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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)

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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 Question: What is the solubility limit at 20C?
limit = 80wt% sugar. Answer: 65wt% sugar.
If Co < 65wt% sugar: syrup
If Co > 65wt% sugar: syrup + sugar. 3
2007, 2008 Moonsub Shim, University of Illinois MSE280

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 ).
(lighter
Aluminum-
phase)
Copper
Alloy (darker
phase) Plain carbon steel

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Temperature and composition

B C

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 T

liquid

liquid 1453oC

1085oC
solid
solid

Cu Ni
What happens when Cu and Ni are mixed? 7
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Binary Isomorphous Systems


2 components Complete liquid and solid solubility

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

T T
For a pure
liquid component,
complete melting
L occurs before T
liquid
1453oC increases (sharp
phase transition).
transition)
But for
1085oC multicomponent
solid systems, there is
S
solid usually a
coexistence of L
0 100 and S.
Ni 8
Cu wt% Ni
2007, 2008 Moonsub Shim, University of Illinois MSE280

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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
3. Amount of the
coexistence
phases.
region
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 2-
phase 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:
S C Co 42.5 35
Liquid: WL = = = = 0.68
R + S C C L 42.5 31.5
R C CL 35 31.5
Solid: W = = o = = 0.32
R + S C C L 42.5 31.5
i.e. 68% of the mass is liquid and 32% of the mass is solid. 11
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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: W = 1 WL


Sub-in to (2): (1 WL )C + WL C L = Co
Solving for WL and W gives :
C Co Co C L
WL = W =
C C L C C L 12
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Lever Rule: Derivation

A geometric interpretation:
CL Co C moment equilibrium:
R S WLR = WS
WL W
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 the +L
ithi th L region.
i If -phase
h
contains 70 wt% Ni, determine:
a. Temperature of the alloy.
b. Composition of the liquid phase.
c. Mass fraction of both p
phases.

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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
reached. p
phase begins
g to nucleate.
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 hhas C = 35wt%Ni.
35 t%Ni
Fast rate of cooling: Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C :
First to solidfy:
46wt%Ni 35wt%Ni
Last to solidfy:
< 35wt%Ni
35 t%Ni

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Binary Eutectic Systems
easily melted
Cu-Ag phase diagram
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

Tie line Calculate


B
composition and
mass fractions of
Tie line each phases at
A points A and B
B.

C = 3wt% Ag C = 97wt% Ag

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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.

Eutectic Isotherm: Horizontal solidus


line at T = TE.
Cu-Ag phase diagram

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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
Pb-Sn phase diagram be added to achieve the same
state (50% liquid)? 22
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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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Microstructures in Eutectic Alloys

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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Microstructures in Eutectic Alloys

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 Eutectic Structure: layered (lamellar)
original composition of the liquid (e.g. structure.
C = 18.3 wt% Sn; C = 97.8 wt% Sn Why does this structure form?
whereas CL = 61.9 wt% Sn).
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Eutectic Structure
Pb-Sn Eutectic
microstructure
i t t

Sn
In order to achieve large
Pb rich homogeneous regions, long
L diffusion lengths are required.
Sn rich
Pb

Lamellar structure forms


because relatively short
diffusion lengths are required. 26
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Microstructures in Eutectic Alloys
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
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and eutectic structures)
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Just above the eutectic isotherm


at C4:
P
WL = All of this
P+Q amount will
turn into
eutectic
structure (We).

Primary structure: Total (primary + eutectic): Total (all in eutectic):

W ' =
Q Q+R P
W = W =
P+Q P+Q+ R P+Q+ R
Note: this is for equilibrium cooling.
Non-equilibrium cooling will lead to: Cored primary phases & Increased fraction
of eutectic microconstituent 28
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T(C)
3 00 L

Adapted from Fig. 9.7, L+


Callister 6e. (Fig. 9.7 2 00 L+ (Pb-Sn
adapted from Binary Phase TE
Diagrams, 2nd ed., Vol. 3,
T.B. Massalski (Editor-in- + System)
Chief), ASM International, 1 00
Materials Park, OH, 1990.)
Co Co
hypoeutectic hypereutectic
0 C o , wt% Sn
0 20 40 60 80 100
18.3 eutectic 97.8
61.9
hypoeutectic: C o =50wt%Sn hypereutectic: (illustration only)
(Figs. 9.12 and 9.15
from Metals
eutectic: C o =61.9wt%Sn
Handbook, 9th ed.,
Vol. 9,

Metallography and
Microstructures,
American Society for
Metals, Materials

Park, OH, 1985.)
175 m 160 m
Adapted from Adapted from Fig. 9.15,
Fig. 9.15, Callister 6e.eutectic micro-constituent Callister 6e. (Illustration only)
Adapted from Fig. 9.12,
Callister 6e. 29
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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 MMg2Pb
melt congruently?

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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


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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.

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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
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Eutectoid and peritectic reactions

Eutectoid reaction: one solid phase turning into two other solid phases upon cooling
cool
e.g. +
heat
Peritectic reaction: one solid phase transforms into liquid and a different solid
phases upon heating cool
e.g. + L 34
heat
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Ceramic phase diagrams
Al2O3-Cr2O3 MgO-Al2O3

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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, Number of
P, and C) components

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Gibbs Phase Rule
e.g. Cu-Ag phase diagram
P+F=C+N
Cu and Ag are the only components ->
C=2

Temperature is the only non-


compositional 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?
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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
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Gibbs Phase Rule
When F = 2, both T and C have to be specified to completely define
the state of the system.

(f region)
e.g.(for 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
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Gibbs Phase Rule


Where in the CuAg diagram, is there a 0 degree of
freedom? (i.e. T, P, and C are all fixed)

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Iron-Carbon System
Typical metal (e.g. Cu) Iron
T T(oC)

Liquid
Liquid
1538
-Fe(BCC)
Tm 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
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Eutectoid cooling

cool
(0.76 wt% C) (0.022 wt% C)
heat + Fe3C (6.7 wt% C)

Pearlite structure

Layered structure forms due to the same reason as eutectic structure formation.
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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.

Co 0.022
Fraction of pearlite = W p =
0.76 0.022
0.76 Co
Fraction of proeutectoid = W ' =
0.76 0.022
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Hypereutectoid Alloys
Cooling above the
eutectoid composition
Compositions and wt% can be
f
foundd similarly
i il l as h
hypoeutectoid
t t id
cooling.

Instead of proeutectoid ,
proeutectoid cementite appears.

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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.

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Influence of other alloying elements

Changes eutectoid T

Changes eutectoid
composition

Useful processing info to control microstructure. 47


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