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Chapter 9:
Phase Diagrams
ISSUES TO ADDRESS...
• When we combine two elements...
what equilibrium state do we get?

• In particular, if we specify...
--a composition (e.g., wt% Cu - wt% Ni), and
--a temperature (T )
then...
1. How many phases do we get?
2. What is the composition of each phase?
3. How much of each phase do we get?

Phase A Phase B

Element (1) atom

Element (2) atom
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Definitions

Components are pure metals and/or compounds of which an alloy is

composed. For example, in a copper–zinc brass, the components are Cu
and Zn.

System it may relate to the series of possible alloys consisting of the

same components, (e.g., the iron–carbon system).

Solid solution consists of atoms of at least two different types; the

solute atoms occupy either substitutional or interstitial positions in the
solvent lattice, and the crystal structure of the solvent is maintained.

Mixtures is a systems composed of two or more phases or

heterogeneous systems. Most metallic alloys, ceramic, polymeric, and
composite systems are heterogeneous.

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Definitions

Phase is defined as a homogeneous portion of a system that has

uniform physical and chemical characteristics. Every pure material is
considered to be a phase; so also, is every solid, liquid, and gaseous
solution.
➢ For example, the sugar–water syrup solution Each has different physical
properties (one is a liquid, the other is a solid); furthermore, each is
different chemically (i.e., has a different chemical composition); one is
virtually pure sugar, the other is a solution of H2O
➢ If more than one phase is present in a given system, each will have its own
distinct properties, and a boundary separating the phases will exist across
which there will be a discontinuous and abrupt change in physical and/or
chemical characteristics
➢ When two phases are present in a system, it is not necessary that there be a
difference in both physical and chemical properties; a disparity in one or
the other set of properties is sufficient. Ex. water and ice

Phase Equilibria: Solubility Limit

– Solutions – solid solutions, single phase

– Mixtures – more than one phase
Sucrose/Water Phase Diagram
10 0
• Solubility Limit: Solubility
Temperature (°C)

Max concentration for which 80 Limit L

only a single phase solution occurs, (liquid)
60 +
at specific temp L
40 (liquid solution S
i.e., syrup) (solid
Question: What is the
20 sugar)
solubility limit at 20°C?

Answer: 65 wt% sugar. 0 20 40 60 65 80 100

Sugar
Water

If Co < 65 wt% sugar: syrup Co =Composition (wt% sugar)

Pure

Pure

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

sugar–water (C12H22O11–H2O) system

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Phase Equilibria: Solubility Limit

Effect of “T” & “Composition (C0)”

• Changing T can change # of phases: path A to B.
• Changing C0 can change # of phases: path B to D.
B (100°C,70) D (100°C,90)
1 phase 2 phases
100

80 L
Temperature (°C)

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

• Free energy is a function of the internal energy of a system, and also

the randomness or disorder of the atoms or molecules (or entropy).
➢A system is at equilibrium if its free energy is at a minimum under
some specified combination of temperature, pressure, and
composition. In a macroscopic sense, this means that the
characteristics of the system do not change with time but persist
indefinitely; that is, the system is stable.

• Phase equilibrium, refers to equilibrium as it applies to systems in

which more than one phase may exist.

• Metastable: non-equilibrium state that may persist for a very long

time (specially in solid systems, that a state of equilibrium is never
completely achieved because the rate of approach to equilibrium is
extremely slow)
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Phase Diagrams

➢ Phase diagram gives information about the control of microstructure or

phase structure of a particular alloy system is conveniently and concisely
displayed (equilibrium or constitutional diagram)
➢ There are three externally controllable parameters that will affect phase
structure – temperature, pressure, and composition – and phase diagram
are constructed when combinations of these parameters are plotted against
one another
One – component
(or unary)
Pressure–temperature phase diagram
for H2O. Intersection of the dashed
horizontal line at 1 atm pressure with
the solid– liquid phase boundary (point
2) corresponds to the melting point at
this pressure (T = 0°C). Similarly, point
3, the intersection with the liquid–vapor
boundary, represents the boiling point
(T = 100°C).

Binary Phase Diagrams

Simple solution system (e.g., Ni-Cu solution)

Crystal electronegativity r (nm)

Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have similar
electronegativities and atomic radii (W. Hume – Rothery rules)
suggesting high mutual solubility.

• Ni and Cu are totally miscible in all proportions.

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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).
T(°C)
• Phase 1600 • 2 phases region :
Diagram L (liquid)
1500 L (liquid)
for Cu-Ni α (FCC solid solution)
system 1400 • 3 phase fields:
L
1300 L+α
α
1200 α
1100
(FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni

Binary Phase Diagrams

• Rule 1: If we know T and Co, then we know:

--the wt% and types of phases present.

T(°C)
1600
• Examples: L (liquid)
1500
B (1250°C,35)

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

1000
0 20 40 60 80 100 wt% Ni

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Binary Phase Diagrams

• Rule 2: If we know T and Co, then we know:

--the composition of each phase.
Cu-Ni
T(°C) system
• Examples:
TA A
C o = 35 wt% Ni tie line
At T A = 1320°C: 1300 L (liquid)
Only Liquid (L) B
C L = C o ( = 35 wt% Ni) TB
α
At T D = 1190°C:
1200 D (solid)
Only Solid ( α ) TD
C α = C o ( = 35 wt% Ni )
20 30 40 50
At T B = 1250°C: C LC o C α wt% Ni
Both a and L 32 35 43
C L = C liquidus ( = 32 wt% Ni here)
C α = C solidus ( = 43 wt% Ni here)

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Binary Phase Diagrams

• Rule 3: If we know T and Co, then we know:

--the amount of each phase (given in wt%).
Cu-Ni
• Examples: T(°C) system
C o = 35 wt% Ni TA A
tie line
At T A : Only Liquid (L) 1300 L (liquid)
W L = 100 wt%, W α = 0 B
At T D : Only Solid ( α ) TB R S
α
W L = 0, W α = 100 wt%
1200 D (solid)
At T B : Both α and L TD
S 43 − 35 20 30 40 50
WL = =
43 − 32
= 73 𝑤𝑡%
C LC o C α wt% Ni
R +S
32 35 43
R
Wα = = 27 wt%
R +S

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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 M
B
TB
a
1200 (solid)
R S R S
20 30C C
L o
40 C
α
50
M  S = M L R
wt% Ni

ML S C − C0 R C − CL
WL = = =  W = = 0
M L + M  R + S C  − CL R + S C  − CL

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Development of Microstructure in Isomorphous Alloys

Equilibrium Cooling (Ex: Cooling in a Cu-Ni Binary)

• Phase diagram: T(°C) L (liquid) L: 35wt%Ni

Cu-Ni system. Cu-Ni
• System is: 130 0 A
system
--binary L: 35 wt% Ni
α : 46 wt% Ni B
i.e., 2 components: 35 46
Cu and Ni. 32 C 43
--isomorphous 24 D
36
L: 32 wt% Ni
i.e., complete α : 43 wt% Ni
solubility of one 120 0 E
component in L: 24 wt% Ni
another; a phase α : 36 wt% Ni
a
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
Co = 35 wt%Ni. 20 30 35 40 50
Co wt% Ni
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Development of Microstructure in Isomorphous Alloys

Non-Equilibrium Cooling (Ex: Cooling in a Cu-Ni Binary)

Schematic representation of the

development of microstructure
during the nonequilibrium
solidification of a 35 wt% Ni-65
wt% Cu alloy.

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Development of Microstructure in Isomorphous Alloys

Non-Equilibrium Cooling (Ex: Cooling in a Cu-Ni Binary)

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

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Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

--Tensile strength (TS) --Ductility (%EL,%AR)

60
Tensile Strength (MPa)

%EL for pure Cu

Elongation (%EL)
400 50 %EL for
TS for pure Ni
pure Ni 40
300
TS for pure Cu 30
200 20
0 20 40 60 80 100 0 20 40 60 80 100
Cu Ni Cu Ni
Composition, wt% Ni Composition, wt% Ni

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

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Phase Diagrams

Binary-Eutectic Systems
2 components has a special composition with a min. melting T.
Cu-Ag
Ex.: Cu-Ag system T(°C) system
• 3 single phase regions 1200
(L, α, β ) L (liquid)
1000
• Limited solubility:
α : mostly Cu α L+ α L+β β
779°C
β : mostly Ag TE 800 8.0 71.9 91.2

• TE : No liquid below TE 600

• CE : Min. melting TE solvus α +β
400
composition
200
• Eutectic transition 0 20 40 60 CE 80 100
Co , wt% Ag
L(CE) (CE) + (CE)

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Binary-Eutectic Systems

Pb-Sn Eutectic System

• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, find...
--the phases present: α+β Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Cα = 11 wt% Sn 300
L (liquid)
Cβ = 99 wt% Sn
--the relative amount α L+ α
200 183°C L+β β
of each phase: 18.3 61.9 97.8
S C - CO 150
Wα = =  R S
R+S C - C 100
α +β
99 - 40 59
= = = 67 wt%
99 - 11 88
C - C 0 11 20 40 60 80 99100
W = R = O C Co C
R+S C - C C, wt% Sn
40 - 11 29
= = = 33 wt%
99 - 11 88 19
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Binary-Eutectic Systems

Pb-Sn Eutectic System

• For a 40 wt% Sn-60 wt% Pb alloy at 200°C, find...

--the phases present: α+L Pb-Sn
--compositions of phases: T(°C) system
CO = 40 wt% Sn
Cα = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+ α
--the relative amount 220
200
α R S L+β β
of each phase: 183°C
CL - CO 46 - 40
Wα = = 100
CL - C 46 - 17 a +β
6
= = 21 wt%
29 100
0 17 20 40 46 60 80
C Co CL
CO - C 23 C, wt% Sn
WL = = = 79 wt%
CL - C 29

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Microstructures in Eutectic Systems

Pb-Sn Eutectic System (Region I)

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

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

100
a +β

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

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Microstructures in Eutectic Systems

Pb-Sn Eutectic System (Region II)

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

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Microstructures in Eutectic Systems

Pb-Sn Eutectic System (Region III)

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

100 160 m
+ : 97.8 wt% Sn
: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
61.9 C, wt% Sn
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Microstructures in Eutectic Systems

Lamellar Eutectic Structure

Schematic representation of the Photomicrograph showing the microstructure

formation of the eutectic structure for of a lead–tin alloy of eutectic composition.
the lead–tin system. Directions of This microstructure consists of alternating
diffusion of tin and lead atoms are layers of a lead-rich 𝛼-phase solid solution
indicated by blue and red arrows, (dark layers), and a tin-rich 𝛽-phase solid
respectively. solution (light layers). 375 ×

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Microstructures in Eutectic Systems

Pb-Sn Eutectic System (Region IV)

• 18.3 wt% Sn < Co < 61.9 wt% Sn
• Result: a crystals and a eutectic microstructure
L: Co wt% Sn
• Just above TE :
T(°C) α L
L
C α = 18.3 wt% Sn
300 α CL = 61.9 wt% Sn
L
Pb-Sn S
L+ α Wα = = 50 wt%
system R+S
200 α R S L+β β WL = (1- W a ) = 50 wt%
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 = 73 wt%
0 20 40 60 80 100 R+S
18.3 61.9 97.8 W β = 27 wt%
Co, wt% Sn

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Microstructures in Eutectic Systems

Hypoeutectic & Hypereutectic

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

α +β System)
100

0 20 40 60 80 100 Co, wt% Sn

eutectic
hypoeutectic: Co = 50 wt% Sn 61.9 hypereutectic: (illustration only)

eutectic: Co = 61.9 wt% Sn

α β
α β
α α β β
α β
α β
175 mm 160 mm
eutectic micro-constituent

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Solid Phases in Phase Diagrams

Terminal solid solution: the solid phase which exist over composition
ranges near the concentration extremities.

Intermediate solid solution:(or intermediate phases )

A solid solution or phase having a composition range that does not
extend to either of the pure components of the system. may be found at
other than the two composition extremes.

Intermetallic compounds: ( for metal – metal system)

A compound of two metals that has a distinct chemical formula. On a
phase diagram it appears as an intermediate phase that exists over a
very narrow range of compositions. Ex. The magnesium – lead system

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Intermediate Solid Solution

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Intermetallic Compounds

Note: intermetallic compound forms a line - not an area - because

stoichiometry (i.e. composition) is exact.

Mg2Pb

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Eutectoid & Peritectic Reactions

• Eutectic - liquid in equilibrium with two solids

L cool  + 
heat

• Eutectoid - solid phase transforms into two solid phases

S2 S1+S3
 cool  + Fe3C (727ºC)
heat

• Peritectic - liquid + solid 1 → solid 2

S1 + L S2
+L cool
 (1493ºC)
heat

Invariants point: the different phases in equilibrium

( ex. Eutectic, eutectoid, peritectic)
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Intermetallic Compounds

The copper–zinc phase diagram.

Peritectic transition  + L 

Eutectoid transition  +

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The Gibbs Phase Rule

Gibbs phase rule for construction of phase diagram

P + F = C +N
Gibbs phase rule: For a system at equilibrium, an equation that
expresses the relationship between the number of phases present and
the number of externally controllable variables.

P is the number of phases present

F is the number of these variables that can be changed independently
without altering the number of phases that coexist at equilibrium(T, p, C)
C is the number of components in the system.
N is the number of non compositional variables (e.g. temperature and
pressure).(p=1atm constant, so N =1)

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The Gibbs Phase Rule

Example: the copper–silver system

✓ Since pressure is constant (1 atm), the parameter N is 1 (temperature is the
only non compositional variable)
✓ The number of components C is 2
(viz Cu and Ag)

F=3-P

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Iron-Carbon (Fe-C) Phase Diagram

• 2 important T (°C)
1600
points 
-Eutectic (A): 1400 L
L   + Fe3C   +L
1200 1148°C
A L+Fe3C
-Eutectoid (B): (austenite)
Fe3C (cementite)

R S
   +Fe3C 1000
 +Fe3C


800 727°C = Teutectoid
B
R S
600
+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 Co, wt% C
C eutectoid

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Iron-Carbon (Fe-C) Phase Diagram

Eutectoid Steel

Photomicrograph of a eutectoid steel

showing the pearlite microstructure
consisting of alternating layers of 𝛼-
ferrite (the light phase) and Fe3C
(thin layers most of which appear
dark). 470×.

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Iron-Carbon (Fe-C) Phase Diagram

Hypoeutectoid Steel
T (°C)
1600

1400 L
  (Fe-C
  +L
  1200 1148°C L+Fe3C System)
Fe3C (cementite)

(austenite)
  1000
   + Fe3C

  800 r s 727°C

  RS
w  =s/(r +s) 600
w  =(1- w )
 + Fe3C
400
 0 1 2 3 4 5 6 6.7
(Fe) C0 Co , wt% C
0.76

pearlite
w pearlite = w 
Hypoeutectoid
w  =S/(R+S) 100 m
steel
w Fe3 =(1-w )
C
pearlite proeutectoid ferrite
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Iron-Carbon (Fe-C) Phase Diagram

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

Fe3C (cementite)
(austenite)
  1000
   +Fe3C
Fe3C
  800 r s
   R S
w Fe3C =r/(r +s) 600  +Fe3C
w  =(1-w Fe3C )
400
0 1 Co 2 3 4 5 6 6.7
0.76

(Fe)
pearlite Co , wt%C
w pearlite = w 
w  =S/(R+S)
w Fe3C =(1-w  ) 60 mHypereutectoid
steel
pearlite proeutectoid Fe3C

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Alloying Steel with More Elements

• Teutectoid changes: • Ceutectoid changes:

(wt%C)

Ti Si
(°C)

Mo Ni
W
Cr
Eutectoid

eutectoid

Cr
Si
Mn
Mn W
Ti Mo
C
T

Ni

wt. % of alloying elements wt. % of alloying elements

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