Phase Diagrams Ternary Systems

TERNARY SYSTEMS
Concentration given in Gibbs‘ Triangle
x1
htriangle
h2 h1
x3
h3
x2 x3 x1
x1 + x2 + x 3 = 1
in the same way:
h1 + h2 + h3 = htriangle
270121 VO Phasendiagramme Ternäre Systeme Folie 1
TERNARY SYSTEMS
Tie Lines
S: 20 % A + 70 % B + 10 % C
L: 40 % A + 30 % B + 30 % C
Mix one part of S with

three parts of L
Composition of P (must be on the line S-L):
Line S-L is a tie line !
Lever Rule can be applied !

Isomorphous Ternary Systems
Space Diagram and possible representations
binary tie lines
Horizontal Sections: Vertical Sections:

“Isotherms” “Isopleths” “Liquidus Projections”

Isothermal Sections
Binary limiting tie line
Solidus
Tie lines in ternary composition range cannot be predicted,

but must be determined experimentally!

Vertical Sections = Isopleths
Tie lines cannot be shown as they

are usually not within this plane

Liquidus Projection
Of course, no information
possible about tie lines !
Gibbs Energy Surface

Application of Phase Rule
F=C–P+2
Single-phase field:
F=3–1+2=4
for p = const
F’= 3 – 1 + 1 = 3
Two-phase field
(for p = const):
• select temperature
F’= 3 – 2 + 1 = 2 • select composition
of A in the solid phase
Two-phase field
(for p = const):
F’= 3 – 2 + 1 = 2
• select composition
of B in the liquid phase
• select composition
of C in the liquid phase

Solidification
All tie lines have to

cross the point of the
gross composition:
X = L1 = α4

Maxima and Minima
Maximum in the
binary System A-B
Tie Lines:
αα
L
Maximum in the
ternary System
Tie Lines:
α L

Ternary Three-Phase Equilibrium
F=3–3+2=2
for p = constant:
F’= 3 – 3 + 1 = 1
“Tie Triangle”
if T selected, no
degree of freedom
left anymore !
P is mixture of 2 parts of R, 3 parts of S, 5 parts of L
Ternary Lever Rule

Space Model
Three-phase equilibria in
ternary systems occur
over a temperature range!
Example: Bi-Pb-Sb

T1
T2-T4
T5
Tie lines
L (α + β)
Binary eutectic
β Tie lines
Lα+β
(L + β)
Tie lines
(L + α)
α
Binary eutectic
Lα+β
Development of Isotherms
T1
T2-T4
T5

Possible and forbidden phase boundaries
Could be demonstrated by use of

Gibbs energy surfaces !

Solidification
X
Freezing of an
L
alloy with the
composition X
Primary
crystallization
of α begins
Secondary
crystallization
of (α+β) begins
Final product:
mixture of (α+β)

Space Model
two peritectic
systems

Space Model
various types
Termination of a three-
phase equilibrium in a
critical tie line

Critical Points and Critical Curves
critical points
critical curve
Participation of a
binary monotectic
critical tie line
critical curves

Maxima and Minima
The three-phase equilibrium

may pass through a
maximum or minimum (α+β+L)
A B
A B
C Example of a maximum
C
A B A B
C C
Vertical Sections

Ternary Diffusion Couples

Ternary Four-Phase Equilibria
Three different types of four-phase equilibria
Class I (or E-type):
Lα+β+γ
(ternary eutectic)
Class II (or U-Type):
L+αβ+γ
(transition reaction)
Class III (or P-type):
L+α+βγ
(ternary peritectic)
Four phase equilibria are invariant:

F=C–P+2=3–4+2=1
with p = const.  F’ = 0

Ternary Four-Phase Equilibrium
Class I
Lα+β+γ
e1
A B
I (E)
e3 e2
Schematic Liquidus Projection
C
Ternary Four-
Phase
Equilibrium
Class I

Class I
Isothermal Sections

Class I
Isopleths
Section at
constant ratio xA/xC
Section at constant xC

Rule of Landau and Palatnik
r1 = r – d– – d+
r = dimension of phase diagram

r1 = dimension of boundary between two
neighboring phase fields
d– = number of phases that disappear
d+ = number of phases that newly appear
Section at ~ 50 at% C
r=2

Class I
Solidification
Four-phase plane
eutectic
troughs
Alloy X: primary crystallization of single-phase β,

secondary crystallization of two-phase mixture α+β,
tertiary crystallization of three-phase mixture α+β+γ
(most common case)
Alloy Y: crystallization of β+γ in equilibrium situation
(in non-equilibrium situation probably some liquid would
be left over, leading to a secondary crystallization of
three-phase α+β+γ – as indicated by blue arrows)
Alloy Z: primary crystallization of single-phase γ,
secondary crystallization of three-phase α+β+γ
(only by incidence possible)

Class I
Ternary
Eutectoid
γα+β+δ

Class I
Participation of a
binary monotectic
LI  α + β + LII
Isothermal Sections

Class II
p1
L+αβ+γ
A B
II (U)
e1
Schematic Liquidus Projection
e2
C
Ternary
Four-Phase
Equilibrium
Class II

Ternary
Four-Phase
Equilibrium
Class II
Isothermal
Sections

Class II
β
T3
α
L+αβ+γ
L
α L
β
γ
T4
α L
γ β β
T5
α L
γ γ

Class II
Isopleths
C

Class III
L+α+βγ
e1
A B
III (P)
Schematic Liquidus Projection p1
p2
C
Ternary
Four-Phase
Equilibrium
Class III
L+α+βγ

L+α+βγ
Ternary
Four-Phase
Equilibrium
Class III
Isothermal
Sections
1: L+ α + β → α + β + γ
2: L+ α + β → L + α + γ
3: L+ α + β → L + β + γ
Class III
Isopleths

Congruent Transformations in
Ternary Systems
Pseudobinary
(quasibinary)
system

Ternary Systems
Isothermal
Sections
Pseudobinary
(quasibinary)
system

Ternary Systems
This is not a pseudobinary

(quasibinary) system !
Ternary Systems
Liquidus
Projections
This is a pseudobinary
(quasibinary) system
This is not a pseudobinary

(quasibinary) system

Ternary Systems
Congruent transformations can be:
• pure components (trivial)
• binary phases with congruent melting point
• ternary phases with congruent melting point
Congruent transformations can give rise to quasibinary

(pseudobinary) sections which divide the ternary phase
diagram into different parts.
For example, the existence of a

congruently melting ternary
phase (δ) can(!) possibly
divide the ternary system into
three different , more or less
independent, systems if it
forms quasibinary sections
with the pure components (but
this is not necessarily so).

Quasibinary Systems
Number of possible quasibinary systems:
n = b + 2•t + 1
n = No. of independent ternary systems
b = No. of binary congruently melting phases
t = No. of ternary congruently melting phases
n = 1 + 2•2 + 1 = 6
“Clear Cross Principle”

Complex Ternary Systems
consist of:
• one-phase equilibria: spaces of any shape
• two-phase equilibria: spaces having two conjugate surfaces

(joined by tie lines at every point)

consist of:
• three-phase equilibria: a trio of conjugate curves
(connected by tie-triangles everywhere)
• four-phase equilibria: three different types
Class I Class II Class III

Ternary Four-Phase Equilibria
Class I
Class III
Class II

Complex Hypothetical
System
I: δ  L + β + γ I
II
II: L + β  γ + η
I
I: L  α + γ + η

Scheil Diagram
(Reaction Scheme after Scheil)
Ternary
e1
A B
α I (E) β
e2 γ e3
Ternary
p1
A B
α β
II (U)
γ e1
p2

Complex Hypothetical
System

Example: Ag-Bi-Tl
From: “Handbook of Ternary Alloy Phase Diagrams”,

P. Villars, A. Prince, H. Okamoto, Eds.,
ASM International

Example: In-Ni-Sb
From: K.W. Richter, K. Micke, and H. Ipser: “Contact Materials

for III-V Semiconductors: Phase Equilibria of InSb in the
Ternary System In-Ni-Sb”; Mater. Sci. Eng. B 55 (1998), 44.

Phase Diagrams Ternary Systems

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Phase Diagrams Ternary Systems

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TERNARY SYSTEMS

Concentration given in Gibbs‘ Triangle

Mix one part of S with

Composition of P (must be on the line S-L):

Line S-L is a tie line !

Lever Rule can be applied !

270121 VO Phasendiagramme Ternäre Systeme Folie 2

binary tie lines

Horizontal Sections: Vertical Sections:

270121 VO Phasendiagramme Ternäre Systeme Folie 3

Binary limiting tie line

Tie lines in ternary composition range cannot be predicted,

270121 VO Phasendiagramme Ternäre Systeme Folie 4

Tie lines cannot be shown as they

270121 VO Phasendiagramme Ternäre Systeme Folie 5

Gibbs Energy Surface

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All tie lines have to

270121 VO Phasendiagramme Ternäre Systeme Folie 8

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P is mixture of 2 parts of R, 3 parts of S, 5 parts of L

Ternary Lever Rule

270121 VO Phasendiagramme Ternäre Systeme Folie 10

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Could be demonstrated by use of

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critical tie line

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The three-phase equilibrium

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Four phase equilibria are invariant:

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r = dimension of phase diagram

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Alloy X: primary crystallization of single-phase β,

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This is not a pseudobinary

This is not a pseudobinary

270121 VO Phasendiagramme Ternäre Systeme Folie 43

Congruent transformations can give rise to quasibinary

For example, the existence of a

270121 VO Phasendiagramme Ternäre Systeme Folie 44

“Clear Cross Principle”

270121 VO Phasendiagramme Ternäre Systeme Folie 45

• two-phase equilibria: spaces having two conjugate surfaces