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10.phase Diagrams (Sudah Di Print
10.phase Diagrams (Sudah Di Print
α (darker
phase)
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© 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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Phases
2. Different chemical compositions
• 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., α and β).
β (lighter
Aluminum-
phase)
Copper
Alloy α (darker
phase) Plain carbon steel
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Temperature and composition
B C
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.
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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
© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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 (α) 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% α phase
B: % solid and % liquid?
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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 = Cα - Co
3. Mass fractions (wt%) of each
phase:
S C − Co 42.5 − 35
Liquid: WL = = α = = 0.68
R + S Cα − C L 42.5 − 31.5
R C − CL 35 − 31.5
Solid: Wα = = o = = 0.32
R + S Cα − C L 42.5 − 31.5
i.e. 68% of the mass is liquid and 32% of the mass is solid. 11
© 2007, 2008 Moonsub Shim, University of Illinois MSE280
WL + Wα = 1 (1)
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Lever Rule: Derivation
• A geometric interpretation:
CL Co Cα moment equilibrium:
R S WLR = WαS
WL Wα
1 − Wα
solving gives Lever Rule
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Example problem
• 65 wt% Ni – 35 wt% Cu alloy is heated to
T within the α+L
ithi th L region.
i If α-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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
Non-equilibrium cooling
Fast cooling, but how fast?
Fast w
w.r.t.
r t diffusion
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Non-equilibrium cooling
a’ (T>1260oC): start as
homogeneous liquid solution.
b’ (T ~ 1260oC): liquidus line
reached. α p
phase begins
g to nucleate.
Cα = 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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Binary Eutectic Systems
“easily melted”
Cu-Ag phase diagram
Single phase regions:
α-phase (solid solution rich in Cu).
β-phase (solid solution rich in Ag).
L-phase (liquid solution).
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
Cα = 3wt% Ag Cβ = 97wt% Ag
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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) α(CαE) + β(CβE)
heat
similar to one component (pure) system
except
p 2 solid p
phases.
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Microstructures in Eutectic Alloys
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Microstructures in Eutectic Alloys
Eutectic Structure
Pb-Sn Eutectic
microstructure
i t t
Sn
In order to achieve large
α Pb rich homogeneous regions, long
L diffusion lengths are required.
β Sn rich
Pb
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Microstructures in Eutectic Alloys
Hypoeutectic 4. Cooling through eutectic
isotherm.
j: homogeneous liquid.
k: α + 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 α
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and eutectic structures)
© 2007, 2008 Moonsub Shim, University of Illinois MSE280
Wα ' =
Q Q+R P
Wα = Wβ =
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
© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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T(°C)
3 00 L
At what overall
composition
iti d
does MMg2Pb
melt congruently?
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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: α
and η.
Intermediate solutions:
β, γ, δ and ε.
Eutectoid reaction: one solid phase turning into two other solid phases upon cooling
cool
e.g. δ γ+ε
heat
Peritectic reaction: one solid phase transforms into liquid and a different solid
phases upon heating cool
e.g. δ + L ε 34
heat
© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Ceramic phase diagrams
Al2O3-Cr2O3 MgO-Al2O3
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
P+F=C+N
Degree of freedom (externally
controllable parameters: i.e. T, Number of
P, and C) components
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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
Or
Cα CL 38
© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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 α region)
e.g.(for i )
If T is specified to be 800oC, Cα can
be any where between 0 to ~8 wt%
Ag)
Or
Cα
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Iron-Carbon System
Typical metal (e.g. Cu) Iron
T T(oC)
Liquid
Liquid
1538
α-Fe(BCC)
Tm 1394
γ-Fe (FCC)
Solid 912
α-Fe (BCC)
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
Iron-Carbon System
Eutectic point
Eutectoid
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Eutectoid cooling
cool
γ (0.76 wt% C) α (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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
Hypoeutectoid Alloys
Cooling below eutectoid
composition.
c: homogeneous γ solid.
e -> f:
- crossing eutectoid isotherm will cause all
remaining γ-phase into eutectoid structure.
- α-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 α = Wα ' =
0.76 − 0.022
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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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 α,
proeutectoid cementite appears.
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
Example problem
For 0.35 wt% C, at T just
below eutectoid
isotherm determine:
isotherm,
b) Fractions of proeutectoid
ferrite and pearlite.
c) Fraction of eutectoid
ferrite.
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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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Influence of other alloying elements
Changes eutectoid T
Changes eutectoid
composition
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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© 2007, 2008 Moonsub Shim, University of Illinois MSE280
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