CHAPTER IX

PHASE SYSTEM
ISSUES TO ADDRESS...

1. When we combine two elements.......... equilibrium state?

2. In particular, if we specify...
-- the composition (e.g., wt% Cu - wt% Ni), and
-- the temperature (T )

 How many phases form?

 What is the composition of each phase?
 What is the amount of each phase?

Phase A Phase B

Nickel atom
2
Copper atom
 Phase Equilibria:
Solubility Limit

Phase  a physically distinctive form of matter, such as a solid, liquid,

gas or plasma.

Phase of matter characterized by having relatively uniform

chemical and physical properties. 

• Solution solid, liquid, or gas solutions,

single phase more than one phase

• Solubility Limit:
Maximum concentration for which only a single
phase solution exists.

3
 Question: What is the solubility limit for sugar in water at 20ºC?

Sugar/Water Phase Diagram

100
Temperature (ºC) Solubility
80 Limit L
(liquid)
60 +
L
40 (liquid solution S
i.e., syrup) (solid
20 sugar)

0 20 40 60 80 100

Sugar
Water

C = Composition (wt% sugar)

Answer: 65 wt% sugar.

At 20ºC, if C < 65 wt% sugar : syrup
At 20ºC, if C > 65 wt% sugar : syrup + sugar
Adapted from Fig. 9.1,
Callister & Rethwisch 8e.
 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
phase)

5
Adapted from chapter-opening photograph, 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)
1 phase
100
D (100ºC,C = 90)
80 L 2 phases
Temperature (ºC)

(liquid)
water- 60 +
sugar L S
system (liquid solution (solid
40 i.e., syrup) sugar)
20 A (20ºC,C = 70)
2 phases
0
0 20 40 60 70 80 100
C = Composition (wt% sugar)
6
Adapted from Fig. 9.1, Callister & Rethwisch 8e.
 Criteria for Solid Solubility

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

Crystal Electrone
Structure gativity r (nm)

Ni FCC 1.9 0.1246

Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

almost similar electronegativities and atomic radii
(W. Hume – Rothery rules) suggesting high mutual solubility.

7
Ni and Cu are totally soluble in one another for all proportions
 Phase Diagrams
• Indicate phases as a function of T, C, and P.
• For this course:
- binary systems: just 2 components.
- independent variables: T and C (P = 1 atm is almost always used).

• 2 phases:
Cu-Ni L (liquid)
system SS (FCC solid solution)
• 3 different phase fields:
L
L + SS
S
FCC

8
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 International,
Materials Park, OH (1991).
 Isomorphous Binary Phase Diagram

• Phase diagram: T(ºC)

Cu-Ni system. 1600

• System is: 1500 L (liquid)

-- binary
i.e., 2 components: 1400 Cu-Ni
Cu and Ni. d us phase
ui a
1300 liq diagram
-- isomorphous L +lidus
i.e., complete 1200 so
solubility of one SS
component in 1100
another; SS phase (FCC solid solution)
field extends from 1000
0 to 100 wt% Ni.
0 20 40 60 80 100 wt% Ni

9
 Phase Diagrams:
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) A(1100ºC, 60 wt% Ni):
1600
L (liquid) 1 phase: SS
B(1250ºC, 35 wt% Ni):
B (1250ºC,35)

1500
u s
id Cu-Ni 2 phases: L + SS
1400 il qu phase
id us
s ol diagram
1300 SS
L + a
(FCC solid
1200
solution)
1100 A(1100ºC,60)

1000
0 20 40 60 80 100 wt% Ni
10
 Phase Diagrams:
Determination of phase compositions

• Rule 2: If we know T and C0, then we can determine:

-- the composition of each phase.
• Examples:
Cu-Ni Consider C0 = 35 wt% Ni
T(ºC) system At TA = 1320ºC:
TA A Only Liquid (L) present
tie line dus
i
1300 L (liquid) l iq u CL = C0 ( = 35 wt% Ni)
S S
L + At TD = 1190ºC:
B idu
s
TB so l Only Solid (a) present
CSS = C0 ( = 35 wt% Ni)
SS
1200 L + D SS (solid) At TB = 1250ºC:
TD
Both SS and L present
20 3032 35 4043 50
CL C 0 CSS wt% Ni CL = C liquidus ( = 32 wt% Ni)
CSS = C solidus ( = 43 wt% Ni)
11
 Phase Diagrams:
Determination of phase weight fractions
• Rule 3: If we know T and C0, then can determine:
-- the weight fraction of each phase.
Cu-Ni
SS=⍺
• Examples: T(ºC) system
Consider C0 = 35 wt% Ni TA A
tie line dus
i
At TA : Only Liquid (L) present 1300 L (liquid) liqu
+ a
WL = 1.00, Wa = 0 B L
id us
At TD : Only Solid ( ) present TB R S so l
 a
WL = 0, W = 1.00 a
a 1200 L+ D (solid)
At TB : Both and L present
 TD

Wa =
S  -
43  35
 0.73
20 3032 35 40 43 50
R +S -
43  32 CL C0 Ca wt% Ni

R
WL = = 0.27
R +S
12
 The Lever Rule
• Tie line (isoterm) connects the phases in equilibrium with
each other

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
d us
TB so li ML M
a SS=⍺
L +a (solid)
1200
R S

20 30 40 50 R S
CL C0 C
wt% Ni

ML S C  C0 R C  CL
WL     W   0
ML  M  R  S C  CL R  S C  CL
13
 Ex: Cooling of a Cu-Ni Alloy

T(ºC) L (liquid) L: 35wt%Ni • Consider

microstuctural
130 0 a changes that
A
L: 35 wt% Ni L+ accompany the
a: 46 wt% Ni B
35
C 46 cooling of a
32
43 C0 = 35 wt% Ni alloy
24 D L: 32 wt% Ni
36
a a: 43 wt% Ni
L+
120 0 E
L: 24 wt% Ni
a: 36 wt% Ni
a
(solid)

110 0
20 30 35 40 50
C0 wt% Ni
14
 Cored vs Equilibrium Structures
• Ca changes as we solidify.
• Cu-Ni case: First a to solidify has Ca = 46 wt% Ni.
Last a to solidify has Ca = 35 wt% Ni.
• Slow rate of cooling: • Fast rate of cooling:
Equilibrium structure Cored structure
Uniform Ca:
35 wt% Ni First a to solidify:
46 wt% Ni
Last a to solidify:
< 35 wt% Ni

15
 Mechanical Properties: Cu-Ni System

• Effect of solid solution strengthening on:

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

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
Tensile strength : the maximum amount of stress that it can take before failure

Ductility : ability of a material to deform under tensile stress

16
Adapted from Fig. 96 (a) and 9.6(b), Callister & Rethwisch 8e.
 Binary - Eutectic Systems
2 components has a special composition
with a minimum melting T.
T(ºC) Cu-Ag system
1200 Ex.: Cu-Ag system
L (liquid) • 3 single phase regions
1000
(L, a, b)
a L+ a L+b b • Limited solubility:
800 779ºC
TE 8.0 71.9 91.2 a: mostly Cu
600 b: mostly Ag
a+ b • TE : No liquid below TE
400
• CE : Composition at
200 temperature TE
0 20 40 60 CE 80 100
C, wt% Ag
• Eutectic reaction
L(CE) (CE) + (CE)
cooling 17
L(71.9 wt% Ag) (8.0 wt% Ag)  (91.2 wt% Ag)
heating
 Ex 1 : Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150ºC, determine:
-- the phases present
T(ºC) Pb-Sn system
Answer: a +
b -- the phase compositions
300
Answer: Ca = 11 wt% Sn L (liquid)
Cb = 99 wt% Sn
-- the relative amount a L+ a
200 183ºC L+b b
of each phase 18.3 61.9 97.8
Answer: 150
S C - C0 R S
W = =  100
 R+S C - C a +b
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
C0 - C  C C0 C, wt% Sn C
W = R =
 R+S C  - C Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
40 - 11 29
= = = 0.33 18
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 system
Answer: a + L T(ºC)
-- the phase compositions
300
Answer: Ca = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+ a
-- the relative amount 220 a
200 R S L+b b
of each phase 183ºC
Answer:
C L - C0 100
46 - 40 a +b
Wa = =
CL - C  46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21
29 C C0 CL C, wt% Sn

C0 - C  23
WL = = = 0.79
CL - C  29 19
Adapted from Fig. 9.8,
Callister & Rethwisch 8e.
 Microstructural Developments
(Eutectic Systems I)

T(ºC) L: C0 wt% Sn
400
L • For alloys for which
a
300 L C0 < 2 wt% Sn
• Result: at room temperature
L+ a -- polycrystalline with grains of
200
a
(Pb-Sn a phase having
TE a: C0 wt% Sn
System)
composition C0
100
a+b

0 10 20 30
C0 C , wt% Sn
2
(room T solubility limit)

20
 Microstructural Developments
(Eutectic Systems II)
L: C0 wt% Sn
T(ºC)
400
• For alloys for which
L
L 2 wt% Sn < C0 < 18.3 wt% Sn
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
0 10 20 30
2 C0 C, wt% Sn
sol. limit at T room ) 18.3
(sol. limit at TE) 21
 Microstructural Developments
(Eutectic Systems III)

• For alloy of composition C0 = CE

• Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of a and b phases.
Pb-Sn system Micrograph of Pb-Sn
T(ºC) Eutectic microstructure
L: C0 wt% Sn
300 L
L+ a
200 a 183ºC L b
TE

100 160 m
a : 97.8 wt% Sn
: 18.3 wt%Sn

0 20 40 60 80 100
18.3 CE 97.8
22
61.9 C, wt% Sn
 Lamellar Eutectic Structure

23
Adapted from Figs. 9.14 & 9.15, Callister & Rethwisch 8e.
 Microstructural Developments
(Eutectic Systems IV)

• For alloys for which 18.3 wt% Sn < C0 < 61.9 wt% Sn
• Result: a phase particles and a eutectic microconstituent
• Just above TE :
T(ºC) L: C0 wt% Sn L
L  Ca = 18.3 wt% Sn
300 L CL = 61.9 wt% Sn

S
L+ Wa = = 0.50
 R+S
200
a R S L+ b WL = (1- Wa ) = 0.50
TE 
R S
• Just below TE :
100 + C = 18.3 wt% Sn
  
primary a C = 97.8 wt% Sn
eutectic a 
eutectic b W = S = 0.73
0 20 40 60 80 100  R+S
18.3 61.9 97.8 W = 0.27
C, wt% Sn  24
Pb-Sn system
Hypoeutectic & Hypereutectic
300
L
T(ºC)
a L+ a
200 L+b b (Pb-Sn System)
TE

a+b
100

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

a b
a b
a a b b
a b
a b
175 mm 160 mm
eutectic micro-constituent
25
 Intermetallic Compounds

Mg2Pb

Note: intermetallic compound exists as a line on the diagram - not an

area - because of stoichiometry (i.e. composition of a compound 26

is a fixed value).
 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)
27
 Eutectoid & Peritectic
Peritectic transformation  + L 

Cu-Zn Phase diagram

Eutectoid transformation  +

28
 Iron-Carbon (Fe-C) Phase Diagram

• 2 important T(ºC)
1600
points d
- Eutectic (A): 1400 L
L Þ g + Fe3C g g +L
1200 1148ºC
A L+Fe3C
- Eutectoid (B): (austenite)

Fe3C (cementite)
g Þ a + Fe3C 1000 g g
a+
g g g+Fe3C
800
a B 727ºC = T eutectoid
g

600
a +Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.76 4.30 C, wt% C
120 mm
Result: Pearlite = Fe3C (cementite-hard)
alternating layers of
a and Fe3C phases a (ferrite-soft)
29
 Hypoeutectoid Steel
T(ºC)
1600
d (Fe-C System)
1400 L
g g g g +L
g g 1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
g g 1000
g g g + Fe3C
a
a g
g 800 727ºC
g ag a
600
a + Fe3C
400
a 0 1 2 3 4 5 6 6.7
(Fe)C C, wt% C
0.76

pearlite

100 mm Hypoeutectoid
steel

pearlite proeutectoid ferrite 30

Adapted from Fig. 9.30, Callister & Rethwisch 8e.
 Hypoeutectoid Steel
T(ºC)
1600
d
1400 L
(Fe-C
a g g +L
System)
ag g 1200 1148ºC L+Fe3C

Fe3C (cementite)
(austenite)
g ag
1000
g + Fe3C
Wa = s/(r + s)
800 r s 727ºC
Wg =(1 - Wa)
a RS
600
a a + Fe3C
pearlite
400
0 1 2 3 4 5 6 6.7
(Fe)C C, wt% C
0.76

Wpearlite = Wg
Wa’ = S/(R + S) 100 mm Hypoeutectoid
steel
WFe3C =(1 – Wa’)
pearlite proeutectoid ferrite 31
Adapted from Fig. 9.30, Callister & Rethwisch 8e.
 Hypereutectoid Steel
T(ºC)
1600
d
1400 L (Fe-C system)
g g g g +L
1200 L+Fe3C
gg 1148ºC

Fe3C (cementite)
(austenite)
g g 1000
gg g +Fe3C
Fe3C
gg 800
gg a
600
a +Fe3C
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
pearlite

60 mmHypereutectoid
steel
pearlite proeutectoid Fe3C
32
Adapted from Fig. 9.33, Callister & Rethwisch 8e.
 Hypereutectoid Steel
T(ºC)
1600
d
1400 L (Fe-C system)

Fe3C g g +L
1200 L+Fe3C
gg 1148ºC

Fe3C (cementite)
(austenite)
gg 1000
g +Fe3C
Wg =x/(v + x)
800 v x
W Fe3C =(1-Wg)
a V X
600
a +Fe3C
pearlite
400
0 1 C0 2 3 4 5 6 6.7
0.76

(Fe) C, wt%C
Wpearlite = Wg
Wa = X/(V + X)
60 mmHypereutectoid
WFe C’ =(1 - Wa) steel
3
pearlite proeutectoid Fe3C
33
Adapted from Fig. 9.33, Callister & Rethwisch 8e.
 Example Problem
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 ().
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite () in the 100 g.
34
Solution to Example Problem
a) Using the RS tie line just below the eutectoid
Ca = 0.022 wt% C
CFe3C = 6.70 wt% C
b) Using the lever rule with 1600
the tie line shown d
1400 L
T(ºC) g+L
g

Fe C (cementite)
1200 1148ºC L+Fe3C
(austenite)
1000
g + Fe3C
800 727ºC
R S
Amount of Fe3C in 100 g 600 a + Fe3C
= (100 g)WFe3C 400
0 1 2 3 4 5 6 6.7
C C0 C , wt% C CFe
3C
= (100 g)(0.057) = 5.7 g 35
 Solution to Example Problem (cont.)
c) Using the VX tie line just above the eutectoid and
realizing that
C0 = 0.40 wt% C
Ca = 0.022 wt% C
Cpearlite = C = 0.76 wt% C 1600
d
1400 L
T(ºC) g+L
g

Fe C (cementite)
1200 1148ºC L+Fe3C
(austenite)
1000
g + Fe3C
800 727ºC
VX
Amount of pearlite in 100 g 600 a + Fe3C
= (100 g)Wpearlite 400
0 1 2 3 4 5 6 6.7
C C C C, wt% C
0
= (100 g)(0.512) = 51.2 g 36
 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.

37
 VMSE: Interactive Phase Diagrams
Microstructure, phase compositions, and phase fractions respond interactively

38
Change alloy composition
 Alloying with Other Elements

• Teutectoid changes: • Ceutectoid changes:

Ceutectoid (wt% C)
Ti Si
T Eutectoid (ºC)

Mo W Ni
Cr
Cr Si
Mn
Mn W
Ti Mo
Ni

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

39
Komponen dan fasa, batas kelarutan,
diagram fasa, kesetimbangan fasa,
sistim biner, sistim terner, aturan
Lever, komposisi fasa
mikrostruktur campuran isomorfi,
sistim eutetic, mikro struktur dalam
campuran eutetic
In general, for a mixture of two or more pure elements, there are two types of solid– solution
alloys that may be obtained. Type I alloys are completely miscible with one another in both
liquid and solid states. As long as the Hume-Rothery rules are satis- fied, a random
substitutional alloy will be produced. We will see many examples of these alloys in this section
for a variety of metal dopants in stainless steels. By com- parison, type II alloys are only
miscible in the molten state, and will separate from one another upon cooling. These alloys
are usually associated with compound forma- tion from the alloying of metals or
metals/nonmetals that are too dissimilar in their reactivities (e.g., Cu and Al to form
CuAl2 precipitates). The eutectic composition is the lowest melting point of type II
alloys.
Type I alloys contain two types of atoms that are arranged within a single lattice. When
solidification of the solution begins, the temperature may be higher or lower than the
freezing point of the pure solvent. Unlike a pure molten metal, most solid solutions will
solidify over a temperature range due to differing diffusion rates of the metals en route
toward their preferred crystal arrangement (Figure 3.8).
 Sifat Material - Jenis/tipe - logam
- Jumlah - keramik
- Bentuk - polimer
- komposit

Fasa
( seragam keadaan fisik dan komposisi kimia)

Berubah bdskan perubahan jumlah

- Keadaan awal
- Keadaan saat terjadi perubahan

Diagram Fasa/
Diagram Eguilibrium
Diagram kontitusional
Diagram Fasa Variabel Dikontrol

- Temperatur
Komponen - Tekanan (konstan 1 atm)
- Komposisi

Perubahan Struktur Temperatur vs Komposisi

Keadaan Setimbang

Pemanasan & Pendinginan Sangat Lambat

(Heating & Cooling)
Waktu

Temperatur vs Waktu
Contoh diagram fasa

Data untuk membuat diagram fasa ditentukan berdasarkan eksperimen

dengan metoda tertentu. Metoda yang biasa digunakan adalah:

1. Metalografi (Metalographic Methods)

2. Difraksi Sinar X ( X – Ray Diffraction Technique)
3. Analisis Thermal (Thermal Analysis )
Metallographic Methods:

This method is applied by heating samples of an alloy to different

temperatures, waiting for equilibrium to be established, and then quickly
cooling to retain their high-temperature structure. The samples then examined
microscopically. This method is difficult to apply to metals at high
temperatures because the rapidly cooled samples do not always retain their
high-temperature structure, and considerable skill is then required to interpret
the observed microstructure correctly.

X-ray Diffraction Technique:

This method is applied by measuring the lattice dimensions and indicating the
appearance of a new phase either by the change in lattice dimension or by the
appearance of a new crystal structure. This method is very precise and very
useful in determining the changes in solid solubility with temperature.

Thermal Analysis:

This is by far the most widely used experimental method. It relies on the
information obtained from the cooling diagrams. In this method, alloys mixed
at different compositions are melted and then the temperature of the mixture is
measured at a certain time interval while cooling back to room temperature.
 Cooling Curve Diagrams
A cooling diagram for each mixture is constructed and the initial and final
phase change temperatures are determined. Then these temperatures are used
for the construction of the phase diagrams.

Cooling Curve of a Pure Metal ( 1 component )

Under equilibrium conditions, all metals exhibit a definite melting or freezing

point. If a cooling curve is plotted for a pure metal, It will show a horizontal line
at the melting or freezing temperature.

Cooling curve for the solidification of a pure metal.

Cooling Curve of a Solid Solution ( 2 component)

A solid solution is a solution in the solid state and consists of two kinds of
atoms combined in one type of space lattice. A solution is composed of two
parts: a solute and a solvent. The solute is the minor part of the solution or the
material which is dissolved, while the solvent constitutes the major portion of
the solution. When solidification of the solution starts, the temperature may be
higher or lower than the freezing point of the pure solvent. Most solid solutions
solidify over a range in temperature.

Cooling curve for a solid solution.

COOLING CURVES FOR DIFFERENT ALLOYS IN A COMPLETELY
SOLUBLE SYSTEM.
Phase Diagram of alloy A+B