ch3. Alloy and Phase Diagram

19/10/2022
HANOI UNIVERSITY OF TECHNOLOGY Solid solution and intermediate phase

ONE LOVE. ONE FUTURE HUST – MSE
Some concepts
Alloy:  A material made from multiple elements that exhibits properties of
a metallic material
Components:  The elements or compounds that are mixed initially (Al,
Cu, Fe3C,….)
β (lighter
Phases:  A phase phase)
maybe defined as a
homogeneous portion of
 (darker
a system that has
phase)
uniform physical and
CHAPTER 3. ALLOY AND PHASE DIAGRAM chemical characteristics
MSE2228 ( and )
Microstructure of Aluminum - Copper alloy

SCHOOL OF MATERIALS SCIENCE & ENGINEERING mse.hust.edu.vn fb.com/mse.hust.5 (fb.com/MSE.EDU) SCHOOL OF MATERIALS SCIENCE & ENGINEERING mse.hust.edu.vn fb.com/mse.hust.5 (fb.com/MSE.EDU)
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Solid solution and intermediate phase Solid solution and intermediate phase
HUST – MSE HUST – MSE
Some concepts (continu…..) Effect of T & Composition (Co)

Single-phase alloy:  An alloy consisting of one phase only
Changing T can change # of phases: path A to B
Multiple-phase alloy:  An alloy that consists of two or more phases
Changing Co can change # of phases: path B to D
Phase Equilibria:  Equilibrium is a
Solubility Limit:
thermodynamic terms describes a
situation in which the characteristics of  Maximum concentration
the system do not change with time but
for which only a single
persist indefinitely; that is, the system is
phase solution exists
stable
A system is at equilibrium if its free Question: What is the

energy is at a minimum under some
solubility limit for sugar in
specified combination of temperature,
pressure, and composition water at 20oC ?
Water sugar system
3 4
The Gibbs Phase Rule The type of interaction available in alloys

 This rule represents a criterion for the number of degree of freedom within 1. Alloying elements + metallic material  solid solution (A solution that
a system at equilibrium contains two or more types of atoms or ions that are dispersed uniformly
throughout the material)
There are 2 types of solid solutions
C – # of components
1. Substitutional solid solution
N – # of variable 2. Interstitial solid solution
thermodynamic parameter Note:
Pmax – maximum # of - Solid solution has the same crystal structure with solvent (metallic
phase(s) material)
F=C–P+2 - Properties of solid solutions (hardness, tensile strength, wear resistance
F=C–P+1 are higher pure metals.
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Substitutional solid solution Conditions for Complete Solubility of substitutional
Hume-Rothery rules
• Size factor – The atoms or ions must be of similar size, with no more
than a 8% difference in atomic radius, in order to minimize the lattice
strain.
• Crystal structure – The materials must have the same crystal

structure.
• Valence – The ions must have the same valence.

If the atoms of the solvent metal and solute element are of similar sizes
(not more, than 15% difference), they form substitution solid solution, • Electronegativity – The atoms must have approximately the same
electronegativity
where part of the solvent atoms are substituted by atoms of the alloying
element • For example: Cu - Ni
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Interstitial solid solution The type of interaction available in alloys
2. Alloying elements + metallic material  intermediate phase
Fe + C  Fe3C
Note:
- Intermediate phase has the different crystal structure with solvent (metallic
material)
- Melting temperature defined

If the atoms of the alloying elements are considerably smaller, than the
- Chemical formula defined
atoms of the matrix metal, interstitial solid solution forms, where the matrix
- Properties of intermediate phase are quite different with staring
solute atoms are located in the spaces between large solvent atoms
components
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Introduction to phase diagram Introduction to phase diagram

Three component:
 The diagram indicate phases as a function of T, C, and P Ternary phase diagram
Single component system: Liquid

Unary Systems
Melting
point Liquid
Melting
point (B)
Liquid Solid
Melting Melting Melting

point point (A) C point
Melting
point
Solid
A Wt%B B Solid
Dual component system:
Binary diagram Systems n component system:
A B
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Binary phase diagram I. Full solubility (contin…)

I. Full solubility  Three parameters are available
 There are three different
regions: 1. Phase presents: just locate
1. Liquid (single phase) the Temperature-
2. Liquid + solid (double phase) Composition point and
3. Solid solution (single phase)
determine the phase(s)
* Liquidus- the boundary line

2. Phase composition.
between the liquid region and the
double phase region.
* Solidus- the boundary line 3. Phase amount (in the double
between the solid solution region phase region) – The Lever rule
and the double phase region
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The Lever Rule At the point B

 Tie line – connects the phases in equilibrium with each other - essentially an Phase amount
isotherm
Amount of the liquid phase is:
• How much of each phase?
• Think of it as a lever (teeter-totter)
Amount of the Solid phase is:
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Work with phase diagram Work with phase diagram

Rule 1: If we know T and Co, then we know: Rule 2: If we know T and C0, then we can determine:
 the composition of each phase.
 which phase(s) is (are) present.
Examples:
Consider C0 = 35 wt% Ni
Examples:
At TA = 1320oC :
A (1100oC, 60 wt%Ni): Only Liquid (L) present
CL = C0 ( = 35 wt%Ni)
1 phase: α
At TD = 1190oC :
B (1250oC, 35 wt%Ni): Only Solid (α) present
2 phases: L + α Cα = C0 ( = 35 wt%Ni)
At TB = 1250oC :
Both α and L present
CL = Cliquidus ( = 32 wt%Ni); Cα = Csolidus ( = 43 wt%Ni)
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Work with phase diagram Microstructures: will vary on the cooling

Rule 3: If we know T and C0, then can determine: rate (i.e. processing conditions)
1. Equilibrium Cooling: Very slow cooling to
 the weight fraction of each phase allow phase equilibrium to be maintained
Examples: during the cooling process
a (T>1260oC): start as homogeneous liquid
Consider C0 = 35 wt% Ni
solution
At TA : Only Liquid (L) present b (T ~ 1260oC): liquidus line reached. α
W L = 1.00, W α = 0 phase begins to nucleate. Cα = 46
At TD : Only Solid (α) present wt%Ni; CL = 35 wt%Ni
W L = 0, W α = 1.00 c (T= 1250oC): calculate composition
and mass fraction of each phase.
At TB : Both α and L present Cα = 43 wt% Ni; CL = 32 wt% Ni
d (T~ 1220oC): solidus line reached.
Nearly complete solidification.
Cα = 35 wt%Ni; CL = 24 wt%Ni
e (T<1220oC): homogeneous solid
solution with 35 wt%Ni
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Microstructures: will vary on the cooling Cored vs Equilibrium Phases

rate (i.e. processing conditions)
Cα changes as we solidify
2. Non-equilibrium cooling: Very fast
cooling to allow phase non equilibrium Cu-Ni case: First α to solidify has Cα = 46 wt% Ni
a’ (T>1260oC): start as homogeneous liquid Last α to solidify has Cα = 35 wt% Ni
solution
Fast rate of cooling: Slow rate of cooling:
b’ (T ~ 1260oC): liquidus line reached. α Cored structure Equilibrium structure
phase begins to nucleate.
Cα = 46 wt%Ni; CL = 35 wt%Ni
c’ (T= 1250oC): solids that formed at point
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
e (T<1220oC): Non-equilibrium solidification Cored structure can be eliminated by a homogenization heat treatment at a
complete (with phase segregation) temperature below the solidus point for the particular alloy composition
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II. Partially solubility (eutectic diagram)

Microstructure
has a special composition with a min. melting T
* 3 single phase regions
* In metal alloys, microstructure is characterized by the number of (L, α, β)
phases, their proportions, and the way they are arranged * Limited solubility: TA
TB
α: mostly A
β: mostly B
* The microstructure depends on:
* TE: No liquid below TE TE
– Alloying elements
* CE: Composition at
– Concentration
………………..temperature TE
– Heat treatment (temperature, time, rate of cooling) CE
* Eutectic reaction:
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II. Partially solubility (conti…)

II. Partially solubility (conti…)
Microstructural Developments in
Eutectic Systems I
For examples:
Co < 2 wt% Sn
• Cu-Ag system
One component rich composition.
a: start with homogeneous liquid.
b: α-phase solids with liquid.
Compositions and mass fractions
can be found via tie lines and lever rule.
c: α-phase solid solution only.
• Pb-Sn system Net result: polycrystalline α solid.
 Cooling at this composition is similar
to binary isomorphous systems (Room T solubility limit)
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II. Partially solubility (conti…) II. Partially solubility (conti…)

Microstructural Developments in Microstructural Developments in Eutectic Systems III * Co = C E
Eutectic Systems II  Result: Eutectic
2 wt% Sn < Co < 18.3 wt% Sn microstructure (lamellar
structure)
One-component rich but cooling to α +
 coexistence. - alternating layers
d: homogeneous liquid. (lamellae) of α and β
e: α + L phase (same as previous but at crystals
different compositions and mass fractions).
f: all α-phase solid solution.
g: α + β phase (passing through solvus
line leads to exceeding solubility limit and
β phase precipitates out).
Net result: polycrystalline α-solid with
18.3 Micrograph of Pb-Sn
fine β crystals (sol. limit at Troom) (sol. limit at TE) Eutectic microstructure Pb-Sn System
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Lamellar Eutectic Structure II. Partially solubility (conti…)

18.3 wt% Sn < Co < 61.9 wt% Sn
Microstructural Developments
 A 2-phase microstructure resulting
in Eutectic Systems IV
from the solidification of a liquid
Result: α crystals and a
having the eutectic composition eutectic microstructure
where the phases exist as a lamellae
that alternate with one another.
 Formation of eutectic layered

microstructure in the Pb-Sn system
during solidification at the eutectic
composition. Compositions of α and β
phases are very different. Solidification
involves redistribution of Pb and Sn
The dark layers are Pb-rich α phase, the
atoms by atomic diffusion light layers are the Snrich β phase Pb-Sn System
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II. Partially solubility (conti…) Calculating amounts

Amount of eutectic
structure
Amount of primary α
Amount of total α phase
Composition (wt% Sn)
Difference of hypoeutectic and hypereutectic microstructures

Amount of total β phase (eutectic)
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Intermediate Phases (Intermediate Solid Solutions)
Note: intermetallic compound exists as a line on the diagram - not an area - because of
stoichiometry (i.e. composition of a compound is a fixed value).
33 34

Eutectic, Eutectoid, & Peritectic Eutectic, Eutectoid, & Peritectic
 Eutectic - liquid transforms to two solid phases
Liquid Solid 1 + Solid 2  Eutectic reaction
 Eutectoid – one solid phase transforms to two other solid phases
Solid 1 Solid 2 + Solid 3  Eutectoid reaction
 Peritectic - liquid and one solid phase transform to a second solid phase
Solid 1 + Liquid Solid 2  Peritectic reaction
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Introduction to phase diagram Phase diagram Fe-Fe3C

Eutectoid, & Peritectic Iron-Carbon System

Pure iron when heated
experiences to changes in crystal
structure before it melts.
 At room temperature the stable
form, ferrite ( iron) has a BCC
crystal structure.
 Ferrite experiences a
polymorphic transformation to
FCC austenite ( iron) at 912˚C.
 At 1394˚C austenite reverts
back to BCC phase  ferrite
Cu Zn and melts at 1538˚C.
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Phase diagram Fe-Fe3C Phase diagram Fe-Fe3C

Iron-Carbon System
Iron-
Carbon
 Iron carbide (cementite or Fe3C) an intermediate compound is System
formed at 6.67 wt%C.
 Typically, all steels and cast irons have carbon contents less
than 6.67 wt%C.
 Carbon is an interstitial impurity in iron and forms a solid
solution with the phases
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Solid Phases in Iron-Carbon System Iron-Carbon System

 Ferrite  2 important points
- Solid solution of carbon in a -iron
- BCC structure
- Carbon only in slightly soluble in the matrix
Maximum solubility of 0.02%C at 723oC to about 0.008%C at room temperature
 Austenite 1147
- Solid solution of carbon in -iron
- FCC structure: can accommodate more carbon than ferrite
Maximum of 2.14%C at 1147oC, decrease to 0.8%C at 723oC
 Ferrite
- Solid solution of carbon in -iron
- BCC crystal structure
Maximum solubility of ferrite being 0.09%C at 1495oC
 Cementite (Fe3C)
0.8
- Intermetallic Fe-C compound
- Fe3C: 6.67%C and 93.3%Fe Result: Pearlite = alternating
layers of  and Fe3C phases,
Fe3C (Cementite – Hard)
Orthorhombic crystal structure: hard and brittle
not a separate phase  (Ferrite – Soft)
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Microstructure of Hypoeutectoid
steels
 Classify Fe-C
alloys
1147o
- Steel
1147
- Cast iron
727
0.8
2.14
0.8
Pearlite Ferrite
43 44

Microstructure of Hypereutectoid steels
1147o
0.
8
Pearlit
e Cementite
45 46
Phase diagram Fe-Fe3C

HUST – MSE
Microstructure of white cast iron
b
a - hypoeutectic white cast iron
b - eutectic white cast iron
c c – hypereutectic white cast iron
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19/10/2022

HANOI UNIVERSITY OF TECHNOLOGY Solid solution and intermediate phase

Microstructure of Aluminum - Copper alloy

Some concepts (continu…..) Effect of T & Composition (Co)

A system is at equilibrium if its free Question: What is the

The Gibbs Phase Rule The type of interaction available in alloys

Substitutional solid solution Conditions for Complete Solubility of substitutional

• Crystal structure – The materials must have the same crystal

• Valence – The ions must have the same valence.

Interstitial solid solution The type of interaction available in alloys

2. Alloying elements + metallic material  intermediate phase

- Melting temperature defined

Introduction to phase diagram Introduction to phase diagram

Single component system: Liquid

Melting Melting Melting

Introduction to phase diagram Introduction to phase diagram

Binary phase diagram I. Full solubility (contin…)

* Liquidus- the boundary line

Introduction to phase diagram Introduction to phase diagram

The Lever Rule At the point B

Amount of the Solid phase is:

Introduction to phase diagram Introduction to phase diagram

Work with phase diagram Work with phase diagram

Introduction to phase diagram Introduction to phase diagram

Work with phase diagram Microstructures: will vary on the cooling

Introduction to phase diagram Introduction to phase diagram

Microstructures: will vary on the cooling Cored vs Equilibrium Phases

Introduction to phase diagram Introduction to phase diagram

II. Partially solubility (eutectic diagram)

Introduction to phase diagram Introduction to phase diagram

II. Partially solubility (conti…)

Introduction to phase diagram Introduction to phase diagram

II. Partially solubility (conti…) II. Partially solubility (conti…)

Introduction to phase diagram Introduction to phase diagram

Lamellar Eutectic Structure II. Partially solubility (conti…)

 Formation of eutectic layered

Introduction to phase diagram Introduction to phase diagram

II. Partially solubility (conti…) Calculating amounts

Amount of total α phase

Composition (wt% Sn)

Difference of hypoeutectic and hypereutectic microstructures

Introduction to phase diagram Introduction to phase diagram

Intermediate Phases (Intermediate Solid Solutions)

Introduction to phase diagram Introduction to phase diagram

Eutectic, Eutectoid, & Peritectic Eutectic, Eutectoid, & Peritectic

 Eutectic - liquid transforms to two solid phases

Liquid Solid 1 + Solid 2  Eutectic reaction

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

Solid 1 Solid 2 + Solid 3  Eutectoid reaction

Solid 1 + Liquid Solid 2  Peritectic reaction

Introduction to phase diagram Phase diagram Fe-Fe3C

Eutectoid, & Peritectic Iron-Carbon System

Phase diagram Fe-Fe3C Phase diagram Fe-Fe3C

formed at 6.67 wt%C.

than 6.67 wt%C.

 Carbon is an interstitial impurity in iron and forms a solid

solution with the phases

Phase diagram Fe-Fe3C Phase diagram Fe-Fe3C

Solid Phases in Iron-Carbon System Iron-Carbon System

Phase diagram Fe-Fe3C Phase diagram Fe-Fe3C

Phase diagram Fe-Fe3C Phase diagram Fe-Fe3C

Microstructure of Hypereutectoid steels