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Chapter 10.

Phase Diagrams

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The Solubility of Sugar

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EFFECT OF T & COMPOSITION

• Changing T can change # of phases: path A to B.


• Changing Co can change # of phases: path B to D.
B(70,97) D(90,97)
1 phase 2 phases
100
L
Temperature (°C)

• water- 80
(liquid)
sugar
60 +
system L S
(liquid solution (solid
40 i.e., syrup) sugar)
20 A(70,20)
2 phases
0
0 20 40 60 70 80 100
Co=Composition (wt% sugar)
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COMPONENTS AND PHASES

• Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions.

Aluminum- β (lighter
Copper
phase)
Alloy

α (darker
phase)

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3
Interpretation of Phase Diagrams

From the phase diagram, we know


1. The phases that are present.
2. The compositions of these phases.
3. The percentages of the phases.

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Cu-Ni Phase Diagram

• Tell us about phases as function


of T, Co, P.
• For this course:
--binary systems: just 2
components.
--independent variables: T and
Co (P = 1atm is always used).

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Complete Solid Solution: Isomorphous Alloys

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Interpretation of Phase Diagrams

• Phases present.

• Determination of phase
compositions.

• Determination of phase
amounts.

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Cu-Ni Phase Diagram

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The Lever Rule: A Proof
• Sum of weight fractions: WL + Wα = 1
• Conservation of mass (Ni): Co = WL CL + Wα Cα
• Combine above equations:
= Cα − Co = S Co − CL = R
WL Wα =
Cα − CL R + S Cα − CL R + S

• A geometric interpretation:
CL Co Cα moment equilibrium:
R S WLR = WαS
WL Wα
1− Wα
solving gives Lever Rule
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Concept Check 10.2

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Development of Microstructure during Equilibrium Solidification
• Phase diagram:
Cu-Ni system.

• System is:
--binary
i.e., 2 components:
Cu and Ni.
--isomorphous
i.e., complete solubility of
one component in
another; a phase field
extends from 0 to 100wt%
Ni.

Overall alloy composition


remains unchanged during
cooling even though there is a
redistribution of Cu and Ni
between the phases.

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Development of Microstructure during Nonequilibrium Solidification

• Diffusion
• Cooling Rate
• Segregation
• Cored Structure

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CORED VS EQUILIBRIUM PHASES

• Cα changes as we solidify.
• Cu-Ni case: First a to solidify has Cα = 46wt%Ni.
Last a to solidify has Cα = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform Cα:
First α to solidfy:
46wt%Ni 35wt%Ni
Last α to solidfy:
< 35wt%Ni

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Mechanical Properties of Isomorphous Alloys

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Solid-Solution Strengthening

Fig. 8.17

Fig. 8.18

Dislocation movement is restricted.


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BINARY-EUTECTIC SYSTEMS
Low melting point
2 components

Ex.: Cu-Ag system


• 3 single phase regions
(L, α, β)
• Limited solubility:
α: mostly Cu
β: mostly Ag
• T E: No liquid below T E
• CE: Min. melting T
composition
Limited solubility

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Cu-Ag Phase Diagram

Invariant Point
(Eutectic Point)

Eutectic Isotherm
(parallel to the composition axis,
Extends between the maximum solubility positions)

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Eutectic Reaction

L(CE) α(CαE) + β(CβE)

• The eutectic reaction, upon cooling, proceeds to completion at a


constant temperature, or isothermally, at TE (similar to solidification
for pure material).

• Along the eutectic isotherm, three phases (α,β, and L) are in


equilibrium.

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Lead-Tin Eutectic System

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H2O-NaCl Phase Diagram

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Microstructure in Eutectic Alloys

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Microstructure in Eutectic Alloys

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Microstructure in Eutectic Alloys

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Microstructure in Eutectic Alloys

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Microstructure in Eutectic Alloys

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Microstructure in Eutectic Alloys

Lead-Tin alloy with composition of 50wt% Sn

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Relative Amount of Each Phase
Fraction of eutectic microconstituent We
Fraction of eutectic liquid WL
Fraction of primary α, Wα’
Fraction of total α, Wα
Fraction of total β, Wβ

We = WL = P/(P+Q)
Wα’ = Q/(P+Q)
Wα = Q+R/(P+Q+R)
Wβ = P/(P+Q+R)

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Intermediate Phases

Intermediate
Phases

Terminal
Phase
Terminal
Phase

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The magnesium-Lead Phase Diagram

Intermetallic
Compound

Two eutectic systems joined back to back


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Eutectoid Reaction
cooling
δ heating
γ+ε
• The eutectoid reaction, upon cooling, proceeds to completion at a
constant temperature.

• Along the eutectoid isotherm, three phases (δ,γ, and ε) are in


equilibrium.

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Peritectic Reaction

δ+L ε
cooling
heating
• The peritectic reaction, upon heating, proceeds to completion at a
constant temperature.

• Along the peritectic isotherm, three phases (δ,L, and ε) are in


equilibrium.

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Congruent and Incongruent Transformations

Congruent melting point

Congruent transformation: no compositional alterations


Example: melting of pure metals
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Concept Check 10.6

β+L

HfV2 + L

Two eutectics, one eutectoid, one congruent melting


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Al3+ and Cr3+ have the same charge and similar radii.

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There are two eutectics.
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One eutectic and two eutectoid reactions.
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Ternary Phase Diagrams

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The Gibbs Phase Rule

P+F=C+N
P: The number of phases

F: The number of degree of freedom


or
The number of externally controllable variables (T, P,
composition)

C: The number of components

N: The number of available noncompositional variables (T and P)

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The Gibbs Phase Rule (example)
P+F=C+N

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The Iron-Iron Carbide Phase Diagram

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Classification of Ferrous Alloys

Iron
(0-0.008 wt% C) Steel
(0.008-2.14 Cast Iron
wt% C) (2.14-6.70 wt% C)

Hypoeutectoid steel Hypereutectoid steel


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Pearlite

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Hypoeutectoid Alloy

0.38 wt% C steel

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Hypereutectoid Alloy

1.4 wt% C steel

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The Influence of Other Alloying Elements

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