Phase Diagram

Dr.-Ing. Alfian Ferdiansyah

  Many of the engineering materials possess mixtures of
phases, e.g. steel, paints, and composites.
Introduction  The mixture of two or more phases may permit interaction
between different phases, and results in properties usually
are different from the properties of individual phases.
• Different components can be
combined into a single material by
means of solutions or mixtures

• The properties of materials reflect

their microstructures, which are
controlled by the composition of
the material and how it is
processed.
Phase diagram is basically a map that
presents the domains of stability of
phases and the limits of stability of
phases in a graphical form

It will tell us:

 at the state when it comes to
equilibrium
 what phases are present, the state
of those phases
 the relative quantities of each phase
 what phase transformations we can
expect when we change one or
more parameters of the system (T, P,
X).
  Solvent: in an alloy, the element or compound
Terminology present in greater amount
 Solute: in an alloy, the element or compound
present in lesser amount.
In metallurgy, the term phase refers to a physically
homogeneous state of matter. It has a particular  Solid Solution are made of a host (the solvent
chemical composition and a distinct type of atomic or matrix) which dissolves the minor
bonding and arrangement of elements. Within an component (solute).
alloy, two or more different phases can be present at
the same time.
The ability to dissolve is called solubility: it has
 For solids: Chemically and structurally distinct
the properties of:
 For liquids: Miscibility
 homogeneous
 For gases: Always 1 phase
 maintains crystal structure
 contains randomly dispersed impurities
• Component: chemically recognizable species
(substitutional or interstitial)
(Fe and C in carbon steel, H2O and NaCl in
salted water), which are mixed initially.
• A unary contains one component, a binary
alloy contains two components, a ternary
alloy contains three components.
 Terminology
 Second Phase: as solute atoms are added, new compounds/structures are formed, or
solute forms local precipitates.
 Liquidus: Temperature at which alloy is completely liquid or solidification begins
 Solidus: Temperature at which alloy is completely solid or liquefaction begins.
 Isomorphous: when the two components have complete liquid and solid solubility
(unlimited solid solubility).
 Solubility Limit of a component in a phase is the maximum
amount of the component that can be dissolved in it (e.g., alcohol
has unlimited solubility in water, sugar has a limited solubility, oil is
virtually insoluble). The same concepts apply to solid phases: Cu
and Ni are mutually soluble in any amount (unlimited solid
solubility), while C has a limited solubility in Fe.
 A typical unary diagram

*The dashed line indicates the exceptional case of water

o In these systems there is no composition change, thus the only

variables are temperature and pressure.
o In region of single phase, two variables (temperature and pressure)
can be varied independently.
o If two phases coexist then, according to phase rule, either
temperature or pressure can be varied independently, but not both.

7
Binary These diagrams constitutes two components,
phase e.g.: two metals (Cu and Ni), or a metal and a
compound (Fe and Fe3C), or two compounds
diagrams (Al2O3 and Si2O3), etc.

8
 We are already dealing with three variables. : pressure,
Binary phase temperature and a composition* variable (P,T,X)

diagrams *The latter is usually defined in terms of a mole fraction. In principle we could
take any concentration unit, but units like molarity are not very useful because
if we want to vary temperature volume can change a lot and this affects
molarity. Mole fractions do not have this problem

9
 1.
2.
Binary phase
diagrams
3.
Hume-Ruthery conditions are summarized in
the following:
 Crystal structure of each element of solid
solution must be the same.
 Size of atoms of each two elements must
not differ by more than 15%.
 Elements should not form compounds
with each other i.e. there should be no
appreciable difference in the electro-
negativities of the two elements.
 Elements should have the same valence.
Binary systems are classified according to their solid solubility.
If both the components are completely soluble in each other,
the system is called isomorphous system, e.g.: Cu-Ni, Ag-Au,
Ge-Si, Al2O3-Cr2O3.
Extent solid solubility for a system of two metallic components
can be predicted based on Hume-Ruthery conditions
In systems other than isomorphous
systems i.e. in case of limited solid
solubility, there exist solid state
miscibility gaps; number of
invariant reactions can take place;
intermediate phases may exist.
These intermediate phases may
undergo polymorphic
transformations, and some may
melt at a fixed
10
Interpretation Of Phase Diagrams
 Interpretation Of Phase Diagrams
Percentage
It is determined by locating the
temperature-composition point on
the diagram and notes the phase(s)
which the corresponding labeled
phase field

Composition Phase present

 Solubility Limit
• Solution – solid, liquid, or gas solutions, single phase
• Mixture – more than one phase Adapted from Fig. 9.1,
Callister & Rethwisch 8e.

• Solubility Limit: Sugar/Water Phase Diagram

Maximum concentration for 100
which only a single phase Solubility

Temperature (ºC)
solution exists. 80 Limit L
(liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit for sugar in i.e., syrup) (solid
water at 20ºC? 20 sugar)

Answer: 65 wt% sugar.

0 20 40 6065 80 100
At 20ºC, if C < 65 wt% sugar: syrup
C = Composition (wt% sugar)

Sugar
Water

At 20ºC, if C > 65 wt% sugar:

syrup + sugar
 Components and Phases
• Components:
The elements or compounds which are present in the alloy
(e.g., Al and Cu)

• Phases:
The physically and chemically distinct material regions
that form (e.g., a and b).

Aluminum- b (lighter
Copper
phase)
Alloy

a (darker
Adapted from chapter-
opening photograph,
phase)
Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.
Effect of Temperature & Composition
• Altering T can change # of phases: path A to B.
• Altering C can change # of phases: path B to D.
B (100ºC,C = 70) D (100ºC,C = 90)
1 phase 2 phases
100

80 L
Temperature (ºC)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
Adapted from Fig. 9.1, 0
Callister & Rethwisch 8e. 0 20 40 60 70 80 100
15
C = Composition (wt% sugar)
 Isomorphous Binary Phase Diagram
T(ºC)
• Phase diagram: 1600
Cu-Ni system.
1500 L (liquid)
• System is:
1400
d us
ui a
1300 liq
L +lidus
-- isomorphous so
1200 a
i.e., complete
solubility of one 1100
(FCC solid
component in solution)
another; a phase 1000
0 20 40 60 80 100 wt% Ni
field extends from
0 to 100 wt% Ni. Cu-Ni phase diagram
Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (Fig. 9.3(a) is adapted
from Phase Diagrams of Binary Nickel Alloys, P. Nash (Ed.), ASM
16 International, Materials Park, OH (1991).
 Determination of phase(s) present

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

-- which phase(s) is (are) present.

• Examples: T(ºC)
1600
A(1100ºC, 60 wt% Ni): L (liquid)
1 phase: a 1500

B (1250ºC,35)
id us Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 u
liq s phase
2 phases: L + a d u
s oli diagram
1300
a
L+ a
(FCC solid
Adapted from Fig. 9.3(a), Callister & 1200
Rethwisch 8e. (Fig. 9.3(a) is adapted from solution)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International, 1100 A(1100ºC,60)
Materials Park, OH (1991).
1000
0 20 40 60 80 100 wt% Ni
17
Determination of phase compositions
• Rule 2: If we know T and C0, then we can determine:
-- the composition of each phase.
Cu-Ni
• Examples: system
T(ºC)
Consider C0 = 35 wt% Ni A
At TA = 1320ºC: TA tie line dus
i
1300 L (liquid) liqu
Only Liquid (L) present a
CL = C0 ( = 35 wt% Ni) B L+
id us
TB sol
At TD = 1190ºC: a
Only Solid (a) present L +a (solid)
1200 D
C = C0 ( = 35 wt% Ni) TD
At TB = 1250ºC: 20 3032 35 4043 50
Both and L present CL C 0 C wt% Ni

CL = C liquidus ( = 32 wt% Ni) Adapted from Fig. 9.3(a), Callister & Rethwisch 8e.
(Fig. 9.3(a) is adapted from Phase Diagrams of

18 C = C solidus ( = 43 wt% Ni) Binary Nickel Alloys, P. Nash (Ed.), ASM

International, Materials Park, OH (1991).
Determination of phase weight fractions

• Rule 3: If we know T and C0, then can determine:

-- the weight fraction of each phase.
• Examples: Cu-Ni
T(ºC) system
Consider C0 = 35 wt% Ni
TA A
At TA : Only Liquid (L) present tie line dus
i
1300 L (liquid) liqu
WL = 1.00, Wa = 0 + a
At TD : Only Solid (  ) present B L
id us
TB R S so l
WL = 0, W = 1.00 a
a a
At TB : Both

and L present 1200 L+ D (solid)
TD
S 43  35
WL =   0.73
R +S 43  32 20 3032 35 40 43 50
CL C0 Ca wt% Ni
R
Wa = = 0.27 Adapted from Fig. 9.3(a), Callister & Rethwisch 8e. (Fig. 9.3(a) is
19
R +S adapted from Phase Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park, OH (1991).
 The Lever Rule
Tie line – connects the phases in equilibrium with each other –
also sometimes called an isotherm
T(ºC) What fraction of each phase?
tie line dus
liq u
i Think of the tie line as a lever
1300 L (liquid)
+ a (teeter-totter)
B L
id us
TB so l ML M
a
L +a (solid)
1200
R S

20 30 40 50 R S
CL C0 C
wt% Ni Adapted from Fig. 9.3(b),
M x S  ML x R
Callister & Rethwisch 8e.

ML S C   C0 R C0  CL
WL    W  
ML  M  R  S C  CL R  S C  CL
20 
 Microstructure development in Cu-Ni Alloy
T(ºC) L (liquid) L: 35wt%Ni
• Phase diagram: Cu-Ni
Cu-Ni system. system
130 0 A a
• Consider L: 35 wt% Ni L+
a: 46 wt% Ni B
microstuctural 32
35
C 46
43
changes that
D
accompany the 24 36 L: 32 wt% Ni

cooling of a a a: 43 wt% Ni
L+
120 0 E
C0 = 35 wt% Ni alloy L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

Adapted from Fig. 9.4,

110 0
Callister & Rethwisch 8e.
20 30 35 40 50
21 C0 wt% Ni
 This transformation is known as eutectic reaction

Many binary systems have components which have limited solid solubility, e.g.: Cu-Ag, Pb-Sn.

The lowest temperature at The regions of limited solid

which the liquid can exist solubility at each end of a
when cooled under phase diagram are called
equilibrium conditions is terminal solid solutions as
known as eutectic they appear at ends of the
temperature. diagram.
The corresponding
point on the phase
diagram is called
When the liquid of eutectic eutectic point
composition is cooled, at or
below eutectic temperature this it consists of specific
liquid transforms simultaneously alloy composition known
into two solid phases (two as eutectic composition
terminal solid solutions,
represented by α and β).
 Binary-Eutectic Systems
has a special composition
2 components with a min. melting T.
Cu-Ag
T(ºC) system
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, a, b) 1000
• Limited solubility: a L + a 779ºC L+b b
a: mostly Cu 800
TE 8.0 71.9 91.2
b: mostly Ag 600
• TE : No liquid below TE
a+ b
• CE : Composition at 400
temperature TE
200
0 20 40 60 CE 80 100
• Eutectic reaction C, wt% Ag
L(CE) (CE) + (CE) Adapted from Fig. 9.7,
Callister & Rethwisch 8e.
cooling
L(71.9 wt% Ag) (8.0 wt% Ag)  (91.2 wt% Ag) 23
heating
 EX 1: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present
Answer: a + Pb-Sn
b -- the phase compositions T(ºC) system
Answer: Ca = 11 wt% Sn
300
Cb = 99 wt% Sn L (liquid)
-- the relative amount
of each phase a L+ a
200 183ºC L+b b
Answer: 18.3 61.9 97.8
S C - C 0 150
W =
 R+S
=
C - C R S
100
99 - 40 59 a +b
= = = 0.67
99 - 11 88
C0 - C 
W = R = 0 11 20 40 60 80 99100
 R+S C  - C C C0 C, wt% Sn C
Adapted from Fig. 9.8,
40 - 11 29
= = = 0.33 Callister & Rethwisch 8e.
24 99 - 11 88
 EX 2: Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220ºC, determine:
-- the phases present:
Pb-Sn
Answer: a + L T(ºC) system
-- the phase compositions
Answer: Ca = 17 wt% Sn 300
L (liquid)
CL = 46 wt% Sn L+ a
-- the relative amount 220 a
of each phase 200 R S L+b b
183ºC
Answer:
C L - C0 46 - 40 100
Wa =
CL - C 
=
46 - 17
a +b
6
= = 0.21 0 17 20 40 46 60 80 100
29
C C0 CL C, wt% Sn
C0 - C  23 Adapted from Fig. 9.8,
WL = = = 0.79 Callister & Rethwisch 8e.
CL - C  29
25
 Microstructural Developments
in Eutectic Systems I
T(ºC) L: C0 wt% Sn
400
• For alloys for which L
C0 < 2 wt% Sn a
300 L

• Result: at room temperature L+ a

a
-- polycrystalline with grains of 200
a: C0 wt% Sn
(Pb-Sn
TE
a phase having System)
composition C0 100
a+b

Adapted from Fig. 9.11, 0 10 20 30

Callister & Rethwisch 8e. C0 C , wt% Sn
2
(room T solubility limit)
26
 Microstructural Developments
in Eutectic Systems II
L: C0 wt% Sn
T(ºC)
400
• For alloys for which
L
2 wt% Sn < C0 < 18.3 wt% Sn L
300 a
L+a
• Result: a: C0 wt% Sn
at temperatures in a + b range a
200
TE
-- polycrystalline with a grains a
and small b-phase particles b
100
a+ b Pb-Sn
system
Adapted from Fig. 9.12,
Callister & Rethwisch 8e. 0 10 20 30
2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE)
27
 Microstructural Developments
in Eutectic Systems III
• For alloy of composition C0 = CE
• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.
T(ºC) Micrograph of Pb-Sn
L: C0 wt% Sn eutectic
300 L microstructure
Pb-Sn
system
L+ a
200 a 183ºC L b
TE

100
a : 97.8 wt% Sn
160 m
Adapted from : 18.3 wt%Sn
Fig. 9.13, Adapted from Fig. 9.14,
Callister & Callister & Rethwisch 8e.
Rethwisch 8e. 0 20 40 60 80 100
18.3 CE 97.8
28 61.9 C, wt% Sn
 Lamellar Eutectic Structure

Adapted from Figs. 9.14 & 9.15, Callister & Rethwisch 8e.

29
 Hypoeutectic & Hypereutectic
300
L
Adapted from Fig. 9.8, T(ºC)
Callister & Rethwisch 8e. a L+ a
(Fig. 10.8 adapted from
200 L+b b (Pb-Sn
TE
Binary Phase Diagrams,
2nd ed., Vol. 3, T.B. a+b System)
Massalski (Editor-in-Chief), 100
ASM International,
Materials Park, OH, 1990.)

0 20 40 60 80 100 C, wt% Sn
eutectic
hypoeutectic: C0 = 50 wt% Sn 61.9 hypereutectic: (illustration only)
(Figs. 9.14 and 9.17
from Metals
eutectic: C0 = 61.9 wt% Sn
Handbook, 9th ed.,
Vol. 9,
a b
Metallography and a b
Microstructures, a a b b
American Society for a b
Metals, Materials
Park, OH, 1985.) a b
175 mm 160 mm
Adapted from eutectic micro-constituent Adapted from Fig. 9.17,
Fig. 9.17, Callister & Adapted from Fig. 9.14, Callister & Rethwisch 8e.
Rethwisch 8e. Callister & Rethwisch 8e. (Illustration only)
30
 Eutectic, Eutectoid, & Peritectic
• Eutectic - liquid transforms to two solid phases
L cool  +  (For Pb-Sn, 183ºC, 61.9 wt% Sn)
heat

• Eutectoid – one solid phase transforms to two other solid

phases
intermetallic compound
S2 S1+S3 - cementite
cool
 heat
 + Fe3C (For Fe-C, 727ºC, 0.76 wt% C)

• Peritectic - liquid and one solid phase transform to a

second solid phase
S1 + L S2
cool
 +L heat  (For Fe-C, 1493ºC, 0.16 wt% C)
31
 Eutectoid & Peritectic
Peritectic transformation  + L 

Cu-Zn Phase diagram

Adapted from Fig. 9.21,

Eutectoid transformation  + Callister & Rethwisch 8e.

32
 Invariant reactions
The eutectic reaction, in which a liquid transforms into two solid
phases, is just one of the possible three-phase invariant reactions that
can occur in binary systems those are not isomorphous.
       

Reaction Symbolic equation Schematic presentation Example

   
Eutectic L↔α+β   Fe-C, 4.27% C,
1147 C
   
Eutectoid α↔β+γ   Fe-C, 0.80% C,
723 C
   
Peritectic L+α↔β   Fe-C, 0.16%C,
1495 C
   
Peritectoid α+β↔γ    
   
Monotectic L1 ↔ L2 + α   Fe-C, 0.51%C,
1495 C