
α
800 B
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
Fe3C (cementite-hard)
α (ferrite-soft)
Chapter 9 - 78
1600
points δ
1200
γ A
1148°C L+Fe3C
Fe3C (cementite)
γ  α + Fe3C
1000 γ γ
γ γ γ +Fe3C
800
α B 727°C = T
eutectoid
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
120 μm (Fe) 0.76 4.30 C, wt% C
Result: Pearlite = alternating
layers of α and Fe3C phases Fe3C (cementite-hard)
α (ferrite-soft)
Chapter 9 - 79
Hypoeutectoid Steel
T(°C)
1600
δ
1400 L
γ γ (Fe-C
γ γ +L
γ γ 1200 1148°C L+Fe3C System)
Fe3C (cementite)
(austenite)
1000
γ + Fe3C
800 727°C

600
α + Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
Chapter 9 - 80
Hypoeutectoid Steel
T(°C)
1600
δ
1400 L
γ γ (Fe-C
γ γ +L
Fe3C (cementite)
(austenite)
γ γ
1000
γ γ γ + Fe3C
 nuclei start to
precipitate 800 727°C
at g grain boundaries.
Why at grain boundaries? 
600
α + Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
Chapter 9 - 81
Hypoeutectoid Steel
T(°C)
1600
δ
1400 L
γ γ (Fe-C
γ γ +L
Fe3C (cementite)
(austenite)
γ γ
1000
γ γ γ + Fe3C
α
α γ γ 800 727°C
γ αγ 
 grows from g 600
grain boundaries. α + Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
Chapter 9 - 82
Hypoeutectoid Steel
T(°C)
1600
δ
1400 L
γ γ (Fe-C
γ γ +L
Fe3C (cementite)
(austenite)
γ γ
1000
γ γ γ + Fe3C
α
α γ γ 800 727°C
γ αγ 
600
α + Fe3C
400
α 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
pearlite
below Teutectoid, the remaining g

(that did not transform into  before)
transforms into pearlite
Chapter 9 - 83
Hypoeutectoid Steel
T(°C)
1600
δ
1400 L
γ γ (Fe-C
γ γ +L
Fe3C (cementite)
(austenite)
γ γ
1000
γ γ γ + Fe3C
α
α γ γ 800 727°C
γ αγ 
600
α + Fe3C
400
α 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
pearlite
Hypoeutectoid
100 μm
steel
pearlite proeutectoid ferrite

Chapter 9 - 84
Hypoeutectoid Steel
T(°C)
1600
Relative phases
δ
composition 1400 L
(Fe-C
α γ γ +L
α
Fe3C (cementite)
(austenite)
γ αγ
1000
γ + Fe3C
Wα = s/(r + s)
800 r s 727°C
Wγ =(1 - Wα)
α
600
α + Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
Hypoeutectoid
100 μm
steel
Chapter 9 - 85
Hypoeutectoid Steel
T(°C)
1600
Relative phases
δ
composition 1400 L
(Fe-C
α γ γ +L
α
Fe3C (cementite)
(austenite)
γ αγ
1000
γ + Fe3C
Wα = s/(r + s)
800 r s 727°C
Wγ =(1 - Wα)
α α RS
600
α + Fe3C
pearlite
400
0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76
Wpearlite = Wγ
Wα’ = S/(R + S) 100 μm
Hypoeutectoid
steel
WFe3C =(1 – Wα’)
Chapter 9 - 86
Hypereutectoid Steel
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ +L
1200 System)
γ γ 1148°C L+Fe3C
Fe3C (cementite)
(austenite)
1000
γ + Fe3C
800 727°C
α
600
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt% C
Chapter 9 - 87
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ +L
1200 System)
Fe3C (cementite)
(austenite)
γ γ 1000
γ γ γ + Fe3C
Fe3C nuclei start to
precipitate 800 727°C
at g grain boundaries.
α
600
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt% C
Chapter 9 - 88
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ +L
1200 System)
Fe3C (cementite)
(austenite)
γ γ 1000
γ γ γ + Fe3C
Fe3C
γ γ 800 727°C
γ γ α
600
Fe3C grows from g
grain boundaries.
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt% C
Chapter 9 - 89
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ +L
1200 System)
Fe3C (cementite)
(austenite)
γ γ 1000
γ γ γ + Fe3C
Fe3C
γ γ 800 727°C
γ γ α
600
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe)C0 C, wt% C
Fe3C pearlite
below Teutectoid, the remaining g

(that did not transform into Fe3C before)
transforms into pearlite
Chapter 9 - 90
T(°C)
1600
δ
1400 L
(Fe-C
γ γ γ γ +L
1200 System)
Fe3C (cementite)
(austenite)
γ γ 1000
γ γ γ + Fe3C
Fe3C
γ γ 800 727°C
γ γ α
600
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe)C0 C, wt% C
Fe3C pearlite
60 μmHypereutectoid
steel
pearlite proeutectoid Fe3C
Chapter 9 - 91
T(°C)
1600
Relative phases
δ
composition 1400 L
(Fe-C
Fe3C γ γ +L
1200 L+Fe3C System)
γ γ 1148°C
Fe3C (cementite)
(austenite)
γ γ 1000
γ + Fe3C
Wγ =x/(v + x)
800 v x 727°C
WFe3C =(1-Wγ)
α
600
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt% C
Chapter 9 - 92
T(°C)
1600
Relative phases
δ
composition 1400 L
(Fe-C
Fe3C γ γ +L
1200 L+Fe3C System)
γ γ 1148°C
Fe3C (cementite)
(austenite)
γ γ 1000
γ + Fe3C
Wγ =x/(v + x)
800 v x 727°C
WFe3C =(1-Wγ)
α V X
Fe3C 600
α + Fe3C
pearlite
400
0 1 C0 2 3 4 5 6 6.7
0.76
(Fe) C, wt% C
Wpearlite = Wγ
Wα = X/(V + X)
60 μmHypereutectoid
WFe =(1 - Wα) steel
3C’
pearlite proeutectoid Fe3C
Chapter 9 - 93
Example Problem
For a 99.6 wt% Fe-0.40 wt% C steel at a temperature just below the eutectoid, determine the
following:
a) The compositions of Fe3C and ferrite (α).
b) The amount of cementite (in grams) that forms in 100 g of steel.
Note : the C concentration at ferrite at Teutoctoid is 0.22 wt%C
1600
δ
1400 L
T(°C) γ +L
γ
Fe3C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°C
600 α + Fe3C
400
0 1 2 3 4 5 6 6.7
C, wt% C
Chapter 9 - 94
Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Cα = 0.022 wt% C
CFe3C = 6.70 wt% C
b) Using the lever rule with 1600

the tie line shown δ
1400 L
R C - Ca T(°C)
WFe C = = 0 γ γ +L
R + S CFe C - Ca
Fe C (cementite)
3 1200 1148°C L+Fe3C
3 (austenite)
0.40 - 0.022 1000
γ + Fe3C
= = 0.057
6.70 - 0.022 800 727°C
R S
Amount of Fe3C in 100 g 600 α + Fe3C
= (100 g)WFe3C 400

0 1 2 3 4 5 6 6.7
Cα C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
Chapter 9 - 95
Classifications of Fe-C alloys
96
▪ < 0.008 wt% Carbon = iron

-ferrite at room T
▪ 0.008 – 2.14 wt% C = steels
- usually < 1 wt %
-  -ferrite + Fe3C at room T
▪ 2.14 – 6.7 wt% C = cast irons
- usually < 4.5 wt % steels cast irons
“pure” iron
97
▪ < 0.008 wt% Carbon = iron

-ferrite at room T
▪ 0.008 – 2.14 wt% C = steels
- usually < 1 wt %
-  -ferrite + Fe3C at room T
▪ 2.14 – 6.7 wt% C = cast irons
- usually < 4.5 wt % steels cast irons
“pure” iron
➢ Magnetic properties:  -ferrite is magnetic, g-austenite is non-magnetic.

➢Mechanical properties: Cementite is very hard and brittle thus it can strengthen steels. Mechanical
properties also depend on the alloy’s microstructure , that is, how ferrite and cementite are mixed.
98
Alloying with Other Elements
Iron (or Iron-C alloys) can be also alloyed with plenty of other metals in a wide range of concentrations.
We refer to as steels as long as Iron is the main component, that is, CFe > 50% wt
• Teutectoid changes: • Ceutectoid changes:
C eutectoid (wt% C)
Ti
T Eutectoid (ºC)
Si
Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni
wt. % of alloying elements wt. % of alloying elements
Chapter 9 - 99
Chapter 12: Structures & Properties of
Ceramics
ISSUES TO ADDRESS...
• How do the crystal structures of ceramic materials
differ from those for metals?
• How do point defects in ceramics differ from those
defects found in metals?
• How are impurities accommodated in the ceramic lattice?
• In what ways are ceramic phase diagrams different from
phase diagrams for metals?
• How are the mechanical properties of ceramics
measured, and how do they differ from those for metals?
Chapter 12 - 1
Classifications of
Ceramics
Chapter 12 -
Atomic Bonding in Ceramics
• Bonding:
-- Can be ionic and/or covalent in character.
-- % ionic character increases with difference in
electronegativity of atoms.
Chapter 12 - 3
• Bonding:
• Degree of ionic character may be large or small:
Chapter 12 - 4
• Bonding:
• Degree of ionic character may be large or small:
CaF2: large
SiC: small
Chapter 12 - 5
Ceramic Crystal Structures
Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions
Chapter 12 - 6
Ceramic Crystal Structures
Oxide structures
– oxygen anions larger than metal cations
– close packed oxygen in a lattice (usually FCC)
– cations fit into interstitial sites among oxygen ions
Mg2+
O2-
Anions (gained electrons) are usually larger than cations (gave up electrons)
Chapter 12 - 7
Factors that Determine Crystal Structure
1. Relative sizes of ions – Formation of stable structures:
--maximize the # of oppositely charged ion neighbors (maximize the coordination number).
Chapter 12 -
For a structure to be stable the surrounding anions must be in contact with the surrounded cation
Chapter 12 -
- - - - - -
+ + +
- - - - - -
unstable stable stable
Chapter 12 - 10
There is thus a minimum
cation radius regarding the
- - - - - - anion one for the structure to
+ + + be stable. In the first
structure in the left the cation
- - - - - - is too small, it cannot touch
all the cations and hence
does not maximize the
unstable stable stable coordination number
Chapter 12 - 11
2. Maintenance of Electroneutrality :
--Net charge in ceramic should be zero.
--Reflected in chemical formula:
Chapter 12 - 12
2. Maintenance of Electroneutrality :
--Net charge in ceramic should be zero. F-
--Reflected in chemical formula:
CaF 2 : Ca 2+ +
cation anions
F-
A m Xp
m, p values to achieve electroneutrality Chapter 12 - 13
Coordination Number and Ionic Radii
r cation
• Coordination Number increases with r
anion
To form a stable structure, how many anions can surround a cation?
r cation Coord. ZnS

r anion Number (zinc blende)
< 0.155 2 linear
0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)
0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic
Chapter 12 - 14
r cation
anion
r cation Coord. ZnS

< 0.155 2 linear

(sodium

(cesium
chloride)
0.732 - 1.0 8 cubic
Chapter 12 - 15
r cation
anion
r cation Coord. ZnS

< 0.155 2 linear

(sodium

(cesium
chloride)
0.732 - 1.0 8 cubic
Chapter 12 - 16
r cation
anion
r cation Coord. ZnS

< 0.155 2 linear

(sodium

(cesium
chloride)
0.732 - 1.0 8 cubic
Chapter 12 - 17
r cation
anion
r cation Coord. ZnS

< 0.155 2 linear

(sodium

(cesium
chloride)
0.732 - 1.0 8 cubic
Chapter 12 - 18
r cation
anion
r cation Coord. ZnS

< 0.155 2 linear

(sodium

(cesium
chloride)
0.732 - 1.0 8 cubic
Chapter 12 - 19
Example Problem: Predicting the Crystal Structure of FeO
• On the basis of ionic radii, what crystal structure

would you predict for FeO?
Cation Ionic radius (nm)
Al 3+ 0.053
Fe 2+ 0.077
Fe 3+ 0.069
Ca 2+ 0.100
Anion
O2- 0.140
Cl - 0.181
F- 0.133
Chapter 12 - 20

Cation Ionic radius (nm)
Al 3+ 0.053
Fe 2+ 0.077
Fe 3+ 0.069
Ca 2+ 0.100
Anion
O2- 0.140
Cl - 0.181
F- 0.133
Chapter 12 - 21

Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069
= 0.550
Ca 2+ 0.100
Anion
O2- 0.140
Cl - 0.181
F- 0.133
Chapter 12 - 22

Cation Ionic radius (nm) • Answer:
Al 3+ 0.053 rcation 0.077
=
Fe 2+ 0.077 ranion 0.140
Fe 3+ 0.069
= 0.550
Ca 2+ 0.100
based on this ratio,
Anion -- coord # = 6 because
0.414 < 0.550 < 0.732
O2- 0.140
-- crystal structure is octahedral
Cl - 0.181
(like NaCl)
F- 0.133
Chapter 12 - 23
Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
 cations (Na+) prefer octahedral sites
Chapter 12 - 24
Rock Salt Structure
Same concepts can be applied to ionic solids in general.
Example: NaCl (rock salt) structure
rNa = 0.102 nm
rCl = 0.181 nm
rNa/rCl = 0.564
 cations (Na+) prefer octahedral sites
So each Na+ has 6 neighbor chloride anions

Chapter 12 - 25
MgO and FeO
MgO and FeO also have the NaCl structure
O2- rO = 0.140 nm
Mg2+ rMg = 0.072 nm
rMg/rO = 0.514
 cations prefer octahedral sites
So each Mg2+ (or Fe2+) has 6 neighbor oxygen atoms
Chapter 12 - 26
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:
r 0.170
Cs+
= = 0.939
r 0.181
Cl-
 Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So each Cs+ has 8 neighbor Cl-
Chapter 12 - 27
AX Crystal Structures
AX–Type Crystal Structures include NaCl, CsCl, and zinc blende
Cesium Chloride structure:
r 0.170
Cs+
= = 0.939
r 0.181
Cl-
 Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So each Cs+ has 8 neighbor Cl-
Conclusion: It is not only the chemical formula which determines the crystal
structure but also the relative sizes of the cations and anions.
Chapter 12 - 28
AX2 Crystal Structures
Fluorite structure
• Calcium Fluorite (CaF2)
• Ca2+ cations in cubic sites
• ZrO2 (zirconia), CeO2 (ceria), UO2, ThO2,
Chapter 12 - 29
AX2 Crystal Structures
Fluorite structure
• Calcium Fluorite (CaF2)
• Ca2+ cations in cubic sites
• ZrO2 (zirconia), CeO2 (ceria), UO2, ThO2,
• Antifluorite structure –
positions of cations and anions reversed
Li2O
Chapter 12 - 30
ABX3 Crystal Structures
• Perovskite structure
Ex: complex oxide BaTiO3
Chapter 12 - 31
Verify the electroneutrality of this crystal
Chapter 12 - 32

As we saw in the crystalline structure chapter:
Chapter 12 - 33

occupies the corners of the cube:

8 corners, 1/8 cation per corner,
1 equivalent cation per cube, valence +2 in the crystal
Chapter 12 - 34


occupies the center of the cube (like in a BCC):

1 cation per cube, valence +4 in the crystal
Chapter 12 - 35



occupies the center of the faces cube (like in a FCC):

6 faces, 1/2 anions per face,
3 equivalent anions per cube, valence -6 in the crystal
Chapter 12 - 36



occupies the center of the faces cube (like in a FCC):

6 faces, 1/2 anions per face,
3 equivalent anions per cube, valence - 6 in the crystal
The crystal (and hence the ceramics) is electroneutral
Chapter 12 - 37
Silicate Ceramics
A large percentage of ceramics is

based on combinations of Silicon,
Aluminum and Oxygen, the three
most abundant elements in the earth
crust (rocks, soils, clays, sand)
Silicate Ceramics

• Basic building block: SiO44- tetrahedron.

• Si-O bonding is largely covalent.
•Note: each SiO4 unit carries with it a net
negative charge of -4.
Silicate Ceramics

• Basic building block: SiO44- tetrahedron.

• Si-O bonding is largely covalent.
•Note: each SiO4 unit carries with it a net
negative charge of -4.
- This does not violate our previous rule
about charge neutrality because isolated
SiO4 tetrahedra do not exist.
• Different ways to arrange SiO44- blocks
→ Various silicate structures
Silicate Ceramics: Silica
SiO2 (silica) polymorphic forms are quartz, crystobalite, & tridymite
Those are complex structures yet based in the
Chapter 12 -
quartz
cristobalite
Chapter 12 -
quartz
cristobalite
Both quartz and cristobalite are built upon the silicate tetrahedron 𝑆𝑖𝑂44− but are denoted 𝑆𝑖𝑂2 . Why and how?
Chapter 12 -
quartz
cristobalite
As the crystal must be electroneutral, the tetrahedra will organize themselves in a complex 3-D layered
structure, so that each “individual” tetrahedron share oxygen anions with other tetrahedra.
Chapter 12 -
quartz
cristobalite
The two blue rectangles in the two pictures surround 4 Si cations and 8 oxygen anions: 𝑆𝑖𝑂2
Chapter 12 -
quartz
cristobalite
The two blue rectangles in the two pictures surround 4 silicon cations and 8 oxygen anions: 𝑆𝑖𝑂2
This illustrates the crucial importance of electroneutrality in ceramics structures Chapter 12 -

Although already complex structures, silica is the simplest silicate structure. Thanks to the
high strength Si-O covalent bonds, it is insoluble in water and also in most acids, except HF
Chapter 12 -
Silicate Ceramics: other forms of structures

Bonding of adjacent SiO44- accomplished by the sharing of common corners edges,
or faces therefore yielding different and more complex structures. Examples:
Chapter 12 -

𝑆𝑖𝑂44− 𝑆𝑖𝑂44−
𝑆𝑖𝑂44−
𝑆𝑖𝑂44−
𝑆𝑖𝑂44−
𝑆𝑖𝑂44− is the base brick of most silicate ceramics
Chapter 12 -

Presence of cations such as Ca2+, Mg2+, Ba2+, Al3+, …

1. maintains charge neutrality, and
2. ionically bond SiO44- to one another
Chapter 12 -


Mg2SiO4 Ca2MgSi2O7 BaTiSi3O9
Chapter 12 -


Mg2SiO4 Ca2MgSi2O7 BaTiSi3O9

(forsterite) (akermanite) (benitoite)
Chapter 12 -
Layered Silicates
• Layered silicates (e.g., clays, mica, talc)
– SiO4 tetrahedra connected
together to form 2-D plane
• A net negative charge is associated

with each (Si2O5)2- unit
• Negative charge balanced by

adjacent plane rich in positively
charged cations
Chapter 12 - 53
Layered Silicates (cont)
• Kaolinite clay alternates (Si2O5)2- layer with Al2(OH)42+ layer
Note: Adjacent sheets of this type are loosely bound to one another by van der Waal’s forces.
Chapter 12 - 54
Silica Glasses
Silica exists in either a crystalline state

(discussed previously) or in a disordered
(amorphous, or vitreous, or glassy) state.
Chapter 12 -
Silica Glasses

Note that the SiO44- tetrahedra form

different networks like the ones
shown in the figure; consequently,
SiO2 and related ceramics are called
“network formers”.
Chapter 12 -
Silica Glasses

Note that the SiO4 tetrahedra form

different networks like the ones
shown in the figure; consequently,
SiO2 and related ceramics are called
“network formers”.
Fused silica: glass with no impurities
Chapter 12 -
Silica Glasses
•Most of our common commercial glasses

consist of a silica network, to which various
other oxide ceramics such as CaO and Na2O
have been added.
•These oxides themselves do not form networks,
but rather modify the networks.
- Consequently, such additives are called
network modifiers
Chapter 12 -
Silica Glasses

have been added.
network modifiers
Chapter 12 -
Silica Glasses

have been added.
network modifiers
•For example, the accompanied schematic
represents the general structure of a sodium
silica glass, where the sodium ions become
incorporated within the silica network.
Network modifiers are added to silica glasses in order to impart
specific properties, such as a reduced softening or vitrification
temperature, a different viscosity, or a particular color or tint.
Chapter 12 -
Polymorphic Forms of Carbon
Diamond
– tetrahedral bonding of
carbon
• hardest material known
• very high thermal
conductivity
– large single crystals –
gem stones
– small crystals – used to
grind/cut other materials
– diamond thin films
• hard surface coatings –
used for cutting tools,
medical devices, etc.
Chapter 12 - 61
Polymorphic Forms of Carbon (cont)
Graphite
– layered structure – parallel hexagonal arrays of carbon atoms
– weak van der Waal’s forces between layers

– planes slide easily over one another -- good lubricant
Chapter 12 - 62
Point Defects in Ceramics (i)
• Vacancies
-- vacancies exist in ceramics for both cations and anions
Cation
Interstitial
Cation
Vacancy
Anion
Vacancy
Chapter 12 - 63
• Vacancies
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites
Cation
Interstitial
Cation
Vacancy
Anion
Vacancy
Chapter 12 - 64
• Vacancies
• Interstitials
-- interstitials exist for cations
-- interstitials are not normally observed for anions because anions
are large relative to the interstitial sites
Cation
Interstitial
Cation
Vacancy
Anion
Vacancy
In an ionic ceramic, a cation vacancy must be accompanied by a

corresponding anion vacancy in order to maintain charge neutrality.
Chapter 12 - 65
Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
Shottky
Defect:
Frenkel
Defect
Chapter 12 - 66
Point Defects in Ceramics (ii)
• Frenkel Defect
-- a cation vacancy-cation interstitial pair.
• Schottky Defect
-- a paired set of cation and anion vacancies.
Schottky
Defect:
Frenkel
Defect
-QD / kT
• Equilibrium concentration of defects µe
Chapter 12 - 67
Imperfections in Ceramics
Electroneutrality (charge balance) must be maintained when impurities are present
• Ex: NaCl
Na + Cl -
cation
Substitutional cation impurity, Ca2+
vacancy
2+
Ca Since the substitution of a
Na+ by a Ca2+ increases the
Na + charge by +1, it imposes the
creation of a Na+ vacancy to
Na + keep electroneutrality
Ca2+
without impurity Ca 2+ impurity with impurity
Substitutional anion impurity, O2-

2-
anion vacancy
O
Since the substitution of a
Cl- by a O2- decreases the
charge by -1, it imposes the
creation of a Cl- vacancy to
Cl - Cl - keep electroneutrality
without impurity O 2- impurity with impurity

Chapter 12 - 68
• Ex: NaCl
Na + Cl -
cation
vacancy
2+
Ca2+

2-
anion vacancy
O

Chapter 12 - 69
• Ex: NaCl
Na + Cl -
cation
vacancy
2+
Ca2+

2-
anion vacancy
O

Chapter 12 - 70
• Ex: NaCl
Na + Cl -
cation
vacancy
2+
Ca2+

2-
anion vacancy
O

Chapter 12 - 71
Ceramic Phase Diagrams
Phase diagrams for ceramic materials obey the same rules as for metal
systems. An important difference is that the components are usually
themselves binary compounds, rather than pure elements.
Chapter 12 -
Cr2O3 -Al2O3
➢One of the simplest ceramic binary
phase diagrams.
• Complete solubility:
✓ Al, Cr atoms possess similar
size and chemical valence
✓Both oxides have the same
crystal structure
✓ Al3+ substitutes for the Cr3+
ion in Cr2O3 (and vice versa)
Chapter 12 -
Cr2O3 -Al2O3
➢One of the simplest ceramic binary
phase diagrams.
• Complete solubility:
✓ Al, Cr atoms possess similar
size and chemical valence
✓Both oxides have the same
crystal structure
✓ Al3+ substitutes for the Cr3+
ion in Cr2O3 (and vice versa)
Chapter 12 -
Note: This system

contains two eutectics,
one on either side of
the spinel (AB2X4) spinel
phase.
Chapter 12 -
Mechanical Properties
Metals/ Graphite/
Ceramics/
Alloys
Semicond
5000
3000
Tensile strength, TS (MPa)

2000 Steel (4140) qt
1000 W (pure) Diamond

Ti (5Al-2.5Sn)aa
Steel (4140)
Cu (71500) cw Si nitride
Cu (71500) hr Al oxide
Steel (1020)
300 Al (6061) ag
Ti (pure) a
200 Ta (pure)
Al (6061) a Si crystal
100 <100>
Glass-soda
40 Concrete
30
20 Graphite
10
1
Chapter 12 -
Ceramic materials are more brittle than metals. Why is this so?
Metals/ Graphite/
Ceramics/
Alloys
Semicond
5000
3000
Tensile strength, TS (MPa)

2000 Steel (4140) qt
1000 W (pure) Diamond

Ti (5Al-2.5Sn)aa
Steel (4140)
Cu (71500) cw Si nitride
Cu (71500) hr Al oxide
Steel (1020)
300 Al (6061) ag
Ti (pure) a
200 Ta (pure)
Al (6061) a Si crystal
100 <100>
Glass-soda
40 Concrete
30
20 Graphite
10
1
Chapter 12 -
Dislocation Characteristics Ceramics

(slide picked up from Chapter 7 Dislocations & Strengthening Mechanisms)
Chapter 12 -

• Ceramics—Covalently Bonded
- Examples: silicon, diamond
- Dislocation motion— relatively
difficult because of Covalent
bonding—directional
Chapter 12 -

• Ceramics—Ionically Bonded + - + - + - +
- Examples: MgO, Al2O3
- + - + - + -
- Dislocation motion—relatively
difficult because of: + - + - + - +
- motion of nearby ions of like charge (+ or -)
restricted by electrostatic repulsive forces
Chapter 12 -

• Ceramics—Ionically Bonded + - + - + - +
- Examples: MgO, Al2O3
- + - + - + -
- Dislocation motion—relatively
difficult because of: + - + - + - +
- motion of nearby ions of like charge (+ or -)
restricted by electrostatic repulsive forces
- Few slip systems
Chapter 12 -
difficult to prepare and shape specimens with the required geometry
Ceramics are typically too brittle to be difficult to grip brittle materials without fracturing them
Submitted to conventional tensile tests
ceramics fail after only about 0.1% strain, specimens should
be perfectly aligned to avoid bending stresses
Chapter 12 - 82
Flexural Tests – Measurement of Elastic Modulus

• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing often used.
cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
Chapter 12 - 83
Flexural Tests – Measurement of Elastic Modulus

• Room T behavior is usually elastic, with brittle failure.
• 3-Point Bend Testing often used.
cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
• Determine elastic modulus according to:
F L3
E= (rect. cross section)
F
d 4bd 3
slope =
δ
F L3
E= (circ. cross section)
linear-elastic behavior
d 12p R 4
Chapter 12 - 84
Flexural Tests – Measurement of Flexural Strength (Eq. Tensile strength)
3-point bend test (till fracture) to measure room-T flexural strength.

cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
location of max tension
Chapter 12 - 85

cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
Flexural strength:
Ff = load on fracture
3Ff L
s fs =
2bd 2
(rect. cross section)
Ff L
s fs =
p R3
(circ. cross section)
Chapter 12 - 86

cross section F
L/2 L/2
d R
b δ = midpoint
rect. circ.
deflection
Flexural strength: Typical values:
Ff = load on fracture Material σ fs (MPa) E(GPa)

Si nitride 250-1000 304
Si carbide 100-820 345
3Ff L Al oxide 275-700 393
s fs =
2bd 2 glass (soda-lime) 69 69
(rect. cross section)
Ff L
s fs =
p R3
(circ. cross section)
Chapter 12 - 87
Classification of Ceramics
Ceramic Materials
Glasses Clay Refractories Abrasives Cements Ceramic Carbon Advanced

products biomaterials ceramics
-optical -whiteware -bricks for -sandpaper -composites -implants -composites -engine

-composite -structural high T - cutting - structural - abrasives rotors
reinforce (furnaces) - polishing valves
-containers/ bearings
household -sensors
Chapter 12 - 88
Ceramics Application: Die Blanks
• Die blanks: die Ad

-- Need wear resistant properties Ao tensile
force
die
• Die surface:
-- 4 μm polycrystalline diamond
particles that are sintered onto a
cemented tungsten carbide
substrate.
-- polycrystalline diamond gives uniform
hardness in all directions to reduce
wear.
Chapter 12 - 89
Ceramics Application:
Cutting Tools
• Tools:
-- for grinding glass, tungsten
carbide, ceramics
-- for cutting Si wafers
-- for oil drilling
• Materials: oil drill bits blades

-- manufactured single crystal
or polycrystalline diamonds Single crystal
diamonds
in a metal or resin matrix.
-- polycrystalline diamonds
polycrystalline
resharpen by microfracturing diamonds in a resin
along cleavage planes. matrix.
Chapter 12 - 90
Refractories
• Materials to be used at high temperatures (e.g., in
high temperature furnaces).
• Consider the Silica (SiO2) - Alumina (Al2O3) system.
• Supports high temperatures, unreactive, thermal
insulation…
2200 3Al2O3-2SiO2
T(ºC)
mullite
2000 Liquid
(L) alumina + L
1800
crystobalite mullite alumina
+L +L +
1600 mullite
mullite
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina)
Chapter 12 - 91
Advanced Ceramics: Materials for Automobile (aircrafts, rockets, …)
(brake discs, fuel injectors,…)
• Advantages:
– Operate at high • Disadvantages:
temperatures – high – Ceramic materials are
efficiencies brittle
– Low frictional losses – Difficult to remove internal
– Operate without a cooling voids (that weaken
system structures)
– Lower weights than – Ceramic parts are difficult
current materials to form and machine
• Potential candidate materials: Si3N4, SiC, & ZrO2

• Possible engine parts: engine block & piston coatings
Chapter 12 - 92
Ceramics Application: Sensors
• Example: ZrO2 as an oxygen sensor
Ca 2+
• Principle: Increase diffusion rate of oxygen
to produce rapid response of sensor signal to
change in oxygen concentration
• Approach: A substituting Ca2+ ion
removes a Zr 4+ ion and
Add Ca impurity to ZrO2: an O2- ion.
-- increases O2- vacancies
-- increases O2- diffusion rate
• Operation: sensor
-- voltage difference produced when gas with an reference
O2- ions diffuse from the external unknown, higher gas at fixed
oxygen content O2-
surface through the sensor to the oxygen content
diffusion
reference gas surface.
-- magnitude of voltage difference
 partial pressure of oxygen at the + -
voltage difference produced!
external surface
Chapter 12 - 93
Advanced Ceramics:
Materials for Ceramic Armor
Components:
-- Outer facing plates
-- Backing sheet
Properties/Materials:
-- Facing plates -- hard and brittle
—
—
-- Backing sheets -- soft and ductile
—
—
Chapter 12 - 94
Advanced Ceramics:
Materials for Ceramic Armor
Components:
-- Outer facing plates
-- Backing sheet
Properties/Materials:
-- Facing plates -- hard and brittle
— fracture high-velocity projectile
— Al2O3, B4C, SiC, TiB2
-- Backing sheets -- soft and ductile
— deform and absorb remaining energy
— aluminum, synthetic fiber laminates
Chapter 12 - 95
Nanocarbons
• Fullerenes – spherical cluster of 60 carbon atoms, C60
– Like a soccer ball
• Carbon nanotubes – sheet of graphite rolled into a tube
– Ends capped with fullerene hemispheres
Chapter 12 - 96
Nanocarbons (cont.)
• Graphene – single-atomic-layer of graphite
– composed of hexagonally sp2 bonded carbon atoms
Chapter 12 - 97
Ceramic Fabrication Methods (i)
GLASS PARTICULATE CEMENTATION

FORMING FORMING
• Blowing of Glass Bottles: • Pressing: plates, cheap glasses
Pressing -- glass formed by application of
Gob
operation
pressure
Parison
-- mold is steel with graphite
mold lining
• Fiber drawing:
Compressed
air
Suspended
parison
Finishing wind up
mold
Chapter 12 - 98
Sheet Glass Forming
• Sheet forming – continuous casting

– sheets are formed by floating the molten glass on a pool of
molten tin
Chapter 12 - 99
Ceramic Fabrication Methods (iia)

FORMING FORMING
Hydroplastic forming:
• Mill (grind) and screen constituents: desired particle size
• Extrude this mass (e.g., into a brick)
Ao
container die holder
force
ram billet extrusion Ad
container die
• Dry and fire the formed piece
Chapter 12 - 10
Ceramic Fabrication Methods (iia)

FORMING FORMING
Slip casting:
• Mill (grind) and screen constituents: desired particle size
• Mix with water and other constituents to form slip
• Slip casting operation
pour slip absorb water pour slip drain “green
into mold into mold into mold mold ceramic”
“green
ceramic”
solid component hollow component
• Dry and fire the cast piece

Chapter 12 - 10
Typical Porcelain Composition
(50%) 1. Clay
(25%) 2. Filler – e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass
Chapter 12 - 10
Drying and Firing
• Drying: as water is removed - interparticle spacings decrease
– shrinkage .
wet body partially dry completely dry

Drying too fast causes sample to warp or crack due to non-uniform shrinkage
micrograph of porcelain
Si02 particle
• Firing: (quartz)
-- heat treatment between glass formed
900-1400°C around
-- vitrification: liquid glass forms the particle
from clay and flux – flows

between SiO2 particles. (Flux 70μm
lowers melting temperature).
Chapter 12 - 10
Ceramic Fabrication Methods (iib)

FORMING FORMING
Powder Pressing: used for both clay and non-clay compositions.
• Powder (plus binder) compacted by pressure in a mold

-- Uniaxial compression - compacted in single direction
-- Isostatic (hydrostatic) compression - pressure applied by
fluid - powder in rubber envelope
-- Hot pressing - pressure + heat
Chapter 12 - 10
Sintering
Sintering occurs during firing of a piece that has
been powder pressed
-- powder particles coalesce and reduction of pore size
Aluminum oxide powder:

-- sintered at 1700°C
for 6 minutes.
15 μm
Chapter 12 - 10
Ceramic Fabrication Methods (iii)

FORMING FORMING
• Hardening of a paste – paste formed by mixing cement
material with water
• Formation of rigid structures having varied and complex
shapes
• Hardening process – hydration (complex chemical
reactions involving water and cement particles)
• Portland cement – production of:
-- mix clay and lime-bearing minerals
-- calcine (heat to 1400°C)
-- grind into fine powder
Chapter 12 - 10
Chapter 17:
Corrosion and Degradation of
Materials
• How does corrosion occur?
• Which metals are most likely to corrode?
• What environmental parameters affect
corrosion rate?
• How do we prevent or control corrosion?
Chapter 17 - 1
THE COST OF CORROSION
• Corrosion:
-- the destructive
electrochemical
attack of a material.
-- Ex: Rusting of
© EHStock/iStockphoto
automobiles and
other equipment
• Cost:
-- 4 to 5% of the Gross National Product (GNP)*
-- in the U.S. this amounts to just over $400 billion/yr**
* H.H. Uhlig and W.R. Revie, Corrosion and Corrosion Control: An Introduction
to Corrosion Science and Engineering, 3rd ed., John Wiley and Sons, Inc.,
1985.
**Economic Report of the President (1998).
Chapter 17 - 2
ELECTROCHEMICAL CORROSION
Ex: consider the corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction: Zn ® Zn2+ + 2e-
-- reduction reaction: 2H+ + 2e- ® H2 (gas)
H+
Oxidation reaction
Zn Zn2+ H+
H+ Acid
Zinc flow of e- 2e-
in the metal H+ + solution
H
H+
H2(gas)
H+
reduction reaction
• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution
O2 + 4H+ + 4e- ® 2H2O O2 + 2H2O + 4e- ® 4(OH)-
Chapter 17 - 3
STANDARD HYDROGEN ELECTRODE
• Two outcomes:
-- Corrosion -- Electrodeposition
e- e- e- e-
H2(gas) H+ 2e -
ne - 2e - ne -
H+
Platinum
Platinum
Mn+
metal, M
Mn+ H+
metal, M
ions ions
H+
H2(gas)
25°C 25°C
1M Mn+ sol’n 1M H + sol’n 1M Mn+ sol’n 1M H+ sol’n
-- Metal is the anode (-) -- Metal is the cathode (+)
o
Vmetal <0 (relative to Pt)
o
Vmetal >0 (relative to Pt)
Standard Electrode Potential

Chapter 17 - 4
STANDARD EMF SERIES
• EMF series o
• Metal with smaller
metal Vmetal o
Vmetal corrodes.
Au +1.420 V
• Ex: Cd-Ni cell
more cathodic
Cu +0.340 o o
Pb - 0.126 V Cd < V Ni  Cd corrodes
Sn - 0.136 - +
Ni - 0.250
Co - 0.277 DV o =
Cd - 0.403 0.153V
Fe - 0.440
more anodic
Cr - 0.744 Cd 25°C Ni
Zn - 0.763
Al - 1.662
1.0 M 1.0 M
Mg - 2.363
Cd 2+ solution Ni 2+ solution
Na - 2.714
Data based on Table 17.1, Fig. 17.2, Callister & Rethwisch 10e.
K - 2.924 Callister 10e.
Chapter 17 - 5
CORROSION IN A GRAPEFRUIT
Cu (cathode) Zn (anode)
+ -
H+
H+ Zn 2+
reduction reactions 2e - oxidation reaction

H+
H+
Acid H+
H+ H+
Chapter 17 - 6
EFFECT OF SOLUTION CONCENTRATION AND
TEMPERATURE
• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with
standard 1 M solutions non-standard solutions
RT X
VNio -VCd
o
= 0.153 V VNi -VCd = VNio -VCd
o
- ln
- + - + nF Y
n = #e-
per unit
oxid/red
Cd 25°C Ni Cd T Ni reaction
(= 2 here)
F=
1.0 M 1.0 M XM YM Faraday's
Cd 2+ solution Ni 2+ solution Cd 2+ solution Ni 2+ solution constant
• Reduce VNi - VCd by = 96,500
C/mol.
-- increasing X
-- decreasing Y
-- increasing T Chapter 17 - 7
GALVANIC SERIES
• Ranking of the reactivity of metals/alloys in seawater
Platinum
more cathodic
Gold
Graphite
(inert)
Titanium
Silver
316 Stainless Steel (passive) Table 17.2, Callister &
Nickel 200 (passive) Rethwisch 9e.
Source is Davis, Joseph R. (senior
Copper editor), ASM Handbook, Corrosion,
Volume 13, ASM International, 1987, p.
Nickel 200 (active) 83, Table 2.
Tin
more anodic
Lead
316 Stainless Steel (active)
(active)
Cast Iron/Low-carbon Steel

Aluminum Alloys
Cadmium
Zinc
Magnesium
Chapter 17 - 8
FORMS OF CORROSION
• Stress corrosion
Corrosion at crack tips
• Uniform Attack when a tensile stress • Erosion-corrosion
Oxidation & reduction is present. Combined chemical attack and
reactions occur uniformly mechanical wear (e.g., pipe
over surfaces. elbows).
• Selective Leaching • Pitting
Preferred corrosion of Forms Downward propagation
one element/constituent of small pits and holes.
of
[e.g., Zn from brass (Cu-Zn)]. Fig. 17.17, Callister &
corrosion Rethwisch 10e. (Photograph
• Intergranular courtesy of Rick Adler/Adler
Engineering LLC of Wyoming
Corrosion along USA)
grain boundaries,
often where precip. • Galvanic • Crevice Narrow and
particles form. Dissimilar metals are confined spaces.
g.b. physically joined in the Rivet holes
prec. presence of an
electrolyte. The
attacked Fig. 17.15, Callister & Rethwisch 10e.
zones more anodic metal (Courtesy LaQue Center for Corrosion
Technology, Inc.)
Fig. 17.18, Callister & corrodes.
Chapter 17 - 9
Rethwisch 10e.
CORROSION PREVENTION (i)
• Materials Selection
-- Use metals that are relatively unreactive in the
corrosion environment -- e.g., Ni in basic solutions
-- Use metals that passivate
Metal oxide
- These metals form a thin, Metal (e.g., Al,
adhering oxide layer that stainless steel)
slows corrosion.
• Lower the temperature (reduces rates of oxidation and
reduction)
• Apply physical barriers -- e.g., films and coatings
Chapter 17 - 10
CORROSION PREVENTION (ii)
• Add inhibitors (substances added to solution that decrease
its reactivity)
-- Slow oxidation/reduction reactions by removing reactants
(e.g., remove O2 gas by reacting it w/an inhibitor).
-- Slow oxidation reaction by attaching species to
the surface.
• Cathodic (or sacrificial) protection

-- Attach a more anodic material to the one to be protected.
Galvanized Steel Using a sacrificial anode
Zn 2+ Cu wire
e-
zinc zinc steel Mg Mg 2+
2e - 2e - pipe anode
steel Earth
e.g., zinc-coated nail e.g., Mg Anode
Chapter 17 - 11
SUMMARY
• Metallic corrosion involves electrochemical reactions
-- electrons are given up by metals in an oxidation reaction
-- these electrons are consumed in a reduction reaction
• Metals and alloys are ranked according to their
corrosiveness in standard emf and galvanic series.
• Temperature and solution composition affect corrosion
rates.
• Forms of corrosion are classified according to mechanism
• Corrosion may be prevented or controlled by:
-- materials selection
-- reducing the temperature
-- applying physical barriers
-- adding inhibitors
-- cathodic protection
Chapter 17 - 12
Chapter 10: What is it about?
This is an equilibrium diagram:
phases present here had all the time they needed to form…
T(°C)
1600
δ
1400 L
γ γ +L
1200
(austenite)
1148°C L+Fe3C
Fe3C (cementite)
1000
γ +Fe
3C
800
α
600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe)
C, wt% C
Chapter 10 -
Chapter 10: Phase Transformations
• Transforming one phase into another takes time.
Fe Fe C
3
Eutectoid
γ transformation (cementite)
(Austenite) +
α
C FCC BCC
(ferrite)
• How does the rate of transformation depend on

time and temperature ?
• Is it possible to manage transformations so that
non-equilibrium structures are formed?
• Are the mechanical properties of non-equilibrium
structures more desirable than equilibrium ones?
Chapter 10 - 2
Phase Transformations
Nucleation
- nuclei (seeds) act as templates on which crystals grow
- for nucleus to form, the rate of addition of
atoms to nucleus must be faster than the
rate of loss. If rate of loss > rate of addition,
the nuclei vanishes
nucleation growth crystal
- once nucleated, growth proceeds until equilibrium is attained
nucleation growth crystal
Chapter 10 - 3
Phase Transformations
Nucleation
Driving force to nucleate increases as we increase ΔT

– supercooling (eutectic, eutectoid)
Small supercooling
slow nucleation rate

few nuclei
large crystals
Large supercooling
rapid nucleation rate

many nuclei
small crystals
Chapter 10 - 4
Solidification: Nucleation Types
• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires considerable supercooling
(typically 100-300°C)
higher supercooling lower supercooling

(higher DT) (lower DT)
Chapter 10 - 5
Solidification: Nucleation Types
• Homogeneous nucleation
– nuclei form in the bulk of liquid metal
– requires considerable supercooling
(typically 100-300°C)
• Heterogeneous nucleation
– much easier since stable “nucleating surface” is already present —
e.g., mold wall, impurities in liquid phase
– only very slight supercooling (0.1-10°C)
higher supercooling lower supercooling

(higher DT) (lower DT)
Chapter 10 - 6
Homogeneous Nucleation & Energy Effects
Surface Free Energy- destabilizes
the nuclei (it takes energy to make
an interface)
>0 γ = surface tension
ΔGT = Total Free Energy
= ΔGS + ΔGV
For r > r*, dDGT/dr < 0
Volume (Bulk) Free Energy –
stabilizes the nuclei (releases energy)
4 3
DGV = p r DGu < 0
3
volume free energy
DGu =
unit volume
r* = critical nucleus: for r < r* nuclei shrink;

for r > r* nuclei grow (to reduce energy) Chapter 10 - 7
Rate of Phase Transformations
Kinetics - study of reaction rates of phase transformations

• To determine reaction rate – measure degree of transformation as
function of time (while holding temperature constant)
How is degree of transformation measured?
X-ray diffraction – many specimens required

electrical conductivity measurements –
on single specimen
measure propagation of sound waves –

on single specimen
Chapter 10 - 8
Rate of Phase Transformation
Fraction transformed, y
transformation complete
Fixed T
0.5 maximum rate reached – from now on, the amount
of unconverted phase decreases and the rate slows
rate increases as the interfacial surface

t0.5 area increases & nuclei grow
log t
Avrami equation => y = 1- exp (-kt n)

fraction time
transformed
– k & n are transformation specific parameters
By convention rate = 1 / t0.5

Chapter 10 - 9
Temperature Dependence of Transformation Rate
135C 119C 113C 102C 88C 43C
1 10 102 104
• For the recrystallization of Cu (rate = 1/t0.5)
rate increases with increasing temperature
Rate often so slow that attainment of equilibrium state not possible!
Chapter 10 - 10
Transformations & Undercooling
Upon crossing a phase boundary on the composition-temperature phase diagram,
phase transformation towards equilibrium state is induced. For instance,
Eutectic transformation: Lα + b A
But the nucleation and growth of the equilibrium structure

(a + b) takes time so that as the system is cooled down
B
the transformation is delayed
Pb Sn
The phase transformations therefore occur at temperatures
lower than predicted by phase diagram: supercooling
(In the same way, during heating, The phase transformations therefore occur at
temperatures higher than predicted by phase diagram: superheating)
The degree of supercooling/superheating increases with the rate of cooling/heating:

The faster the system is cooled, the lower will be the temperature in
which transformation will take pace
Microstructures are strongly affected by the rate of cooling: metastable

states can even be formed due to fast temperature changes.
Example with 10% Sn cooled down from 250 ⁰ to room temperature (A →B)
Chapter 10 - 11
• Eutectoid transf. (Fe-Fe3C system): γ  α + Fe3C

• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727 C 0.022 wt% C
T(C)
1600
δ
1400 L
γ γ +L
1200 1148 C L+Fe3C
Fe3C (cementite)
(austenite)
1000
α γ +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. = 727 C
727 C
α +Fe3C
600
0.022
0.76
400
0 1 2 3 4 5 6 6.7
(Fe) C, wt%C
Chapter 10 - 12
• Eutectoid transf. (Fe-Fe3C system): γ  α + Fe3C

• For transf. to occur, must 0.76 wt% C 6.7 wt% C
cool to below 727 ⁰C 0.022 wt% C
T(⁰C)
1600
δ
1400 L
γ γ +L
1200 1148 C L+Fe3C
Fe3C (cementite)
(austenite)
1000
α γ +Fe3C
Eutectoid:
ferrite 800 Equil. Cooling: Ttransf. = 727 C
727C
ΔT α +Fe3C
600 Undercooling by Ttransf. < 727 C
0.022
0.76
400
0 1 2 3 4 5 6 6.7
(Fe) C, wt%C
Chapter 10 - 13
The Fe-Fe3C Eutectoid Transformation
Transformation of austenite to pearlite:
C diffusion during transformation
Austenite (γ) cementite (Fe3C) α

grain α Ferrite (α)
α γ
boundary γ γ
γ α α
α pearlite growth
α
α direction α
Carbon
diffusion
100 650 ⁰C
y (% pearlite)
600 ⁰C
the g – pearlite transformation (ΔT
larger)
rate increases with 50
675 ⁰C
ΔT = [T – Teutectoid (727 ⁰C)]. (ΔT
smaller)
0
Chapter 10 - 14
Back to slide #3… Phase Transformations
Nucleation
Driving force to nucleate increases as we increase ΔT

– supercooling (eutectic, eutectoid)
Small supercooling
slow nucleation rate

few nuclei
large crystals
Large supercooling
rapid nucleation rate

many nuclei
small crystals
Chapter 10 - 15
The Fe-Fe3C Eutectoid Transformation
Transformation of austenite to pearlite:
C diffusion during transformation
Austenite (γ) cementite (Fe3C) α

grain α Ferrite (α)
α γ
boundary γ γ
γ α α
α pearlite growth
α
α direction α
Carbon
diffusion
100 650 ⁰C
y (% pearlite)
600 ⁰C
the g – pearlite transformation (ΔT
larger)
rate increases with 50
675 ⁰C
ΔT = [T – Teutectoid (727 ⁰C)]. (ΔT
smaller)
0
Coarse pearlite forms at higher temperatures – relatively soft
The a, Fe3C layers thickness depend on the transformation temperature:

10 mm The higher the temperature, the thicker the layers.
Fine pearlite forms at lower temperatures – relatively hard 10 -mm

Chapter 10 16
Generation of Isothermal Transformation Diagrams
(or Time-Temperature-Transformation, TTT diagrams)
Consider:
• The Fe-Fe3C system, for C0 = 0.76 wt% C
• A transformation temperature of 675 ºC.
% transformed
100
T = 675 ⁰C
y,
50
0
1 10 2 10 4 time (s)
T( ⁰C)
Austenite (stable)
TE (727 ⁰C)
700 Austenite
(unstable)
600 Pearlite
isothermal transformation at 675°C

500
400
time (s)
1 10 10 2 10 3 10 4 10 5 Chapter 10 - 17
Austenite-to-Pearlite Isothermal Transformation
• Eutectoid composition, C0 = 0.76 wt% C
• Begin at 727°C
• Rapidly cool to 625°C
• Hold T (625°C) constant (isothermal treatment)
T(ºC) Austenite (stable)
TE (727 ⁰C)
700 Austenite
(unstable)
600 Pearlite
γ γ
γ γ γ γ
500
400
1 10 10 2 10 3 10 4 10 5
time (s)
Chapter 10 - 18
Martensite: a highly important microstructure
Let us first consider that austenite dissolves
up to ~2%C while ferrite only dissolves 0.022% max.
Now, what happens if an austenitic structure with
medium to high-carbon is quenched (rapidly cooled)
down to temperatures in which g is not stable?
Due to the fast cooling, the C atoms do not have time to diffuse
out of the FCC g and remain trapped in solid solution. They
thus force the crystal reorganization forming an elongated
body-centered tetragonal phase (BCT) called martensite
iron Thanks to this crystalline distorted structure, martensite

is a very hard phase (thus brittle) yielding steels to be used where
very high-strength is requested
carbon
Martensite is a metastable phase that

does not appear in the phase diagram
Martensite BCT crystal unit

Martensite Microstructure
• Diffusionless transformation:
g→ a-martensite (very fast)
60 μm
• Needle-like or lath-like appearance
• microstructure almost always contains
retained austenite (the part of austenite that
did not transform into martensite) Martensite needles and laths
Austenite
• microstructural development of martensite
defined by transformation curves as TTT Isothermal Transf. Diagram (TTT curve)
• alloying elements affect the 800 Austenite (stable)
ease of martensite formation T(⁰C) TE
A
P
600
The system must be cooled fast enough to
avoid entering the g -transforming region 400 B
A
0%
200 M+A 50%
% transformation depends only on T M+A 90%
to which the system is rapidly cooled M
10-1 10 103 105 time (s)
Tempered Martensite
Heat treat martensite to form tempered martensite
(remember martensite is a metastable (non-equilibrium) phase)
tempered martensite less brittle than martensite

TS(MPa)
YS(MPa)
1800
1600 TS
tempering decreases
Tensile strength, Yield strength, 1400 YS
but increases ductility,
here represented by %RA 1200
9 μm
60
(reduction of area)
1000 50
%RA %RA
40
800 30
200 400 600
Tempering T ( ⁰C)
tempering produces small Fe3C particles surrounded by α.
Chapter 10 -
Bainite: Another Fe-Fe3C Transformation Product
obtained at moderate cooling rates, between pearlite (slow) and martensite (fast)
Bainite:
-- plate-like (elongated) Fe3C particles in α-ferrite matrix formed at temperatures
lower than pearlite
-- diffusion controlled transformation
-- the a-ferrite has a high dislocations density which therefore makes bainite
harder than pearlite
α (ferrite)
TTT Diagram, C0 = 0.76 wt% C

800 Austenite (stable)
T(⁰C) A
TE
P
600 100% pearlite
100% bainite Note that in some TTT diagrams in the literature,

400 B Austenite is referred to as A instead of g.
A P and B refer to Pearlite and Bainite, respectively.
200
10-1 10 103 105

time (s) Chapter 10 - 22
Spheroidite: Another Microstructure for the Fe-Fe3C System
• Spheroidite: α
(ferrite)
-- Fe3C particles within an α-ferrite matrix
-- formation requires diffusion
Fe3C
(cementite)
Obtained by heating bainite or pearlite at

temperature just below eutectoid 60 μm
for long times
The softest (most ductile) steel
microstructure. We thus proceed to
spheroidization to increase steels formability
Chapter 10 - 23
Precipitation Hardening
• Particles hinder or impede dislocations movement.
• Things that slow down/hinder/impede dislocation movement
will increase y and TS
• Including other phases - especially very small, well dispersed particles.

In some alloys, we can get small, uniform particles to precipitate out of
(solid) solution. Hence named “precipitation hardening” also known as
"AGE" - hardening. Examples include:
✓ Al-Cu
✓ Cu-Be
✓ Cu-S
✓ Mg-Al
✓ Some alloy and stainless steels
• Many Al-alloys are precipitation hardenable

• Al - Cu is best known alloy, e.g. Al - 4%Cu
Precipitation Hardening
We consider a A + B binary alloy with C0 wt% of B, microstructure a + b at room T
Procedure:
• Heat to To and hold until only a - phase
present.
•Quench (rapid cooling) to T1
because no diffusion has time to occur,
B atoms remain “trapped” in a:
A super-saturated solid solution (SSSS) of
a forms. Not thermodynamically stable.
•Reheat to T2 where diffusion can occur
and small precipitates of b-phase form.
M = Max. solubility of
metal B in metal A.
Solid solubility decreases
to N as T
0
Summary of Possible Transformations
Austenite (γ)
slow moderate rapid

cool cool quench
Pearlite Bainite Martensite

(α + Fe3C layers + a (α + elong. Fe3C particles) (BCT phase
proeutectoid phase) diffusionless
transformation)
Martensite reheat
T Martensite
Strength
Ductility
bainite Tempered
fine pearlite Martensite
coarse pearlite (α + very fine
spheroidite Fe3C particles)
General Trends
Chapter 10 - 26
Isothermal Heat Treatment Example
Problems
On the isothermal transformation diagram for a 0.76 wt% C, Fe-C
alloy, sketch and label the time-temperature paths to produce the
following microstructures:
a) 100% martensite
b) coarse pearlite
c) 50% fine pearlite and 50% bainite
Chapter 10 - 27
Solutions to Part (a) Example Problem
a) 100% martensite
Chapter 10 - 28
Solution to Part (b) of Example
Problem
b) coarse pearlite
Chapter 10 - 29
Solution to Part (c) of Example
Problem
c) 50% fine pearlite and 50% bainite
Chapter 10 - 30

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Phase Diagrams

Recall a previous example (solid solubility)

•Phase: a chemically homogeneous portion of a microstructure; a

•System: a series (family) of possible alloys, compounds, and

Equilibrium: The stable configuration of a system, when a sufficient amount of time

➢ This is an alloy of Fe with 4 wt.% C.

Phase diagrams will help us to understand and predict

In one-component systems (as pure A or B in the figure)

T1 In multi-component systems melting occurs over a range of temperatures,

a 60%A – 40%B solid alloy will melt

Pure copper along this axis

Pure nickel along this axis

What 1085°C and 1453°C stand for?

Indeed, any extra amount of sugar beyond 70% (at 70° C )

Indeed, any extra amount of sugar beyond 70% (at 70° C )

Indeed, any extra amount of sugar beyond 70% (at 70° C )

Solving… L = 2 / 3 (or 66.7%) ; S = 1 / 3 (or 33.3%)

Indeed, any extra amount of sugar beyond 70% (at 70° C )

The lever rule is a mechanical analogy to the mass balance

The lever rule is a mechanical analogy to the mass balance

1) All material must be in one phase or the other:

2) Mass of a component that is present in both phases

3) Solution of these equations gives us the lever rule.

W  = (C - Co) / (C - C )

1) All material must be in one phase or the other:

2) Mass of a component that is present in both phases

3) Solution of these equations gives us the lever rule.

W  = (C - Co) / (C - C )

This is what we did in our previous example (water + sugar)

Total concentration of sugar at point 4, C4 = 0.7 L + 1S = 0.8

1) All material must be in one phase or the other:

2) Mass of a component that is present in both phases

3) Solution of these equations gives us the lever rule.

W  = (C - Co) / (C - C )

This is what we did in our previous example (water + sugar)

Total concentration of sugar at point 4, C4 = 0.7 L + 1S = 0.8

0.36 L + 0.53 = 0.45 with  + L = 1

0.36 (1 −  ) + 0.53 = 0.45

Co = 35 wt. %, CL = 31.5 wt. %, C = 42.5 wt. %

W = R / (R+S) = (Co - CL) / (C - CL) = 0.32

How much sugar (in g) can you dissolve in 2 L of water at 50 C?

How much sugar (in g) can you dissolve in 2 L of water at 50 C?

How much sugar (in g) can you dissolve in 2 L of water at 50 C?

Answer = 4250 g !!!

How much sugar (in g) can you dissolve in 2 L of water at 50 C?

Answer = 4250 g !!!

How much sugar (in g) can you dissolve in 2 L of water at 50 C?

Answer = 4250 g !!!

How much sugar (in g) can you dissolve in 2 L of water at 50 C?

Answer = 4250 g !!!

EX 1: Pb-Sn Eutectic System

EX 1: Pb-Sn Eutectic System

EX 1: Pb-Sn Eutectic System

EX 1: Pb-Sn Eutectic System

The lamellar − layered structure grows as indicated by the arrow.

The lamellar − layered structure grows as indicated by the arrow.

This local exhaustion of the liquid in Pb (ahead of ) and Sn (ahead of ) creates

eutectic: C0 = 61.9 wt% Sn

eutectic: C0 = 61.9 wt% Sn

• Eutectoid – one solid phase transforms to two other solid phases

• Eutectoid – one solid phase transforms to two other solid phases

Eutectoid transformation δ γ+e

below Teutectoid, the remaining g