Lecture 14.

Phase Diagrams (1)

Learning Objectives

After this lecture, you should be able to do the following:

1. Understand terminology associated with phase diagrams and

interpretate phase diagrams.
2. Sketch isomorphous phase diagrams and label the various regions
and liquidus, solidus, and solvus lines.
3. Given a binary phase diagram, the composition of an alloy, and its
temperature, determine what phases are present, the compositions of
the phases, and the mass fractions of the phases.

Reading
Chapter 9: Phase Diagrams (9.19.10)

Multimedia
Virtual Materials Science & Engineering (VMSE):
http://www.wiley.com/college/callister/CL_EWSTU01031_S/vmse/
MSE 3300 / 5300 UTA Spring 2015

Lecture 14 - 1

1. Definitions and Basic Concepts

Components: pure metals and/or compounds of which an alloy is composed

(e.g., in a copperzinc brass, Cu and Zn).
Solute and solvent
System: (1) a specific body of material under consideration and (2) the series
of possible alloys consisting of the same components, but without regard to
alloy composition (e.g., the ironcarbon system).

Solubility limit: maximum

concentration of solute
atoms that may dissolve in
the solvent to form a solid
solution.

Figure 9.1: The solubility of

sugar in a sugarwater syrup.

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Lecture 14 - 2

Phases

Phase: a homogeneous portion of a system that has uniform physical and

chemical characteristics (e.g., phase 1: sugarwater syrup solution; phase 2:
solid sugar).
Single-phase system: homogeneous system
Systems with two or more phases: mixtures or heterogeneous systems

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Equilibrium: The free energy of a

system is at a minimum under
some specified combination of
temperature, pressure, and
composition; the characteristics of
the system do not change (or the
system is stable).
Phase equilibrium: a constancy
with time in the phase
characteristics of a system (sugar
water syrup in contact with solid
sugar at 20 C).
Metastable state (Non-equilibrium)

Lecture 14 - 3

Phase Equilibria: Solubility Limit

Solution solid, liquid, or gas solutions, single phase
Mixture more than one phase
Adapted from Fig. 9.1,

Callister & Rethwisch 9e.

Sugar/Water Phase Diagram

Question: What is the

solubility limit for sugar in

water at 20C?

Answer: 65 wt% sugar.

80
60
40
20

syrup + sugar

Water

At 20C, if C < 65 wt% sugar: syrup

At 20C, if C > 65 wt% sugar:

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Solubility
Limit

(liquid solution
i.e., syrup)

(liquid)

+
S

(solid
sugar)

20
40
6065 80
100
C = Composition (wt% sugar)

Sugar

Maximum concentration for

which only a single phase
solution exists.

10 0

Temperature (C)

Solubility Limit:

Lecture 14 - 4

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., and ).

AluminumCopper
Alloy

Adapted from chapteropening photograph,

Chapter 9, Callister,
Materials Science &
Engineering: An
Introduction, 3e.

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(lighter
phase)
(darker
phase)

Lecture 14 - 5

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 (100C,C = 70)D (100C,C = 90)
1 phase

watersugar
system

Temperature (C)

100

Fig. 9.1, Callister &

Rethwisch 9e.

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80

(liquid)

60

(liquid solution

40

i.e., syrup)

+
S

(solid
sugar)

A (20C,C = 70)

20
0

2 phases

2 phases

20
40
60 70 80
100
C = Composition (wt% sugar)
Lecture 14 - 6

2. One-component (or Unary)

Phase Diagrams

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Lecture 14 - 7

3. Binary Isomorphous Systems

Binary Isomorphous Systems: coppernickel system

Isomorphous: the complete liquid and solid solubility of the two components

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Lecture 14 - 8

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.
MSE 3300 / 5300 UTA Spring 2015

Lecture 14 - 9

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).

Phase
Diagram
for Cu-Ni
system

L (liquid)

(FCC solid
solution)
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2 phases:

L (liquid)
(FCC solid solution)

3 different phase fields:

L
L+

Lecture 14 - 10

Isomorphous Binary Phase Diagram

Phase diagram:

T(C)

System is:

1500

Cu-Ni system.

-- binary

i.e., 2 components:
Cu and Ni.

-- isomorphous

i.e., complete
solubility of one
component in
another; phase
field extends from
0 to 100 wt% Ni.

1600

L (liquid)

Cu-Ni
phase
diagram

1400
1300

(FCC solid
solution)

1200
1100
1000

20

40

60

80

100

wt% Ni

Fig. 9.3(a), Callister & Rethwisch 9e.

(Adapted from Phase Diagrams of Binary

Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
Park, OH.)

MSE 3300 / 5300 UTA Spring 2015

Lecture 14 - 11

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(C)
1600

L (liquid)
B (1250C,35)

A(1100C, 60 wt% Ni):

1500
1 phase:
B (1250C, 35 wt% Ni): 1400
2 phases: L +
1300
1200
Fig. 9.3(a), Callister & Rethwisch 9e.

(Adapted from Phase Diagrams of Binary

Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
Park, OH.)

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(FCC solid
solution)
A(1100C,60)

1100
1000

Cu-Ni
phase
diagram

20

40

60

80

100

wt% Ni
Lecture 14 - 12

Determination of Phase
Composition
1. A tie line is constructed
across the two-phase
region at the temperature of
the alloy.
2. The intersections of the tie
line and the phase
boundaries on either side
are noted.
3. Perpendiculars are dropped
from these intersections to
the horizontal composition
axis, from which the
composition of each of the
respective phases is read.

MSE 3300 / 5300 UTA Spring 2015

Lecture 14 - 13

Phase Diagrams:

Determination of phase compositions

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

-- the composition of each phase.

Examples:

Consider C0 = 35 wt% Ni
At TA = 1320C:
Only Liquid (L) present
CL = C0 ( = 35 wt% Ni)
At TD = 1190C:
Only Solid () present
C = C0 ( = 35 wt% Ni)
At TB = 1250C:
Both and L present
CL = C liquidus ( = 32 wt% Ni)
C = C solidus ( = 43 wt% Ni)

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Cu-Ni
system

T(C)
TA
1300

TB
1200
TD
20

L (liquid)

tie line

B
D
3032 35

C L C0

(solid)
4043

50

C wt% Ni

Fig. 9.3(b), Callister & Rethwisch 9e.

(Adapted from Phase Diagrams of Binary

Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
Park, OH.)

Lecture 14 - 14

Determination of Phase Amounts:

Lever Rule

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Lecture 14 - 15

Phase Diagrams:

Determination of phase weight fractions

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

-- the weight fraction of each phase.

Examples:
Consider C0 = 35 wt% Ni

At TA : Only Liquid (L) present

WL = 1.00, W = 0
At TD : Only Solid ( ) present
WL = 0, W = 1.00
At TB : Both and L present

WL =
W =

S
R +S
R
= 0.27
R +S

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Cu-Ni
system

T(C)
TA
1300

TB
1200
TD
20

L (liquid)

tie line

B
R S
D
3 032 35

C L C0

(solid)

4 0 43

50

C wt% Ni

Fig. 9.3(b), Callister & Rethwisch 9e.

(Adapted from Phase Diagrams of Binary

Nickel Alloys, P. Nash, Editor, 1991. Reprinted
by permission of ASM International, Materials
Park, OH.)

Lecture 14 - 16

The Lever Rule

Tie line connects the phases in equilibrium with
each other also sometimes called an isotherm
T(C)
1300

tie line

L (liquid)
B

TB
1200
20

R
3 0CL

What fraction of each phase?

Think of the tie line as a lever
(teeter-totter)

(solid)

50
C0 4 0 C
Adapted from Fig. 9.3(b),

wt% Ni

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ML

Callister & Rethwisch 9e.

Lecture 14 - 17

Equilibrium Colling

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Lecture 14 - 18

Ex: Cooling of a Cu-Ni Alloy

Phase diagram:
Cu-Ni system.

Consider
microstuctural
changes that
accompany the
cooling of a

T(C)L (liquid)
130 0
L: 35 wt% Ni
: 46 wt% Ni

C0 = 35 wt% Ni alloy

L: 35 wt%Ni

Cu-Ni
system

A
32

35

B
C

43

24

46
L: 32 wt% Ni

36

120 0

: 43 wt% Ni

L: 24 wt% Ni
: 36 wt% Ni

(solid)
110 0
20

30

Adapted from Fig. 9.4,

Callister & Rethwisch 9e.
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: 35 wt% Ni

35
C0

40

50

wt% Ni
Lecture 14 - 19

Nonequilibrium Colling
Equilibrium

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Nonequilibrium

Lecture 14 - 20

Equilibrium vs Cored Structures

C changes as we solidify.
Cu-Ni case: First to solidify has C = 46 wt% Ni.
Last to solidify has C = 35 wt% Ni.

Slow rate of cooling:

Equilibrium structure

Uniform C:
35 wt% Ni

Fast rate of cooling:

Cored structure

First to solidify:
46 wt% Ni
Last to solidify:
< 35 wt% Ni

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Lecture 14 - 21

Summary
1. Definitions and basic concepts: phases, phase
equilibrium, phase diagrams
2. One-component phase diagrams
3. Phase diagrams: Binary isomorphous systems

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Lecture 14 - 22