10.phase Diagrams PDF

Phase Diagrams
Reading: Callister Ch. 10

What is a phase?
What
Wh t iis th
the equilibrium
ilib i
state
t t when
h diff
differentt elements
l
t are
mixed?
What phase diagrams tell us.
How phases evolve with temperature and composition
(microstructures).
(lighter
phase)
(darker
phase)
2007, 2008 Moonsub Shim, University of Illinois
MSE280
Phases
Phase: A homogeneous portion of a system that has
uniform physical and chemical characteristics.
1 Diff
1.
Differentt physical
h i l states:
t t
vapor, liliquid,
id solid
lid
e.g. water
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Phases
2. Different chemical compositions
e.g. sugar water

Solubility Limit:
Max concentration for
which only a solution
occurs.
Solubility limit increases
with T:
e.g., if T = 100C, solubility
limit = 80wt% sugar.
Question: What is the solubility limit at 20C?

Answer: 65wt% sugar.
If Co < 65wt% sugar: syrup
3
If Co > 65wt% sugar: syrup + sugar.
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Components:
elements or compounds which are mixed initially
(e.g., Al and Cu)
Phases:
physically
p
ys ca y and
a d chemically
c e ca y d
distinct
s c regions
eg o s that
a result
esu
(e.g., and ).
AluminumCopper
Alloy
(lighter
phase)
(darker
phase)
Plain carbon steel
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Temperature and composition

B
A: 2 phases present (liquid solution and solid sugar)

B: Single phase
C: back to 2 phases but at different composition
Note: this is an equilibrium phase diagram
(What does it mean to have phase equilibrium?)
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Phase Equilibrium
Equilibrium: minimum energy state for a given T, P,
and composition (i
(i.e.
e equilibrium state will persist
indefinitely for a fixed T, P and composition).
An equilibrium phase will stay constant over time.
Phase diagrams tell us about equilibrium phases as a
function of T, P and composition (here, well always
keep P constant for simplicity)
simplicity).
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Unary Systems
Single component system
Consider 2 elemental metals separately:
Cu has melting T = 1085oC
Ni has melting T = 1453oC
(at standard P = 1 atm)

T
liquid
liquid
1453oC
1085oC
solid
solid
Ni
7
What happens when Cu and Ni are mixed?
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Cu
Binary Isomorphous Systems

2 components
Complete liquid and solid solubility
Expect Tm of solution to lie in between Tm of two pure components

T
liquid
liquid
L
1453oC
1085oC
solid
0
Cu
wt% Ni
solid
100
Ni
For a pure
component,
complete melting
occurs before T
increases (sharp
phase transition).
transition)
But for
multicomponent
systems, there is
usually a
coexistence of L
and S.
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Binary Isomorphous Systems

What can we learn from
this phase diagram?
1. Phase(s) present.
A: solid () only
B: solid and liquid
2. Composition of those
phases
A: 60 wt% Ni
B: 35 wt% Ni overall (how
about in L and S
separately?)
Solid-liquid
coexistence
region
3. Amount of the
phases.
A: 100% phase
B: % solid and % liquid?
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Determining phase composition

in 2-phase region:
1. Draw the tie line.
2. Note where the tie line
intersects the liquidus and
solidus lines (i.e. where the tie
line crosses the phase
boundaries).
3. Read off the composition at the
boundaries:
Liquid is composed of CL
amount of Ni (31
(31.5
5 wt% Ni)
Ni).
Solid is composed of C
amount of Ni (42.5 wt% Ni).
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Lever Rule
Determining phase amount in the 2phase region:
1. Draw the tie line.
2 Determine
2.
D t
i th
the di
distance
t
ffrom th
the
point of interest (B) to each of the
phase boundaries.
R = Co CL
S = C - Co
3. Mass fractions (wt%) of each
phase:
C Co
S
42.5 35
=
=
= 0.68
R + S C C L 42.5 31.5
C CL
R
35 31.5
Solid: W =
= o
=
= 0.32
R + S C C L 42.5 31.5
Liquid: WL =
i.e. 68% of the mass is liquid and 32% of the mass is solid.
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Lever Rule: Derivation

Since we have only 2 phases:
WL + W = 1
(1)
Conservation of mass requires that:

Amount of Ni in -phase + amount of Ni in liquid phase = total amount of Ni
or
W C + WL C L = Co
(2)
From 1st condition, we have:
Sub-in to (2):
W = 1 WL
(1 WL )C + WL C L = Co
Solving for WL and W gives :
WL =
C Co
C C L
W =
Co C L
C C L
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Lever Rule: Derivation

A geometric interpretation:
Co
CL
C
R
S
WL
moment equilibrium:
WLR = WS
1 W
solving gives Lever Rule
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Microstructures in Isomorphous Alloys

Microstructures will vary on the cooling rate (i.e. processing conditions)
1. Equilibrium Cooling: Very slow cooling to allow phase equilibrium to
be maintained during the cooling process.
a (T>1260oC): start as
homogeneous liquid solution.
b (T ~ 1260oC): liquidus line

reached. phase begins to
nucleate. C = 46 wt% Ni; CL = 35 wt% Ni
c (T= 1250oC): calculate composition
and mass fraction of each phase.
d (T~ 1220oC): solidus line reached.

Nearly complete solidification.
C = 35 wt% Ni; CL = 24 wt% Ni
e (T<1220oC): homogeneous solid

solution with 35 wt% Ni.
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Example problem
65 wt% Ni 35 wt% Cu alloy is heated to

T within
ithi th
the +L
L region.
i
If -phase
h
contains 70 wt% Ni, determine:
a. Temperature of the alloy.
b. Composition of the liquid phase.
phases.
c. Mass fraction of both p
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Non-equilibrium cooling
Fast cooling, but how fast?
Fast w
w.r.t.
r t diffusion
Since diffusion rate is especially low in solids, consider
case where:
Cooling rate >> diffusion rate in solid
Cooling rate << diffusion rate in liquid
(equilibrium maintained in liquids phase)
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Non-equilibrium cooling
a (T>1260oC): start as
homogeneous liquid solution.
b (T ~ 1260oC): liquidus line
phase begins
g
to nucleate.
reached. p
C = 46 wt% Ni; CL = 35 wt% Ni
c (T= 1250oC): solids that formed at pt b

remain with same composition (46wt%)
and new solids with 42 wt% Ni form around
the existing solids (Why around them?).
d (T~ 1220oC): solidus line reached.

Nearly complete solidification.
Previously solidified regions maintain original
composition and further solidification occurs at
35 wt% Ni.
e (T<1220oC): Non-equilibrium
solidification complete (with phase
segregation).
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Cored vs. Equilibrium phases

C changes as we solidify.
Cu-Ni case: First to solidify has C = 46wt%Ni.
L t to
Last
t solidify
lidif h
has C = 35wt%Ni.
35 t%Ni
Fast rate of cooling:

Cored structure
Slow rate of cooling:

Equilibrium structure
First to solidfy:
46wt%Ni
Last to solidfy:
< 35wt%Ni
35 t%Ni
Uniform C :
35wt%Ni
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Binary Eutectic Systems

Cu-Ag phase diagram
easily melted
Single phase regions:
-phase (solid solution rich in Cu).
-phase (solid solution rich in Ag).
L-phase (liquid solution).
2-Phase coexistence regions:
+ phases (limited solubility of Ag
in Cu and vice versa lead to 2
different solid solution phases).
+L and +L phase regions.
Tie lines and Lever Rule can be
applied in the 2-phase regions.
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Binary Eutectic System

Cu-Ag phase diagram
C =7wt% Ag
CL = 50wt% Ag
Calculate
composition and
mass fractions of
each phases at
points A and B
B.
Tie line
Tie line
A
C = 3wt% Ag
C = 97wt% Ag
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10
Eutectic Point
Eutectic point: Where 2 liquidus lines
meet (pt. E).
Sometimes also referred to as invariant
point.
Eutectic Reaction:
cool
L(CE)
(CE) + (CE)
heat
similar to one component (pure) system
except
p 2 solid p
phases.
Cu-Ag phase diagram
Eutectic Isotherm: Horizontal solidus

line at T = TE.
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Eutectic System: Example

At 150oC for a 40wt% Sn/ 60
wt% Pb alloy:
1 What phases are present?
1.
2. What are the compositions of
the phases present?
3. What are the mass fractions of
the phases?
4. What are the volume
fractions?
For a 10wt% Sn/ 90wt% Pb alloy:
1. At what T, can a state with 50%
liquid be achieved?
2. At 250oC, how much Sn must
be added to achieve the same
Pb-Sn phase diagram
state (50% liquid)?
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11
Microstructures in Eutectic Alloys
1. One component rich composition.

a: start with homogeneous liquid.
b: -phase solids with liquid.
Compositions and mass fractions can be
found via tie lines and lever rule.
c: -phase solid solution only.
Net result: polycrystalline solid.
Cooling at this composition is similar to
binary isomorphous systems.
Partial Pb-Sn phase diagram

23
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2. One-component rich but cooling to +
coexistence.
d: homogeneous liquid.
e: + L phase (same as previous but at
different compositions and mass fractions).
f: all -phase solid solution.
g: + phase (passing through solvus line
leads to exceeding solubility limit and phase
precipitates out).
Net result: polycrystalline -solid with fine
crystals.
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12
3. Cooling through eutectic point.

h: homogeneous liquid.
i: solidification via eutectic reaction
cool
L(CE)
(CE) + (CE)
heat
note: and phases have very
different compositions than the
original composition of the liquid (e.g.
C = 18.3 wt% Sn; C = 97.8 wt% Sn
whereas CL = 61.9 wt% Sn).
Eutectic Structure: layered (lamellar)

structure.
Why does this structure form?
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Eutectic Structure
Pb-Sn Eutectic
microstructure
i
t t
Sn
Pb rich
Sn rich
In order to achieve large

homogeneous regions, long
diffusion lengths are required.
Pb
Lamellar structure forms

because relatively short
diffusion lengths are required.
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13

Hypoeutectic
4. Cooling through eutectic

isotherm.
j: homogeneous liquid.
k: + L phases: use tie lines
and lever rule.
l: just above eutectic isotherm
compositions given but what
about mass fraction?
m: remaining liquid transforms
to eutectic structure upon
crossing eutectic isotherm.
Microconstituent: an element
of a microstructure with
identifiable and characteristic
structure (at pt. m there are 2
microconstituents: primary
27
and eutectic structures)
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Just above the eutectic isotherm

at C4:
WL =
Primary structure:
W ' =
Q
P+Q
Total (primary + eutectic):
W =
Q+R
P+Q+ R
P
P+Q
All of this
amount will
turn into
eutectic
structure (We).
Total (all in eutectic):
W =
P
P+Q+ R
Note: this is for equilibrium cooling.

Non-equilibrium cooling will lead to: Cored primary phases & Increased fraction
of eutectic microconstituent
28
MSE280
14
T(C)
L
3 00
Adapted from Fig. 9.7,

Callister 6e. (Fig. 9.7
adapted from Binary Phase
Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-inChief), ASM International,
Materials Park, OH, 1990.)
2 00
TE
L+
L+
+
1 00
Co
hypoeutectic
0
20
40
hypoeutectic: C
o =50wt%Sn
Co
hypereutectic
60
80
eutectic
18.3
(Figs. 9.12 and 9.15

from Metals
Handbook, 9th ed.,
Vol. 9,
Metallography and
Microstructures,
American Society for
Metals, Materials
Park, OH, 1985.)
(Pb-Sn
System)
61.9
hypereutectic: (illustration only)
Adapted from
Fig. 9.15, Callister 6e.eutectic
C o , wt% Sn
eutectic: C o =61.9wt%Sn

175 m
100
97.8
160 m
micro-constituent

Callister 6e. (Illustration only)

Callister 6e.
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Congruent phase transformation

Congruent transformation: no change in composition upon phase
transformation.
Incongruent transformation: phase transformation where at least one of the
phases go through composition change.
At what overall
composition
iti d
does M
Mg2Pb
melt congruently?
30
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15
Intermetallic compounds
Intermediate (intermetallic) compounds: discrete metal compounds rather
than solutions (i.e. distinct chemical formula).
AxBy: in solution x and y can vary
in compounds x and y are fixed (always fixed composition of A and B)
B).
Mg-Pb phase diagram
Can be considered as two

phase diagrams put
together back to back.
Mg-Mg2Pb phase diagram
Mg2Pb-Pb phase diagram

31
MSE280
Intermetallic compounds: Example

Within the + Mg
g2Pb
coexistence region,
each of the two phases
is found to have 50%
mass fraction. If the
overall composition is
50wt%Pb, determine
the composition of each
of the phases and
temperature.
32
MSE280
16
Intermediate phases
Intermediate solid solutions (intermediate phases): Solid solutions that do
not extend to pure components in the phase diagram.
Cu-Zn
Terminal solutions:
and .
Intermediate solutions:
, , and .
Tie lines and lever rule can
be used to determine
compositions and wt% of
phases.
e.g. at 800oC with 70 wt%
Zn
CL = 78 wt% Zn
C = 67 wt% Zn
33
MSE280
Eutectoid and peritectic reactions
Eutectoid reaction: one solid phase turning into two other solid phases upon cooling
e.g.
cool
heat
Peritectic reaction: one solid phase transforms into liquid and a different solid
phases upon heating
cool
e.g. + L
heat
34
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17
Ceramic phase diagrams

Al2O3-Cr2O3
MgO-Al2O3
35
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Gibbs Phase Rule

Number of non-compositional
variables (Temperature &
P
Pressure)
)
Number of phases
present
P+F=C+N
Degree of freedom (externally
controllable parameters: i.e. T,
P, and C)
Number of
components
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18
Gibbs Phase Rule

P+F=C+N
e.g. Cu-Ag phase diagram

Cu and Ag are the only components ->
C=2
Temperature is the only noncompositional variable here (i.e. fixed
pressure). -> N = 1 (but in general N =
2)
When 2 phases are present -> P = 2
which leads to F = C+N-P
C+N P = 2+1-2
2+1 2 = 1
When only 1 phase is present -> P = 1
which leads to F = 2
What does this mean? Why should
you care?
37
MSE280
Gibbs Phase Rule

In the previous example of Cu-Ag phase diagram, when F = 1, only one
parameter (T or C) needs to be specified to completely define the system.
e.g. (for +L region)

If T is specified to be 1000oC,
compositions are already
determined (C and CL).
Or
If composition of the a phase is
specified to be C then both T and
CL are already determined.
C
CL
38
MSE280
19
Gibbs Phase Rule

When F = 2, both T and C have to be specified to completely define
the state of the system.
e.g.(for
(f region)
i )
If T is specified to be 800oC, C can
be any where between 0 to ~8 wt%
Ag)
Or
If composition of the a phase is
specified to be C = 3 wt%, then T
and can be any where between
~600 to 1100oC.
C
39
MSE280
Gibbs Phase Rule

Where in the CuAg diagram, is there a 0 degree of
freedom? (i.e. T, P, and C are all fixed)
40
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20
Iron-Carbon System
Typical metal (e.g. Cu)
T
Liquid
Tm
Iron
T(oC)
Liquid
1538
-Fe(BCC)
1394
-Fe (FCC)
Solid
912
-Fe (BCC)
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Iron-Carbon System
Eutectic point
Eutectoid
Note: only goes out to 6.7

wt% C (100 wt% Fe3C
intermediate compound)
FCC -phase has highest C concentration (2.14 wt% C) whereas BCC phase has low solubility (0.022 wt% C). Recall FCC is close packed (i.e.
larger APF). Why is C more soluble in FCC?
42
MSE280
21
Eutectoid cooling
cool
(0.76 wt% C)
heat
(0.022 wt% C)
+ Fe3C (6.7 wt% C)
Pearlite structure
Layered structure forms due to the same reason as eutectic structure formation.
43
MSE280
Hypoeutectoid Alloys
Cooling below eutectoid
composition.
c: homogeneous solid.
d: + coexistence. -phase nucleate
at the grain boundaries (Why?).
e -> f:
- crossing eutectoid isotherm will cause all
remaining -phase into eutectoid structure.
- -phase that formed prior to eutectoid isotherm
are called proeutectoid ferrite.
Fraction of pearlite = W p =
Co 0.022
0.76 0.022
Fraction of proeutectoid = W ' =
0.76 Co
0.76 0.022
44
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22
Hypereutectoid Alloys
Cooling above the
eutectoid composition
Compositions and wt% can be
f
found
d similarly
i il l as h
hypoeutectoid
t t id
cooling.
Instead of proeutectoid ,
proeutectoid cementite appears.
45
MSE280
Example problem
For 0.35 wt% C, at T just
below eutectoid
isotherm determine:
isotherm,
a) Fractions of total ferrite
and cementite phases.
b) Fractions of proeutectoid
ferrite and pearlite.
c) Fraction of eutectoid
ferrite.
46
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23
Influence of other alloying elements

Changes eutectoid T
Changes eutectoid
composition
Useful processing info to control microstructure.
47
MSE280
Concepts to remember
Phases, physical states, chemical composition, phase
equilibrium.
Phase diagrams tell us about:
Number
N b and
d ttypes off phases
h
present.
t
Composition of each phase.
Mass fraction (wt%) of each phase.
Binary isomorphous systems.

Binary eutectic systems.
Intermediate compounds.
phases.
Intermediate p
Fe-C phase diagram.
Microstructure evolution.
Phase diagrams help us to determine the equilibrium
microstructures which in turn determines the
properties of materials!
48
MSE280
24

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Phase Diagrams

Reading: Callister Ch. 10

2007, 2008 Moonsub Shim, University of Illinois

2007, 2008 Moonsub Shim, University of Illinois

e.g. sugar water

Question: What is the solubility limit at 20C?

2007, 2008 Moonsub Shim, University of Illinois

Plain carbon steel

2007, 2008 Moonsub Shim, University of Illinois

Temperature and composition

A: 2 phases present (liquid solution and solid sugar)

2007, 2008 Moonsub Shim, University of Illinois

2007, 2008 Moonsub Shim, University of Illinois

(at standard P = 1 atm)

Binary Isomorphous Systems

Complete liquid and solid solubility

Expect Tm of solution to lie in between Tm of two pure components

Binary Isomorphous Systems

2007, 2008 Moonsub Shim, University of Illinois

Determining phase composition

2007, 2008 Moonsub Shim, University of Illinois

Lever Rule: Derivation

Conservation of mass requires that:

Solving for WL and W gives :

2007, 2008 Moonsub Shim, University of Illinois

Lever Rule: Derivation

2007, 2008 Moonsub Shim, University of Illinois

Microstructures in Isomorphous Alloys

b (T ~ 1260oC): liquidus line

d (T~ 1220oC): solidus line reached.

e (T<1220oC): homogeneous solid

2007, 2008 Moonsub Shim, University of Illinois

65 wt% Ni 35 wt% Cu alloy is heated to

2007, 2008 Moonsub Shim, University of Illinois

2007, 2008 Moonsub Shim, University of Illinois

homogeneous liquid solution.

b (T ~ 1260oC): liquidus line

c (T= 1250oC): solids that formed at pt b

d (T~ 1220oC): solidus line reached.

2007, 2008 Moonsub Shim, University of Illinois

Cored vs. Equilibrium phases

Fast rate of cooling:

Slow rate of cooling:

2007, 2008 Moonsub Shim, University of Illinois

Binary Eutectic Systems

2007, 2008 Moonsub Shim, University of Illinois

Binary Eutectic System

2007, 2008 Moonsub Shim, University of Illinois

Cu-Ag phase diagram

Eutectic Isotherm: Horizontal solidus

2007, 2008 Moonsub Shim, University of Illinois

Eutectic System: Example

Microstructures in Eutectic Alloys

1. One component rich composition.

Partial Pb-Sn phase diagram

Microstructures in Eutectic Alloys

2007, 2008 Moonsub Shim, University of Illinois

Microstructures in Eutectic Alloys

3. Cooling through eutectic point.

Eutectic Structure: layered (lamellar)

2007, 2008 Moonsub Shim, University of Illinois

In order to achieve large

Lamellar structure forms