LECTURE 2

PHASE DIAGRAMS
 TWO-COMPONENTS (OR BINARY)
PHASE DIAGRAMS
 These diagrams constitutes two components, e.g.: two
metals (Cu and Ni), or a metal and a compound (Fe and
 Fe3C),
Binary or two compounds
phase diagrams are (Al2O3
maps and
thatSi2O3), etc.the
represent
relationships between temperature and the
compositions (at constant pressure, 1 atm) and
quantities of phases at equilibrium, which influence the
BINARY microstructure of an alloy.
SYSTEMS ARE CLASSIFICATION
Binary systems are classified according to their solid
solubility.
a) Binary Isomorphous System
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.
b) Binary Eutectic System
Many binary systems have components which have limited solid
solubility, e.g.: Cu-Ag, Pb-Sn.
 BINARY ISOMORPHOUS SYSTEM
• Indicate phases as a function of T, C, and P.
• For this discussion:
- binary systems: 2 components.
- independent variables: T and C (P = 1 atm is almost always used).
Phase T(ºC)
Diagram 1600 • 2 phases:
for Cu-Ni L (liquid)
1500 L (liquid)
system a (FCC solid solution)
1400 • 3 different phase fields:
id us L
u a
1300 liq
L +lidus L+a
so a
1200 a Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
1100
(FCC solid Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
solution) Materials Park, OH (1991).
1000
3 0 20 40 60 80 100 wt% Ni
 BINARY ISOMORPHOUS SYSTEM
• Phase diagram: T(ºC) Melting
1600 Pt of Ni
Cu-Ni system.
-- isomorphous 1500 L (liquid) Cu-Ni
i.e., complete
solubility of one 1400 phase
component in us diagram
uid a
another; a phase 1300 liq
field extends from L +lidus
0 to 100 wt% Ni. so
1200 a
1100
(FCC solid
Melting
Pt of
solution)
Cu 1000
Liquidus 0 20 40 60 80 100 wt% Ni
line separates liquid from liquid +
solid Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
Solidus Phase Diagrams of Binary Nickel Alloys,
line separates solid from liquid + P. Nash (Ed.), ASM International,
4solid Materials Park, OH (1991).
 Ni & Cu SOLID SOLUBILITY

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

Crystal electroneg r (nm)

Structure
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.

5
 INTERPRETATION OF PHASE DIAGRAM

For a binary system of known composition and

temperature that is at equilibrium, at least
three kinds of information are available:

(1)The phases that are present

(2) The compositions of these phases

(3) The percentages or fractions of the

phases.
 DETERMINATION OF PHASE(S) PRESENT

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

-- which phase(s) is (are) present.
T(ºC)
• Examples: 1600
A(1100ºC, 60 wt% Ni): L (liquid)
1500

B (1250ºC,35)
1 phase: a s
idu Cu-Ni
B(1250ºC, 35 wt% Ni): 1400 il qu phase
id us
2 phases: L + a so
l diagram
1300 a
L+ a
(FCC solid
1200
Adapted from Fig. 9.3(a), Callister &
solution)
Rethwisch 8e. (Fig. 9.3(a) is adapted from 1100 A(1100ºC,60)
Phase Diagrams of Binary Nickel Alloys,
P. Nash (Ed.), ASM International,
Materials Park, OH (1991). 1000
0 20 40 60 80 100 wt% Ni
7
 DETERMINATION OF PHASE COMPOSITIONS

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

-- the composition of each phase. Cu-Ni
T(ºC) system
• Examples:
TA A
Consider C0 = 35 wt% Ni tie line dus
l iqui
At TA = 1320ºC: 1300 L (liquid)
+ a
Only Liquid (L) present B L s
T o l id u
CL = C0 ( = 35 wt% Ni) B s
a a
At TD = 1190ºC:
1200 L+ D (solid)
Only Solid (a) present TD
C = C0 ( = 35 wt% Ni) 20 3032 35 4043 50
At TB = 1250ºC: CL C0 C wt% Ni
Both and L present Adapted from Fig. 9.3(a), Callister &
 Rethwisch 8e. (Fig. 9.3(a) is adapted from
CL = C liquidus ( = 32 wt% Ni) Phase Diagrams of Binary Nickel Alloys, P.
Nash (Ed.), ASM International, Materials
C = C solidus ( = 43 wt% Ni) Park, OH (1991).

8
Text book reference
DETERMINATION OF PHASE WEIGHT FRACTIONS

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

-- the weight fraction of each phase. Cu-Ni
• 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 s
TB id u
At TD : Only Solid ( ) present R S s ol
 a
WL = 0, W = 1.00 a
a 1200 L+ D (solid)
At TB : Both and L present
 TD
S 43  35 20 3032 35 40 43 50
WL =  0.73
R +S 43  32 CL C0 Ca wt% Ni
Adapted from Fig. 9.3(a), Callister &
Rethwisch 8e. (Fig. 9.3(a) is adapted from
R Phase Diagrams of Binary Nickel Alloys, P.
Wa = = 0.27 Nash (Ed.), ASM International, Materials
R +S Park, OH (1991).
10
 THE LEVER RULE
 Tie line – connects the phases in equilibrium
with each other – also sometimes called an
T(ºC)isotherm What fraction of each phase?
tie line dus
liqu
i Think of the tie line as a lever
1300 L (liquid)
+ a
B L s
TB id u
s ol 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),
Callister & Rethwisch 8e.

ML S C  C0 R C  CL
WL     W   0
M L  M  R  S C   CL R  S C   CL
12
Derivation of the Lever Rule
 DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS
ALLOYS
[Equilibrium (very slow) cooling]

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

Cu-Ni system. Cu-Ni
system
• Consider 130 0 A a
microstuctural L: 35 wt% Ni L+
changes that a: 46 wt% Ni
35 B
46
accompany the 32 C 43
cooling of a
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
Adapted from Fig. 9.4, C0 wt% Ni
14 Callister & Rethwisch 8e.
DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS
ALLOYS
[Equilibrium (very slow) cooling]
DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS
ALLOYS

[Equilibrium (very slow) cooling]

 Solidification in the solid + liquid phase occurs
gradually upon cooling from the liquidus line.
 Nuclei of the solid phase form and they grow to
consume all the liquid at the solidus line.

Conditions of equilibrium solidification and the development of

microstructures, as described in the previous section, are realized only
for extremely slow cooling rates. The reason for this is that with
changes in temperature, there must be readjustments in the
compositions of the liquid and solid phases in accordance with
the phase diagram (i.e., with the liquidus and solidus lines), as
discussed. These readjustments are accomplished by diffusional
processes—that is, diffusion in both solid and liquid phases
and also across the solid–liquid interface. Inasmuch as diffusion
is a time-dependent phenomenon (Section 5.3), to maintain
 DEVELOPMENT OF MICROSTRUCTURE IN ISOMORPHOUS
ALLOYS
[Non - Equilibrium (fast) cooling]

The implication of this non-

equilibrium solidification is that
solidus line on the phase diagram
 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

19
Cored structure can be eliminated by a homogenization
heat treatment at a temperature below the solidus point for