Phase diagram my new

lecture
Lecture 4 phase diagram
 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
 Components and Phases
• Components:
The elements or compounds which are present in the mixture
(e.g., Al and Cu)
• Phases:
The combination of two or more elements in specific form to
consist a certain region of material with distinct physical and
chemical properties. (e.g., α and β).

β (lighter
phase)
Aluminum-
Copper α (darker
Alloy
phase)
Adapted from
chapter-opening
photograph,
Chapter 9,
Callister 3e.
 Phase Equilibria: Solubility Limit
– Solutions – solid solutions, single phase
– Mixtures – more than one phase Adapted from Fig. 9.1,
Callister 7e.

Sucrose/Water Phase Diagram

• Solubility Limit: 100
Max concentration for Solubility

Temperature (°C)
which only a single phase 80 Limit L
solution occurs. (liquid)
60 +
L
Question: What is the 40 (liquid solution S
solubility limit at 20°C? i.e., syrup) (solid
20 sugar)
Answer: 65 wt% sugar.
If Co < 65 wt% sugar: syrup 0 20 40 6065 80 100
If Co > 65 wt% sugar: syrup + sugar.

Sugar
Water

Co =Composition (wt% sugar)

Pure
Pure
 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°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
Adapted from 0
Fig. 9.1, 0 20 40 60 70 80 100
Callister 7e.
Co =Composition (wt% sugar)
 Definition and types of phase
diagrams
• Phase diagrams;
indicate phases as function of Temp (T) ,
Composition (C0), and Pressure (P).

- just 2 components in phases diagrams wil be studied in this course.

- independent variables are: T and Co only while (P = 1 atm is
constant, almost always used).

• Types of phase diagrams

• 1- Solid solution type
• 2- Simple eutectic type
• 3- Binary or combination eutectic type
 Methods of construction phase
diagrams
• 1- From cooling curve
• 2- By high temperature X-ray diffraction
measurement
• 3- From thermal expansion curves
(Dilatometer).
• 4- By high temperature microscopy.
• 5- From electrical resistivity
measurements
1- solid solution type of Phase diagram
Solid solution system: the two elements dissolve in each
other with any percentages (e.g., Ni-Cu solution)

Crystal electronega r (nm)

Structure tivity

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.

1- solid solution type of Phase diagram
cont.
T(°C)
1600 Present phases:
L (liquid)
1500 L (liquid) α (FCC solid solution)
1400
• Phase us
i d
Diagram 1300 il qu + α L+α
L lidus
for Cu-Ni so
1200 α
system
1100 (FCC solid
solution)
1000
0 20 40 60 80 100 wt% Ni
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH (1991).
Cu
Cooling curve of pure metal
Construction of phase diagram from series
of cooling curves
1- solid solution type of Phase diagram cont.
Number and types of phases
• Rule 1: If we know T and Co, then we know:
--the nomber and types of phases present.
T(°C)
• Examples: 1600
A(1100°C, 60): L (liquid)
1500

B (1250°C,35)
1 phase: α s Cu-Ni
du
ui phase
B(1250°C, 35): 1400 liq us
li d
2 phases: L + α so diagram
1300 +α α
L (FCC solid
1200 solution)
Adapted from Fig. 9.3(a), Callister 7e.
(Fig. 9.3(a) is adapted from Phase 1100 A(1100°C,60)
Diagrams of Binary Nickel Alloys, P. Nash
(Ed.), ASM International, Materials Park,
OH, 1991). 1000
0 20 40 60 80 100 wt% Ni
1- solid solution type of Phase diagram
cont.
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 = 35 wt% Ni tie line dus
l i qui
At T A = 1320°C: 1300 L (liquid)
L +α
Only Liquid (L) B s
T li du
CL = Co ( = 35 wt% Ni) B s o
α α
At T D = 1190°C:
1200 L+ D (solid)
Only Solid ( α) TD
Cα = Co ( = 35 wt% Ni)
20 3032 35 4043 50
At T B = 1250°C: CLCo Cα wt% Ni
Both α and L Adapted from Fig. 9.3(b), Callister 7e.
CL = C liquidus ( = 32 wt% Ni here) (Fig. 9.3(b) is adapted from Phase Diagrams
of Binary Nickel Alloys, P. Nash (Ed.), ASM
Cα = C solidus ( = 43 wt% Ni here) International, Materials Park, OH, 1991.)
 1- solid solution type of Phase diagram
cont.
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: T(°C) system
Co = 35 wt% Ni A
TA tie line dus
At T A : Only Liquid (L) l i qui
1300 L (liquid)
W L = 100 wt%, W α = 0 + α
B L
s
At T D: Only Solid ( α) TB o li du
R S s
W L = 0, Wα = 100 wt% α α
1200 L+ D (solid)
At T B : Both α and L TD
S 43 − 35
WL = = = 73 wt % 20 3032 35
CLCo
40 43 50
R + S 43 − 32 Cα wt% Ni
Adapted from Fig. 9.3(b), Callister 7e.
R (Fig. 9.3(b) is adapted from Phase Diagrams of
Wα = = 27 wt% Binary Nickel Alloys, P. Nash (Ed.), ASM
R +S International, Materials Park, OH, 1991.)
 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 dus
liqu
i Think of it as a lever (teeter-totter)
1300 L (liquid)
+ α Mα
L ML
B us
TB id
s ol
α
L +α (solid)
1200
R S R S
20 30C C 40 C 50
L o α M α ⋅S = M L ⋅R
wt% Ni
Prove of Lever Rule
 Example
• Find the types, composition and weight
fraction of phases present at the points’
A,B,C,D,E shown in the figure, during
cooling in a Cu-Ni Binary
 Solution
• Phase diagram: T(°C) L (liquid) L: 35wt%Ni
Cu-Ni system. Cu-Ni
• System is: system
1300 A + α
--binary L: 35 wt% Ni L
i.e., 2 components: α: 46 wt% Ni
35 B
46
Cu and Ni. 32 C 43
--isomorphous 24 D
36 L: 32 wt% Ni
i.e., complete α α: 43 wt% Ni
solubility of one 120 0
L + E
L: 24 wt% Ni
component in
another; α phase α: 36 wt% Ni
α
field extends from (solid)
0 to 100 wt% Ni.
• Consider 110 0
Co = 35 wt%Ni. 20 30 35 40 50
Adapted from Fig. 9.4, Co wt% Ni
Callister 7e.
 Cored vs Equilibrium Phases
• Cα changes as we solidify.
• Cu-Ni case: First α to solidify has Cα = 46 wt% Ni.
Last α to solidify has Cα = 35 wt% Ni.
• Fast rate of cooling: • Slow rate of cooling:
Cored structure Equilibrium structure
Uniform C α:
First α to solidify:
46 wt% Ni 35 wt% Ni
Last α to solidify:
< 35 wt% Ni
 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 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
Adapted from Fig. 9.6(a), Callister 7e. Adapted from Fig. 9.6(b), Callister 7e.

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