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...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?

Phase A Phase B

Nickel atom
Copper atom
ESO205: Nature & Properties of Materials Instructor: Dr. Anish Upadhyaya
 THE SOLUBILITY LIMIT
• Solubility Limit: 100
Max concentration for Solubility

Temperature (°C)
which only a solution 80 Limit L
(liquid)
occurs. 60 +
L
• Ex: Phase Diagram: 40 (liquid solution S
i.e., syrup) (solid
Water-Sugar System 20 sugar)
Question: What is the
solubility limit at 20C? 0 20 40 6065 80 100

Sugar
Water
Co=Composition (wt% sugar)

Pure

Pure
Answer: 65wt% sugar.
If Co < 65wt% sugar: sugar
If Co > 65wt% sugar: syrup + sugar.

• Solubility limit increases with T:

e.g., if T = 100C, solubility limit = 80wt% sugar.
 COMPONENTS AND PHASES
• Components:
The elements or compounds which are mixed initially
(e.g., Al and Cu)
• Phases:
The physically and chemically distinct material regions
that result (e.g.,  and ).

Aluminum-  (lighter
Copper
phase)
Alloy

(darker
phase)
 EFFECT OF T & COMPOSITION (Co)
• Changing T can change # of phases: path A to B.
• Changing Co can change # of phases: path B to D.
B(100,70) D(100,90)
1 phase 2 phases
100
L
Temperature (°C)

• water- 80
(liquid)
sugar +
system 60 L S
(liquid solution (solid
40 i.e., syrup) sugar)
20 A(70,20)
2 phases
0
0 20 40 60 70 80 100
Co=Composition (wt% sugar)
P-T Diagram of Single-Component System

e.g. H2O e.g. Fe

Free-Curves for the Phases in a One-Component System
Corresponding to Three Different Pressures
Determination of Phase Diagram by Thermal Analysis

• Binary Isomorphous System

 PHASE DIAGRAMS
• Tell us about phases as function of T, Co, P.
• For this course:
--binary systems: just 2 components.
--independent variables: T and Co (P = 1atm is always used).
T(°C)
• Phase
1600 • 2 phases:
Diagram L (liquid)
1500 L (liquid)
for Cu-Ni  (FCC solid solution)
system 1400 • 3 phase fields:
u s
u d
i  L
q
L +lidus
1300 li L + 
so 
1200 
1100
(FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni
PHASE DIAGRAMS: # and types of phases
• Rule 1: If we know T and Co, then we know:
--the # and types of phases present.

T(°C)
• Examples: 1600
A(1100, 60):
1500 L (liquid)
1 phase:  u s Cu-Ni

B(1250,35)
u id
B(1250, 35): 1400 liq us phase
2 phases: L +  o lid diagram
s
1300 +  
L (FCC solid
1200 solution)
1100 A(1100,60)

1000
0 20 40 60 80 100 wt% Ni
 PHASE DIAGRAMS: composition of phases
• Rule 2: If we know T and Co, then we know:
--the composition of each phase.
Cu-Ni
T(°C) system
• Examples:
TA A
Co = 35wt%Ni tie line dus
i
At TA: 1300 L (liquid) liqu
+ 
Only Liquid (L) B L s
o lidu
CL = Co ( = 35wt% Ni) TB s

 
At TD: +
1200 L D (solid)
Only Solid () TD
C = Co ( = 35wt% Ni)
20 3032 35 4043 50
At TB: CLCo C wt% Ni
Both  and L
CL = Cliquidus ( = 32wt% Ni here)
C = Csolidus ( = 43wt% Ni here)
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%).
Cu-Ni
• Examples: system
T(°C)
Co = 35wt%Ni
TA A
tie line dus
At TA: Only Liquid (L) i
1300 L (liquid) liqu
WL = 100wt%, W = 0 + 
B L s
At TD: Only Solid () ol idu
TB R S
s
WL = 0, W = 100wt%
+  
At TB: Both  and L 1200 L D
TD (solid)
S 43  35
WL     73wt % 20 3032 35 4043 50
R S 43  32 CLCo C
wt% Ni
R
W   = 27wt%
R S
 THE LEVER RULE: A PROOF
• Sum of weight fractions: WL  W  1
• Conservation of mass (Ni): Co  WL CL  W C
• Combine above equations:
 C  Co  S Co  CL  R
WL W 
C  CL R S C  CL R  S

• A geometric interpretation:
Co moment equilibrium:
CL C
WLR  WS
R S

WL W 1 W
solving gives Lever Rule
 COOLING IN A Cu-Ni BINARY
• Phase diagram: T(°C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• System is: system
1300 A + 
--binary L: 35wt%Ni L
: 46wt%Ni B
i.e., 2 components: 35 46
32 C
Cu and Ni. 43
--isomorphous 24 D
36 L: 32wt%Ni
i.e., complete  : 43wt%Ni
solubility of one 1200
L + E
L: 24wt%Ni
component in
another;  phase : 36wt%Ni

field extends from (solid)
0 to 100wt% Ni.
• Consider 1100
Co = 35wt%Ni. 20 30 35 40 50
Co wt% Ni
Instructor: Dr. Anish Upadhyaya
 CORED VS EQUILIBRIUM PHASES
• C changes as we solidify.
• Cu-Ni case: First  to solidify has C = 46wt%Ni.
Last  to solidify has C = 35wt%Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C:
First  to solidfy:
46wt%Ni 35wt%Ni
Last  to solidfy:
< 35wt%Ni

Instructor: Dr. Anish Upadhyaya

MECHANICAL PROPERTIES: Cu-Ni System
• Effect of solid solution strengthening
on:
--Tensile strength (TS) --Ductility (%EL,%AR)
Tensile Strength (MPa)

60

Elongation (%EL)
%EL for pure Cu
400 %EL for
50
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

 BINARY-EUTECTIC SYSTEMS
has a special composition
2 components with a min. melting T.
T(°C)
Ex.: Cu-Ag system 1200
• 3 single phase regions L (liquid)
(L, ) 1000
• Limited solubility:  L +  L+
T 800 779°C
: mostly Cu E 8.0 71.9 91.2
: mostly Ni 600
• TE: No liquid below TE 
• CE: Min. melting T 400

composition 200
0 20 40 60 CE 80 100
Co, wt% Ag

Cu-Ag System
Determination of Phase Diagram by Thermal Analysis

• Binary Eutectic System

Pb-Sn Phase Diagram
 Pb-Sn EUTECTIC SYSTEM (1)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present:  + 
--the compositions of the phases:
T(°C)

300
L (liquid)

200  L +  183°C L+ 

Pb-Sn System 18.3 61.9 97.8
150
100 

0 20 40 60 80 100
Co
Co, wt% Sn
 Pb-Sn EUTECTIC SYSTEM (2)
• For a 40wt%Sn-60wt%Pb alloy at 150C, find...
--the phases present:  + 
--the compositions of T(°C)
the phases:
C = 11wt%Sn 300
L (liquid)
C = 99wt%Sn
--the relative amounts 200  L +  183°C L+ 
of each phase: 18.3 61.9 97.8
150
59 R S
W  67wt % 100
88 
29
W  33wt %
88 0 11 20 40 60 80 99100
Co
Co, wt% Sn

Pb-Sn System
MICROSTRUCTURES IN EUTECTIC SYSTEMS-I
• Co < 2wt%Sn
• Result: --polycrystal of 
grains. T(°C) L: Cowt%Sn
400
L

300 L

L+

200
TE (Pb-Sn
: Cowt%Sn
System)

100
+

0 10 20 30
Co Co, wt% Sn
2
(room T solubility limit)
MICROSTRUCTURES IN EUTECTIC SYSTEMS-II
• 2wt%Sn < Co < 18.3wt%Sn
• Result: -- polycrystal with fine 
crystals. T(°C) L: Cowt%Sn
400
L
L
300 
L+
: C owt%Sn

Pb-Sn System 200
TE


100
+

0 10 20 30
2 Co Co, wt% Sn
(sol. limit at Troom) 18.3
(sol. limit at TE)
MICROSTRUCTURES IN EUTECTIC SYSTEMS-III
• Co = CE
• Result: Eutectic microstructure
— alternating layers of  and  crystals.
T(°C)
L: Cowt%Sn Micrograph of Pb-Sn
300 L eutectic
microstructure
L+
200
TE  183°C L+ 

100 +
: 97.8wt%Sn
: 18.3wt%Sn 160m
0
0 20 40 60 80 100
18.3 CE 97.8
61.9 Co, wt% Sn
Pb-Sn System
MICROSTRUCTURES IN EUTECTIC SYSTEMS-IV

• 18.3wt%Sn < Co < 61.9wt%Sn

• Result:  crystals and a eutectic microstructure
• Just above TE:
T(°C) L: Cowt%Sn  L
C = 18.3wt%Sn
L
300 L  CL = 61.9wt%Sn
S
L+ W = =50wt%
R+S
200  R S L+  WL = (1-W) =50wt%
TE
R S
• Just below TE:
100
+ C = 18.3wt%Sn
primary 
eutectic  C = 97.8wt%Sn
0
0 20 40 60 80 100
eutectic 
W = S =73wt%
18.3 Co 61.9 97.8 R+S
Co, wt% Sn W = 27wt%
HYPOEUTECTIC & HYPEREUTECTIC
Pb-Sn System
T(°C)
300 L

L+
200
TE  L+ (Pb-Sn

 +  System)
100

Co Co
hypoeutectic hypereutectic
0 Co, wt% Sn
0 20 40 60 80 100
18.3 eutectic 97.8
61.9
hypoeutectic: Co=50wt%Sn hypereutectic: (illustration only)

eutectic: Co=61.9wt%Sn
 
 
   
 
 
175m 160m
eutectic micro-constituent
Phase Transformation in Pb-Sn
Pb-Sn Alloy: Hypo-Eutectic Composition
Pb-Sn Alloy: Eutectic Composition
Ice-Brine Phase Diagram
Peritectic System
Peritectoid System
Eutectoid System
Montectic System
Syntectic System
Congruent Melting System
Congruent Melting System
Compounds in Binary System
Compounds in Binary System
Cu-Zn Phase Diagram
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
 + B 727°C = Teutectoid

R S
600
+Fe3C
400
0 1 2 3 4 5 6 6.7
(Fe) 0.77 4.30 Co, wt% C
120m
Ceutectoid

Result: Pearlite = Fe3C (cementite-hard)

alternating layers of
 and Fe3C phases. (ferrite-soft)
 HYPOEUTECTOID STEEL
T(°C)
1600

1400 L
(Fe-C
   +L System)
  1200 1148°C L+Fe3C
austenite)

Fe3C (cementite)
  1000
  +Fe3C
 r s
  800 727°C
  RS
w =s/(r+s) 600 +Fe3C
w =(1-w )
400
0 Co 1 2 3 4 5 6 6.7
0.77


 pearlite Co, wt% C
 wpearlite = w
w =S/(R+S) 100m
Hypoeutectoid
wFe3C =(1-w ) steel
 HYPEREUTECTOID STEEL
T(°C)
1600

1400 L
(Fe-C
   +L System)
  1200 1148°C L+Fe3C
austenite)

Fe3C (cementite)
  1000
  +Fe3C
Fe3C
  800 r s
   R S
wFe3C =r/(r+s)600 +Fe3C
w =(1-w Fe3C)
400
0 1 2 3 4 5 6 6.7
0.77

Co
pearlite Co, wt% C
wpearlite = w
w =S/(R+S) 60m Hypereutectoid
wFe3C =(1-w ) steel
 ALLOYING STEEL WITH MORE ELEMENTS

• Teutectoid changes: • Ceutectoid changes:

Ceutectoid (wt%C)
0.8
TEutectoid (°C)

1200 Ti Si
Mo W 0.6 Ni
1000 Cr
Cr 0.4
Si
800 Mn
Mn 0.2 W
Ti Mo
600 Ni
0
0 4 8 12 0 4 8 12
wt. % of alloying elements wt. % of alloying elements
 SUMMARY
• Phase diagrams are useful tools to determine:
--the number and types of phases,
--the wt% of each phase,
--and the composition of each phase
for a given T and composition of the system.
• Alloying to produce a solid solution usually
--increases the tensile strength (TS)
--decreases the ductility.
• Binary eutectics and binary eutectoids allow for
a range of microstructures.