PHASE DIAGRAM AND PHASE RULE

 Phase
 Phase equilibrium
 Component
 Phase diagram
 Phase rule
 Lecture Outline
 Introduction
 Solubility Limits
 Phases
 Phase Equilibrium
 Interpretation of Phase Diagrams
• Binary Isomorphous Systems (Cu-Ni)
• Development of Microstructure
• Mechanical Properties
• Binary Eutectic Systems
• Development of Eutectic Alloy Microstructure
2
 Components and Phases
• Components:
The elements or compounds that are mixed initially (Al and Cu).
• Phases:
A phase is a homogenous, physically distinct and mechanically
separable portion of the material with a given chemical composition
and structure ( and ).

Aluminum-  (lighter
Copper
Alloy phase)

(darker
phase)

3
 Phase Equilibria: Solubility Limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase
Sugar/Water Phase Diagram
• Solubility Limit:
Maximum concentration for 100
Solubility
which only a single phase L

Temperature (°C)
80 Limit
solution exists. (liquid)
60 L +
Question: What is the
(liquid solution S
solubility limit for sugar in 40
water at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
At 20°C, if C < 65 wt% sugar: syrup 0 20 40 6065 80 100
At 20°C, if C > 65 wt% sugar: syrup + sugar C = Composition (wt% sugar)
Water

Sugar
 Equilibrium

• A system is at equilibrium if its free energy is at

a minimum, given a specified combination of
temperature, pressure and composition.
• The (macroscopic) characteristics of the system
do not change with time — the system is stable.
• A change in T, P or C for the system will result in
an increase in the free energy and possible
changes to another state whereby the free
energy is lowered.

5
One Component Phase Diagram

6
 Importance of Phase Diagrams
• There is a strong correlation between
microstructure and mechanical properties,
and the development of alloy
microstructure is related to the
characteristics of its phase diagram.
• Phase diagrams provide valuable
information about melting, casting,
crystallization and other phenomena.

7
 Microstructure

• In metal alloys, microstructure is

characterized by the number of phases,
their proportions, and the way they are
arranged.
• The microstructure depends on:
– Alloying elements
– Concentration
– Heat treatment (temperature, time, rate of
cooling)

8
 Eutectic
• A eutectic or eutectic mixture is a mixture of two or
more phases at a composition that has the lowest
melting point.
• It is where the phases simultaneously crystallize from
molten solution.
• The proper ratios of phases to obtain a eutectic is
identified by the eutectic point on a binary phase
diagram.
• The term comes from the Greek 'eutektos', meaning
'easily melted.‘

9
 Two Component Phase Diagram
 Type 1: a binary alloy has
o Infinite solubility in the liquid state
o Zero solubility in the solid state
 Type 2: a binary alloy has
o Infinite solubility in the liquid state
o Infinite solubility in the solid state
 Type 3: a binary alloy has
o Infinite solubility in the liquid state
o Limited solubility in the solid state
Phase Diagrams: type 1

11
 Phase Diagrams: type 2
• Indicate phases as a function of Temp, Comp and Pressure.
• Focus on:
- binary systems: 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
T(°C)
1600 • 2 phases:
L (liquid)
1500 L (liquid)  (FCC solid solution)

1400 • 3 different phase fields:

Cu-Ni d us L
ui 
system 1300 liq L + s L+
l idu
1200 so  
(FCC solid
1100
solution)
1000
0 20 40 60 80 100 wt% Ni 12
 Effect of Temperature & Composition (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
T(°C)
1600

1500 L (liquid)

1400 id us
u D
B liq
1300 +
Cu-Ni L
dus
li
system 1200 so 
(FCC solid solution)
1100 A

1000 wt% Ni
0 20 40 60 80 100
Cu 13
 Determination of phase(s) present
• Rule 1: If we know T and Co, then we know:
--how many phases and which phases are present.
T(°C)
160 0
• Examples: L (liquid)
150 0
A(1100, 60): d us
ui

B(1250,35)
1 phase:  140 0 liq us
l id Cu-Ni
B(1250, 35): so
130 0 +   phase
2 phases: L +  L (FCC solid diagram
120 0 solution)
110 0 A(1100,60)
Melting points: Cu =
1085°C, Ni = 1453 °C 100 0
0 20 40 60 80 10 0 wt% Ni
Solidus - Temperature where alloy is completely solid. Above this line, liquefaction begins.
Liquidus - Temperature where alloy is completely liquid. Below this line, solidification
begins. 14
 Phase Diagrams: composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase.
Cu-Ni
• Examples: system
T(°C)
TA A
tie line
At TA = 1320°C: qu idus
130 0 L (liquid) li
Only Liquid (L) present + 
B L
CL = C0 ( = 35 wt% Ni) ol idus
TB s
At TD = 1190°C: 
Only Solid () present L + (solid)
120 0 D
C = C0 ( = 35 wt% Ni) TD

At TB = 1250°C: 20 3 032 35 4 0 43 50
C LC o C  wt% Ni
Both and L present

CL = C liquidus ( = 32 wt% Ni)
C = C solidus ( = 43 wt% Ni)
15
 Phase Diagrams: weight fractions of phases
• Rule 3: If we know T and Co, then we know:
--the amount of each phase (given in wt%).
• Examples:
C o = 35wt%Ni
T(°C) Cu-Ni system
At T A: Only Liquid (L)
TA A
WL = 100wt%, W  = 0 tie line
i dus
liqu
At T D: Only Solid ( ) 130 0 L (liquid)

WL = 0, W  = 100wt% B L+ us
l id
TB so
At T B : Both  and L R S

120 0 L+ D

C SS  C 43S 35 TD R (solid)
W L 
  o  
WWLL R S   73 wt %
R SCL R43S32
C 20 R35 S4 0 43
3 032 50
C LC o C
RR wt% Ni
W  o  CL  R
 C
W R S = 27wt
 %
R S
C   CL R S 16
 Binary Isomorphous Systems
Cu-Ni system:
• The liquid L is a homogeneous liquid solution composed of
Cu and Ni.
• The α phase is a substitutional solid solution consisting of
Cu and Ni atoms with an FCC crystal structure.
• At temperatures below 1080 C, Cu and Ni are mutually
soluble in each other in the solid state for all compositions.
• The complete solubility is explained by their FCC structure,
nearly identical atomic radii and electro-negativities, and
similar valences.
• The Cu-Ni system is termed isomorphous because of this
complete liquid and solid solubility of the 2 components.
17
18
 Criteria for Solid Solubility

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

Crystal
Structure electroneg r (nm)

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 soluble in one another for all proportions.

19
 Isomorphous Binary Phase Diagram
• Phase diagram:
Cu-Ni system. T(°C)
• System is: 1600
Cu-Ni
-- binary 1500 L (liquid) phase
2 components:
diagram
Cu and Ni. 1400
-- isomorphous id us
u 
i.e., complete 1300 liq + s
L idu
solubility of one l
1200 so 
component in
another;  phase (FCC solid
1100
field extends from solution)
0 to 100 wt% Ni. 1000
0 20 40 60 80 100 wt% Ni

20
Phase Diagrams: type 3

21
• The phase diagram displays a simple binary system composed of two components, A and B,
which has a eutectic point.
• The phase diagram plots relative concentrations of A and B along the X-axis, and
temperature along the Y-axis. The eutectic point is the point where the liquid phase borders
directly on the solid α + β phase; it represents the minimum melting temperature of any
possible A B alloy.
• The temperature that corresponds to this point is known as the eutectic temperature.
• Not all binary system alloys have a eutectic point: those that form a solid solution at all
concentrations, such as the gold-silver system, have no eutectic. An alloy system that has a
eutectic is often referred to as a eutectic system, or eutectic alloy.
• Solid products of a eutectic transformation can often be identified by their lamellar structure,
as opposed to the dendritic structures commonly seen in non-eutectic solidification. The
same conditions that force the material to form lamellae can instead form an amorphous solid
if pushed to an extreme.
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.

Cu-Ag system T(°C)

1200
• 3 single phase regions L (liquid)
(L, , ) 1000
• Limited solubility:  L + 
: mostly Cu TE 800 779°C L+
8.0 71.9 91.2
: mostly Ag
600
• TE : No liquid below TE   
• CE : Composition at 400
temperature TE
200
• Eutectic reaction 0 20 40 60 CE 80 100
C , wt% Ag
L(CE) (CE) + (CE)
cooling
L(71.9 wt% Ag) (8.0 wt% Ag)  (91.2 wt% Ag) 23
heating
Copper-Silver Phase Diagram
 Eutectic Reaction
• Solvus – (solid solubility line) BC, GH
• Solidus – AB, FG, BEG (eutectic isotherm)
• Liquidus – AEF
• Maximum solubility: α = 8.0 wt% Ag, β = 8.8 wt %Cu
• Invariant point (where 3 phases are in equilibrium) is at E;
CE = 71.9 wt% Ag, TE = 779C (1434F).
• An isothermal, reversible reaction between two (or more)
solid phases during the heating of a system where a
single liquid phase is produced.
Eutectic reaction
L(CE) (CE) + (CE)

cooling
L(71.9 wt% Ag) (8.0 wt% Ag)  (91.2 wt% Ag)
heating 25
 Pb-Sn Phase Diagram

Liquidus
Solidus
Solidus

Solidus

Solvus Solvus
 Solidification of Eutectic Mixtures
• Mixtures of some metals, such as copper & nickel, are completely
soluble in both liquid and solid states for all concentrations of both
metals. Copper & nickel have the same crystal structure (FCC) and
have nearly the same atomic radii. The solid formed by cooling can
have any proportion of copper & nickel. Such completely miscible
mixtures of metals are called isomorphous.
• By contrast, a mixture of lead & tin that is eutectic is only partially
soluble when in the solid state. Lead & tin have different crystal
structures (FCC versus BCT) and lead atoms are much larger. No
more than 18.3 weight % solid tin can dissolve in solid lead and no
more than 2.2% of solid lead can dissolve in solid tin (according to
previous phase diagram).
• The solid lead-tin alloy consists of a mixture of two solid phases,
one consisting of a maximum of 18.3 wt% tin (the alpha phase) and
one consisting of a maximum of 2.2 wt% lead (the beta phase).
27
 (Ex 1) Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
T(°C)
Answer: +  system
-- the phase compositions
300 L (liquid)
Answer: C = 11 wt% Sn
C = 99 wt% Sn
 L+ 
-- the relative amount 200 183°C L+ 
of each phase 18.3 61.9 97.8
Answer: 150
C - C 0 100
W =  + 
 C - C
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C C
W = C0 - C  C0 C, wt% Sn
 C - C 
40 - 11 29
= = = 0.33 28
99 - 11 88
 (Ex 2) Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present:
T(°C)
Answer: + L
-- the phase compositions
300 L (liquid)
Answer: C = 17 wt% Sn
CL = 46 wt% Sn L+
-- the relative amount 220 
200 L+ 
of each phase 183°C
Answer:
CL - C 0 100
46 - 40  + 
W = =
CL - C  46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 C
29 C0 CL C, wt% Sn

C0 - C  23
WL = = = 0.79
CL - C  29 29
 Pb-Sn
• For lead & tin the eutectic composition is
61.9 wt% tin and the eutectic temperature
is 183ºC -- which makes this mixture
useful as solder.
• At 183ºC, compositions of greater than
61.9 wt% tin result in precipitation of a tin-
rich solid in the liquid mixture, whereas
compositions of less than 61.9 wt% tin
result in precipitation of lead-rich solid.

30
 Lamellar Eutectic Structure
A 2-phase microstructure
resulting from the
solidification of a liquid
having the eutectic
composition where the
phases exist as a lamellae
that alternate with one Pb-rich
another.
Formation of eutectic Sn-rich
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 atoms by
atomic diffusion. 31
 (part 2)
• Equilibrium Diagrams with Intermediate Phases
or Compounds
• Eutectoid and Peritectic Reactions
• Ceramic Phase Diagrams
• The Gibbs Phase Rule
• The Iron-Iron Carbide Phase Diagram
• Development of Microstructures in Iron-Carbon
Alloys
• Hypoeutectoid Alloys
• Hypereutectoid Alloys
• Influence of Other Alloying Elements
32
 Intermetallic Compounds

19 wt% Mg-81 wt% Pb

Mg2Pb

Note: intermetallic compounds exist as a line on the diagram - not a

phase region. The composition of a compound has a distinct chemical33
formula.
34
 Ceramic Phase Diagrams
MgO-Al2O3 diagram:

35
 APPLICATION: REFRACTORIES
• Need a material to use in high temperature furnaces.
• Consider Silica (SiO2) - Alumina (Al2O3) system.
• Phase diagram shows: mullite, alumina and crystobalite (made up
of SiO2) are candidate refractories.

2200 3Al 2 O 3 -2SiO 2

T(°C)
mullite
20 00 Liquid
(L) alumina + L

1800
mullite alumina
crystobalite
+L +
+L
1600 mullite
mullite
+ crystobalite
1400
0 20 40 60 80 100
Composition (wt% alumina) 36
Ceramic Phases and Cements

37
 Gibbs Phase Rule
• Phase diagrams and phase equilibria are subject to the laws of thermodynamics.
• Gibbs phase rule is a criterion that determines how many phases can coexist within a
system at equilibrium.
P+F=C+N
P: # of phases present
F: degrees of freedom (temperature, pressure, composition)
C: components or compounds
N: noncompositional variables
For the Cu-Ag system @ 1 atm for a single phase P:
N=1 (temperature), C = 2 (Cu-Ag), P= 1 (, L)
F = 2 + 1 – 1= 2

This means that to characterize the alloy within a single phase

field, 2 parameters must be given: temperature and composition.
If 2 phases coexist, for example, L L, then according to GPR, we have 1
degree of freedom: F = 2 + 1 – 2= 1. So, if we have Temp or composition, then we can
completely define the system.
If 3 phases exist (for a binary system), there are 0 degrees of freedom. This means the
composition and Temp are fixed. This condition is met for a eutectic system by the
eutectic isotherm. 38
4 Solid Phases
 Iron carbide (Cementite or Fe3C)
• Forms when the solubility limit of carbon in 
ferrite is exceeded at temperatures below
727 ˚C.
• Mechanically, cementite is very hard and
brittle.
• For ferrous alloys there are 3 basic types,
based on carbon content:
 Iron (ferrite phase): <0.008 wt% C room temp
 Steel ( + Fe3C phase): 0.008 to 2.14 wt% C
 Cast iron: 2.14 to 6.70 wt% C
40
41
Alloying steel with other elements changes the Eutectoid
Temperature, Position of phase boundaries and relative
Amounts of each phase

42
 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
For a given temperature and composition of the system.

• The microstructure of an alloy depends on

-- its composition, and
-- rate of cooling equilibrium

43
Review

44
• Heating a copper-nickel alloy of composition 70 wt% Ni-30 wt% Cu from 1300°C.
At what temperature does the first liquid phase form?
• Solidus - Temperature where alloy is completely solid. Above this line,
liquefaction begins.
• Answer: The first liquid forms at the temperature where a vertical line at this
composition intersects the α-(α + L) phase boundary--i.e., about 1350°C;

T(°C)
160 0 • 2 phases:
L (liquid)
150 0 L (liquid)  (FCC solid solution)
140 0 • 3 phase fields:
d us L
130 0 u i
liq + s

L lidu L+
so 
120 0 
110 0
(FCC solid
solution)
100 0 Wt% Ni 45
0 20 40 60 80 10 0 wt% Ni
• (b) What is the composition of this liquid phase?
• Answer: The composition of this liquid phase corresponds to the
intersection with the (α + L)-L phase boundary, of a tie line
constructed across the α + L phase region at 1350°C, 59 wt% Ni;

T(°C)
160 0 • 2 phases:
L (liquid)
150 0 L (liquid)  (FCC solid solution)
140 0 • 3 phase fields:
dus L
130 0 ui
liq + s

L lidu L+
so 
120 0 
110 0 (FCC solid
solution)
100 0
0 20 40 60 80 10 0 wt% Ni
Wt% Ni 46
• (c) At what temperature does complete melting of the alloy occur?
• Liquidus - Temperature where alloy is completely liquid. Below this line, solidification
begins.
• Answer: Complete melting of the alloy occurs at the intersection of this same vertical line
at 70 wt% Ni with the (α + L)-L phase boundary--i.e., about 1380°C;

T(°C)
160 0 • 2 phases:
L (liquid)
150 0 L (liquid)  (FCC solid solution)
140 0 • 3 phase fields:
L
130 0 L+

120 0 
110 0
(FCC solid
solution)
100 0
0 20 40 60 80 10 0 wt% Ni
Wt% Ni
47
• (d) What is the composition of the last solid remaining prior to complete melting?
• Answer: The composition of the last solid remaining prior to complete melting
corresponds to the intersection with α-(α + L) phase boundary, of the tie line
constructed across the α + L phase region at 1380°C--i.e., about 78 wt% Ni.

T(°C)
160 0 • 2 phases:
L (liquid)
150 0 L (liquid)  (FCC solid solution)
140 0 • 3 phase fields:
L
130 0 L+

120 0 
110 0
(FCC solid
solution)
100 0
0 20 40 60 80 10 0 wt%
Wt%Ni
Ni
48