Fall 2024

Phase Diagrams

Outline
▪ Definitions and Basic Concepts
▪ Solubility Limit
▪ Phases
▪ Microstructure
▪ Phase Equilibria

▪ Binary Phase Diagrams

▪ Isomorphous Binary Phase Diagram
▪ Interpretation of Phase Diagrams
▪ Development of Microstructure in Isomorphous Alloys
▪ Mechanical Properties of Isomorphous Alloys
▪ Binary Eutectic Systems
▪ Development o Microstructure in Eutectic Alloys

▪ Iron-Carbon System
▪ Iron-Carbon Phase Diagram
▪ Development of Microstructure in Iron-Carbon Alloys
 Phase Diagrams

Definitions and Basic Concepts: Introduction

Why phase diagrams are important?

▪ There is a strong correlation between microstructure and mechanical

properties.

▪ Phase diagrams provide information about melting and crystallization.

▪ Topics discussed:
1. Terminology phase diagrams/phase transformations;
2. Pressure–temperature phase diagrams for pure materials;
3. Interpretation of phase diagrams;
4. Binary phase diagrams (iron–carbon system);
5. Development of equilibrium microstructures, upon cooling.
 Phase Diagrams

Definitions and Basic Concepts: Definitions

▪ Components/chemical constituent: pure metals and/or compounds

of which an alloy is composed (can be an atom (Au-Ni), more than
one atom SiO2- Al2O3).

▪ Solvent: element with the greatest amount and Solute is an

element or compound present in a minor concentration.

▪ System: specific body under consideration (at a specific

temperature) or series of possible alloys (iron-carbon system).

▪ Solid solution: consists of atoms of at least two different types.

▪ Solution: solid, liquid, or gas solutions, single phase and mixture –

more than one phase.
 Phase Diagrams

Definitions and Basic Concepts: Solubility Limit

Solubility Limit: Max concentration for which only a single phase solution occurs.

▪ Maximum concentration of solute

atoms that may dissolve in the Sucrose/Water Phase Diagram
solvent to form a solid solution;
100
▪ Solute in excess (beyond solubility Solubility
L

Temperature (°C)
limit) results in the formation of 80 Limit
another solid solution that has a (liquid)
distinctly different composition 60 L +
(liquid solution S
40
Question: What is the i.e., syrup) (solid
solubility limit at 20°C? 20 sugar)

Answer: 65 wt% sugar. 0 20 40 6065 80 100

Co =Composition (wt% sugar)
Water

If Co < 65 wt% sugar: syrup

Sugar
Pure
Pure

If Co > 65 wt% sugar: syrup + sugar.

 Phase Diagrams

Definitions and Basic Concepts: Phases

Phases: Homogeneous portion of a system with physically and
chemically distinct properties (e.g., α and β)

▪ Every pure material is considered to be

a phase including solid, liquid or gas.
▪ Has a different chemical composition Aluminum-Copper Alloy
(Syrup and Water both liquid)
▪ physical properties (water is liquid and
sugar is a solid)
▪ BCC or FCC can be used to differentiate
between phases

Separating boundaries: abrupt change in

physical/ chemical characteristics
 Phase Diagrams

Definitions and Basic Concepts: Phases

▪ Water and Ice = same chemical properties but

different physical properties.
Phase 2 = Ice

▪ A single-phase system is termed homogeneous.

▪ Systems composed of two or more phases are

termed mixtures or heterogeneous systems.

▪ Most metallic alloys are heterogeneous.

Phase 1 = Water
 Phase Diagrams

Definitions and Basic Concepts: Microstructure

Microstructure is characterized by:

• Number of phases present

• Distribution/ arrangements
• Alloying elements present
• Concentration of each element
• Heat treatment

Highly influence the Mechanical Properties

 Phase Diagrams

Definitions and Basic Concepts: Phase Equilibria

▪ Phase equilibrium is reflected by a constancy with time in the phase
characteristics of a system (Free Energy).
▪ In a macroscopic sense, the characteristics of the system do not
change with time; that is, the system is stable.
▪ A change in temperature, pressure, and/or composition for a
system in equilibrium will result in an increase in the free energy
and in a possible change to another state whereby the free energy is
lowered.
▪ When a state of equilibrium is never achieved due to slow rate of
approach this is Metastable/ non-equilibrium state (used to control
the development of microstructure).
▪ Speed or rate to achieve equilibrium is crucial.
 Phase Diagrams

Definitions and Basic Concepts

Effect of Temperature and Composition
▪ Altering T can change # of phases: path A to B.
▪ Altering C can change # of phases: path B to D.
 Phase Diagrams

Definitions and Basic Concepts: Phase Diagrams

▪ Information about the control of the phase structure is called a

phase diagram, or equilibrium diagram.
▪ Phase structure is affected by—temperature, pressure, and
composition.
▪ Simplest phase diagram is that for a one-component system (Unary
phase diagram), in which composition is held constant (pure
substance) and pressure and temperature are the variables.
▪ Unary phase diagrams are called a pressure–temperature (or P–T)
diagram.
 Phase Diagrams

Definitions and Basic Concepts: Phase Diagrams

Pressure-Temperature Phase Diagram for H2O

Solidification Melting
Condensation Vaporization
Cooling Heating

Triple Point
(Invariant Point)
Phase Boundaries
 Phase Diagrams

Binary Phase Diagrams

▪ Common phase diagram: temperature and composition are variable

parameters, and pressure is held constant (1 atm).
▪ More than two components are present, phase diagrams become
extremely complicated and difficult to represent – in this topic only
two components are considered.
▪ Binary phase diagrams are maps - relationships between
temperature and the compositions and quantities of phases at
equilibrium (influence the microstructure of an alloy).
▪ Many microstructures develop from phase transformations, the
changes that occur when the temperature is altered (ordinarily upon
cooling).
 Phase Diagrams

Binary Phase Diagrams

▪ Indicate phases as function of T, Co, and P.
▪ For this course:
▪ Binary systems: just 2 components.
▪ Independent variables: T and Co (P = 1 atm is almost always used).

Phase Diagram for Cu-Ni system

▪ 2 phases: L (Liquid)
α (FCC Solid Solution)

▪ 3 phase fields: L
L+a
a
 Phase Diagrams

Binary Phase Diagrams: Rule 1

▪ Rule 1: If we know T and Co, then we know: # and types of
phases present.
Examples: T(°C)
1600
L (liquid)
A(1100°C, 60): 1500

B (1250°C,35)
Cu-Ni
1 phase: a
1400 phase
diagram
1300 a
B (1250°C, 35):
2 phases: L + a (FCC solid
1200 solution)
1100 A(1100°C,60)

1000
0 20 40 60 80 100 wt% Ni
 Phase Diagrams

Binary Phase Diagrams: Rule 2

▪ Rule 2: If we know T and Co, then we know: the composition of
each phase.
Examples: Cu-Ni
C o = 35 wt% Ni T(°C) system
At T A = 1320°C: TA A
tie line
Only Liquid (L) 1300 L (liquid)
C L = Co ( = 35 wt% Ni)
B
At T D = 1190°C: TB
Only Solid ( a) a
C a = Co ( = 35 wt% Ni) 1200 D (solid)
TD
At T B = 1250°C:
20 3032 35 40 4 3 50
Both and L
a C LC o C a wt% Ni
C L = C liquidus ( = 32 wt% Ni here)
C a = C solidus ( = 43 wt% Ni here)
 Phase Diagrams

Binary Phase Diagrams: Rule 3

▪ Rule 3: If we know T and Co, then we know: the amount of each
phase (Given in wt%).
Examples: Cu-Ni
Co = 35 wt% Ni T(°C) system
At T A : Only Liquid (L) TA A
tie line
W L = 100 wt%, W a = 0 1300 L (liquid)
At T D: Only Solid ( a)
B
W L = 0, Wa = 100 wt% TB R S
a
At T B : Both a and L
1200 D (solid)
S 43 − 35 TD
WL = = = 73 wt %
R + S 43 − 32 20 3032 35 40 4 3 50
C LC o C a wt% Ni
R
Wa = = 27 wt%
R +S
 Phase Diagrams

Binary Phase Diagrams: The Lever Rule

▪ Tie line – connects the phases in equilibrium with each other -
essentially an isotherm
T(°C) How much of each phase?
tie line Think of it as a lever (teeter-totter)
1300 L (liquid)
ML Ma
B
TB
a
1200 (solid)
R S R S
20 30C C
L o
40 C
a
50
M a S = M L R
wt% Ni

ML S C − C0 R C − CL
WL = = = a Wa = = 0
M L + M a R + S C a − CL R + S C a − CL
 Phase Diagrams

Binary Phase Diagrams: The Lever Rule

▪ For an alloy consisting of α and β phases, the volume fraction
of the α phase, Vα, is defined as
T(°C)
tie line
1300 L (liquid)
B
TB
a
▪ Conversion from mass fraction to 1200 (solid)
volume fraction (or vice versa) R S

20 30C C 40 C 50
L o a
wt% Ni
 Phase Diagrams

Binary Phase Diagrams: Example

Phase Diagram of Cu-Ni System
T(°C) L (liquid) L: 35wt%Ni
▪ Equilibrium Cooling of a
Cu-Ni Alloy (Development Cu-Ni
of Microstructure in 130 0 system
A
Isomorphous Alloys) L: 35 wt% Ni
a: 46 wt% Ni B
35 46
▪ System is: 32 C 43
1. Binary i.e., 2 components: D
24 36 L: 32 wt% Ni
Cu and Ni.
a: 43 wt% Ni
2. Isomorphous i.e., complete 120 0 E
L: 24 wt% Ni
solubility of one component
in another; a phase field a: 36 wt% Ni
a
extends from 0 to 100 wt% (solid)
Ni.
110 0
Consider Co = 35 wt% Ni 20 30 35 40 50
Co wt% Ni
 Phase Diagrams

Binary Phase Diagrams: Mechanical Properties

▪ Effect of solid solution strengthening on (At room Temperature):
Tensile strength (TS) Ductility (%EL)

Peak as a function of Co Min. as a function of Co

 Phase Diagrams

Binary Phase Diagrams: Binary Eutectic Systems

Copper-Silver Phase Diagram
▪ Three single-phase regions exist (α, β and liquid).
▪ α phase solid solution rich in Cu (FCC), Ag is the Solute.
▪ β phase solid solution rich in Ag (FCC), Cu is the Solute.

▪ Solubility in each of these

solid (α, β) phases is limited.
▪ Limited concentration of Ag
will dissolve in Cu, and
similarly for Cu in Ag.
▪ The solid solubility limit line
separating the α and α+β
phase regions is termed a
Solvus Line;
 Phase Diagrams

Binary Phase Diagrams: Binary Eutectic Systems

Copper-Silver Phase Diagram
▪ The α+L and β+L phases also coexist in their respective phase regions.
▪ Silver reduces the temperature of complete melting along the other Liquidus
Line, AE. (Same for FE)

▪ The two Liquidus Lines meet

at point E.
▪ Line BEG extends between the
maximum solubility limits.
▪ BEG is considered as Solidus
Line.
▪ The Horizontal Solidus line
through E known as the
Eutectic Isotherm Line.
 Phase Diagrams

Binary Phase Diagrams: The Eutectic Reaction

T(°C)
Cu-Ag system
1200
• 3 single phase regions L (liquid)
(L, α, β) 1000
• Limited solubility: α L+α L+β β
800 779°C
α: mostly Cu TE 8.0 71.9 91.2
β: mostly Ag 600

• TE : No liquid below TE α+β

400
• CE : Composition at
200
temperature TE 0 20 40 60 CE 80 100
C, wt% Ag
• Eutectic reaction - “easily melted”
L(CE) α(CαE) + β(CβE)
cooling

heating
 Phase Diagrams

Binary Phase Diagrams: Pb-Sn Eutectic System (1)

▪ For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
1. The phases present: a + b
2. Compositions of phases:
T(°C) Lead-Tin (Pb-Sn) system
CO = 40 wt% Sn
Ca = 11 wt% Sn 300
Cb = 99 wt% Sn L (liquid)
Relative amount of each phase: a L+ a
200 183°C L+b b
S Cb - CO 18.3
Wa = = 61.9 97.8
R+S Cb - Ca 150
R S
=
99 - 40
=
59
= 67 wt%
100
a+b
99 - 1188
R CO - Ca
Wb = =
R+S Cb - Ca 0 11 20 40 60 80 99100
Ca Co Cb
40 - 11 29
= = = 33 wt% C, wt% Sn
99 - 11 88
 Phase Diagrams

Binary Phase Diagrams: Pb-Sn Eutectic System (2)

▪ For a 40 wt% Sn-60 wt% Pb alloy at 220°C, find...
1. The phases present: a + L
2. compositions of phases: Pb-Sn system
T(°C)
CO = 40 wt% Sn
Ca = 17 wt% Sn
300
CL = 46 wt% Sn L (liquid)
L+ a
Relative amount of each phase: 220 a R S L+b b
200
CL - CO 46 - 40 183°C
Wa = =
CL - Ca 46 - 17
6
100
a+b
= = 21 wt%
29
CO - Ca 23 0 17 20 40 46 60 80 100
WL = = = 79 wt% Ca Co CL
CL - Ca 29 C, wt% Sn
 Phase Diagrams

Binary Phase Diagrams: Development of Microstructures

• Co < 2 wt% Sn T(°C)
400
L: Co wt% Sn

• Result: L
a
--at extreme ends
300 L
--polycrystal of a grains
i.e., only one solid phase. L+ a
200
a
a: Co wt% Sn
(Pb-Sn
TE
System)

a+ b
100

0 10 20 30
Co Co, wt% Sn
2
(room T solubility limit)
 Phase Diagrams

Binary Phase Diagrams: Development of Microstructures

L: Co wt% Sn
• 2 wt% Sn < Co < 18.3 wt% Sn 400T(°C)
• Result: L
▪ Initially liquid + a L
a
▪ then a alone 300
L+a
▪ finally two phases a: Co wt% Sn
a
➢ a polycrystal 200
TE
➢ fine b-phase inclusions a
b
100
a+ b Pb-Sn
system
0 10 20 30
2 Co Co , wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
 Phase Diagrams

Binary Phase Diagrams: Development of Microstructures

• Co = CE
• Result: Eutectic microstructure (lamellar structure)
--alternating layers (lamellae) of a and b crystals.
T(°C) Micrograph of Pb-Sn
L: Co wt% Sn
eutectic
microstructure
300 L
Pb-Sn
system
L+ a
a 183°C L+b b
200
TE

100
a+b b: 97.8 wt% Sn 160 m
a: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn
 Phase Diagrams

Binary Phase Diagrams: Lamellar Eutectic Structure

Alternating layers

Micrograph of Pb-Sn
microstructure eutectic

160μm

α and β layered eutectic grow and replace the liquid phase. Redistribution of
lead and tin occurs by diffusion in the liquid ahead. Arrows indicate the
directions of diffusion of lead and tin atoms.
 Phase Diagrams

Binary Phase Diagrams: Development of Microstructures

• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: α phase particles and a eutectic microconstituent
• Just above TE :
T(°C) L: C0 wt% Sn α L
L
Cα = 18.3 wt% Sn
300 L α CL = 61.9 wt% Sn
Pb-Sn
L+α Wα = S = 0.50
system R +S
200
α R S L+β β WL = (1- W α ) = 0.50
TE S
R
• Just below TE :
100 α+ β C α = 18.3 wt% Sn
primary α C β = 97.8 wt% Sn
eutectic α
eutectic β Wα = S = 0.73
0 20 40 60 80 100 R +S
18.3 61.9 97.8 Wβ = 0.27
C, wt% Sn
 Phase Diagrams

Binary Phase Diagrams: Hypoeutectic & Hypereutectic

300
L
T(°C)
α L+ α
200 L+β β (Pb-Sn
TE

α+β System)
Two solid phases α, and β
100
these are sometimes
termed terminal solid
solutions 0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)

eutectic: C0 = 61.9 wt% Sn

α β
α β
α α β β
α β
α β
175 μm 160 μm
eutectic micro-constituent
 Phase Diagrams

Iron Carbon System

The iron–carbon system may be divided into two parts: an iron-rich portion and the other (not
shown) for compositions between 6.70 and 100 wt% C (graphite).

BCC (α-ferrite), only small concentrations

of carbon are soluble; the maximum
solubility is 0.022 wt% at 727˚C (1341˚F).
Limited solubility due to the shape and size
of the BCC interstitial positions.
Soft material, may be made magnetic at
temperatures below 768oC.

Austenite, or γ phase of iron, when alloyed

with carbon alone, is not stable below
727˚C.
Maximum solubility of carbon in austenite,
2.14 wt%, occurs at 1147˚C. FCC interstitial
positions are larger. Strains imposed on the
surrounding iron atoms are much lower.
Austenite is nonmagnetic.
 Phase Diagrams

Iron Carbon System

δ ferrite is virtually the same as α-ferrite, except for the range of temperatures over
which each exists. Stable only at relatively high temperatures

Cementite (Fe3C) forms when the

solubility limit of carbon in α-
ferrite is exceeded at a
temperature below 727˚C.

Very hard and brittle.

 Phase Diagrams

Iron Carbon System

➢ Pure iron contains less than 0.008

wt% Carbon (ferrite)

➢ Iron–carbon alloys that contain

between 0.008 wt% and 2.14 wt%
C are classified as steels, α and
Fe3C phases

➢ Carbon concentrations rarely

exceed 1.0 wt% in steel.

➢ Cast irons are classified as ferrous

alloys that contain between 2.14
and 6.70 wt% C.
 Phase Diagrams

Iron Carbon System

T(°C) melts at 1538oC

Fe3C (cementite)/iron carbide

• 2 important 1600
δ-ferrite (BCC)
points 1400 L
- Eutectic (A): γ +L
L  γ + Fe3C 1200
γ A
1148°C L+Fe3C
(austenite)
- Eutectoid (B):
γ  α + Fe3C
1000 γ γ γ +Fe3C
γ γ
800
α B 727°C = T
eutectoid

600
α +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 μm Fe3C (cementite-hard)
Result: Pearlite = alternating
layers of α and Fe3C phases
α (ferrite-soft) – stable form at RT
BCC
 Phase Diagrams

Iron Carbon System

 Phase Diagrams

T(°C)
Hypoeutectoid 1600
Steel δ
1400 L
γ γ (Fe-C
γ γ +L
γ γ 1200 1148°C L+Fe3C System)

Fe3C (cementite)
(austenite)
γ γ
1000
γ γ γ + Fe3C
α
α γ γ 800 727°C
γ αγ a
600
α + Fe3C
400
α 0 1 2 3 4 5 6 6.7
(Fe)C0 C, wt% C
0.76

Pearlite
(8:1 – a to Fe3C )
100 μm Hypoeutectoid
layer thickness is steel
approximately 8 to Pearlite
1 proeutectoid ferrite
Where a is the
Adapted from Fig. 11.29, Callister & Rethwisch 9e.
eutectoid ferrite (Photomicrograph courtesy of Republic Steel Corporation.)
 Phase Diagrams

Hypereutectoid T(°C)
1600
Steel δ
1400 L
(Fe-C
γ γ γ γ +L
1200 System)
γ γ 1148°C L+Fe3C

Fe3C (cementite)
(austenite)
γ γ 1000
γ γ γ + Fe3C
Fe3C
γ γ 800 727°C
γ γ α
600
α + Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe)C0 C, wt% C
pearlite

60 μmHypereutectoid
steel
pearlite proeutectoid Fe3C
Adapted from Fig. 11.32, Callister & Rethwisch 9e.
(Copyright 1971 by United States Steel Corporation.)
 Phase Diagrams

Hypereutectoid T(°C)
1600
Steel δ
1400 L
(Fe-C
Fe3C γ γ +L
1200 L+Fe3C System)
γ γ 1148°C

Fe3C (cementite)
(austenite)
γ γ 1000
γ + Fe3C
Wγ =x/(v + x)
800 v x 727°C
WFe3C =(1-Wγ)
α V X
600
α + Fe3C
pearlite
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe)C0 C, wt% C
Wpearlite = Wγ
Wα = X/(V + X)
60 μmHypereutectoid
WFe =(1 - Wα) steel
3C’
pearlite proeutectoid Fe3C
Adapted from Fig. 11.32, Callister & Rethwisch 9e.
(Copyright 1971 by United States Steel Corporation.)
 Phase Diagrams

Iron Carbon System: Example

For a 99.6 wt% Fe-0.40 wt% C steel at a temperature just

below the eutectoid, determine the following:
a) The compositions of Fe3C and ferrite (α).
b) The amount of cementite (in grams) that forms in 100 g
of steel.
c) The amounts of pearlite and proeutectoid ferrite (α) in
the 100 g.
 Phase Diagrams

Iron Carbon System: Example

a) Using the RS tie line just below the eutectoid
Cα = 0.022 wt% C
CFe3C = 6.70 wt% C
b) Using the lever rule with 1600
the tie line shown δ
1400 L
T(°C) γ +L
γ

Fe C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°C
R S
Amount of Fe3C in 100 g 600 α + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
Cα C0 C, wt% C CFe
3C
= (100 g)(0.057) = 5.7 g
 Phase Diagrams

Iron Carbon System: Example

c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Cα = 0.022 wt% C
1600
Cpearlite = Cγ = 0.76 wt% C δ
1400 L
T(°C) γ +L
γ

Fe3C (cementite)
1200 1148°C L+Fe3C
(austenite)
1000
γ + Fe3C
800 727°°C
VX
Amount of pearlite in 100 g 600 α + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
Cα C0 Cγ C, wt% C
= (100 g)(0.512) = 51.2 g
 Phase Diagrams

Example 2
Determine:
(a) Solubility of tin in solid lead
at 100°C
(b) Maximum solubility of lead
in solid tin
(c) Amount of that forms if a
Pb-10% Sn alloy is cooled to
0°C
(d) Masses of tin contained in
the and phases
(e) Mass of leadcontained in the
and phases. Assume that the
total mass of the Pb-10% Sn
alloy is 100 grams.
 Phase Diagrams

Example 2
 Phase Diagrams

Example 3
a) Determine the amount
and composition of each
phase in 200 g of a lead-
tin alloy of eutectic
composition immediately
after the eutectic reaction
has been completed.
b) Calculate the mass of
phases present.
c) Calculate the masses of
lead and tin in each phase
 Phase Diagrams

Example 4

For a Pb-30% Sn alloy,

determine the phases present,
their amounts, and their
compositions at 300°C, 200°C,
184°C, 182°C, and 0°C.
 Phase Diagrams

Example 4
 Phase Diagrams

Summary
• Phase diagrams are useful tools to determine:
-- the number and types of phases present,
-- the composition of each phase,
-- and the weight fraction of each phase
given the temperature and composition of the system.
• The microstructure of an alloy depends on
-- its composition, and
-- whether or not cooling rate allows for maintenance of
equilibrium.
• Important phase diagram phase transformations include eutectic,
eutectoid, and peritectic.

End of Topic #7: Phase Diagrams