2.

CERAMIC PHASE
DIAGRAMS

1
 CERAMIC PHASE DIAGRAMS

Graphical representation of phase relationship at equilibrium

with temperature-composition as x and y axes.
Provides information on following:
1.  Melting temperature and polymorphic changes of
pure compounds
2.  Reduction in melting temperature,
e.g. eutectics, peritectics
3.  Interaction between compounds, e.g. new
phase formation
4.  Solid solution behaviour
5.  Changes in solubility with temperature
6.  Amounts and composition of phases are obtained
by the lever rule.
7.  Liquid immiscibility
2
 The Gibbs Phase Rule

P+F=C+2

P = number of phases
F = number of degrees of freedom
C = number of components

- pressure is usually not a variable

- a phase is a physically homogeneous and mechanically
separable entity

3
Invariant Points - eutectic, peritectic, eutectoid

Eutectic Reaction

L → 2 solids (at fixed Temp and composition)

Peritectic Reaction
L1 → solid + L2

Congruent Melting
Solid → Liquid

Incongruent Melting
S1 → S2 + L (at peritectics)
4
 CERAMIC PHASE DIAGRAMS

1. Complete solid solubility: Al2O3-Cr2O3

(also MgO – NiO system)

•  Al3+: r = 0.072nm
• Cr3+: r = 0.044nm
• Isostructural (HCP)

5
2.LIMITED SOLID
SOLUBILITY
WITH EUTECTIC
(also ZrO2 - Al2O3)

Mg2+ = 0.072nm Ca2+ = 0.1nm

6
3. Al2O3 - SiO2

Compound:
3Al2O3 . 2SiO2
called Mullite
peritectic

Observe: eutectic
- eutectic
- peritectic

INCONGRUENT
MELTING of
Mullite
7
 Complex Binaries

•  CaO-Al2O3
•  Calcium Aluminates

•  several compounds
and eutectics

8
Complex Binary: CaO - SiO2

Liquid immiscibility

- several compounds
- several eutectics
- liquid immiscibility 9
 Polymorphism - ZrO2
CaO- ZrO2

TETRAGONAL 1000OC MONOCLINIC

(HIGH T) (+3.25 vol% CHANGE)

t-ZrO2

c-ZrO2
m-ZrO2

10
Polymorphs of Zirconia

11
 ZrO2-MgO Binary
MgO and Y2O3
stabilize
tetragonal phase

t-ZrO2
m-ZrO2
c-ZrO2

Eutectoid at 800oC
t-ZrO2 is stabilized to to
room temperature
t-ZrO2 m-ZrO2 + MgO is
suppressed kinetically
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 TERNARY DIAGRAMS

3-D
REPRESENTATION

Binary eutectics: e1, e2 & e3

Ternary eutectic E

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 2-D REPRESENTATION

2. PSEUDO-BINARY SECTION
1. LIQUIDUS CONTOURS

BC is a
compound

a, b and c are primary fields of

solutions of A,B and C 14
 3. ISOTHERMAL SECTIONS

T7
T3

15
 CONGRUENTLY MELTING INCONGRUENT MELTING
COMPOUND “AB” COMPOUND “AB3”

Alkamade line C
Primary fields
c
a, b c and ab
e3
E1 E2 e4

b ab
a 16
B A
AB
Al2O3 - SiO2
INCONGRUENT
MELTING OF
MULLITE in the
BINARY SYSTEM

17
 TERNARY COMPOUNDS

CONGRUENT MELTING INCONGRUENT

of Ternary eutectic MELTING: eutectic not
within abc primary field18
 MgO - FeO - SiO2 TERNARY

(SS)

(SS)

extensive BINARY
solid EUTECTIC

solution

(SS) 19
 MgO-Al2O3-SiO2 System

Cordierite primary field

(Cordierite):
Incongruent melting

(Sapphirine)

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 PLOTTING COMPOSITIONS

Method 1 Method 2

Composition “Y”
Composition “X”
10%A-30%B-60%C
20% A-40%B-40%C
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“ISOPLETHAL” STUDY OF
TERNARY SYSTEMS
- simplify by using pseudobinary
sections (SC) and liquidus projections

Cooling of composition “X”steps are:

1. T3 solidification starts (C+L)
2. T3 - T6 primary phase
formation (C+L)
3. T7 on boundary HE (eutectic valley)
B forms (C + B + L)
4. >TE have C+B+LE
5. <TE have C+B+ Eutectic A+B+C

22
PSEUDO-BINARY SECTION BASAL PROJECTION

Cooling of composition “X”

1. T3 solidification starts (C+L)
2. T3 - T6 primary phase
formation (C+L)
3. T7 on boundary HE (eutectic valley)
B forms (C + B + L)
4. >TE have C+B+LE
5. <TE have C+B+ Eutectic A+B+C 23
 NON-EQUILIBRIUM BEHAVIOUR
Reactions between 2 components
ceramic/metal powders

Heating:
Sintering

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Overall
composition

24
Metastable Eutectics

Equilibrium: Compound
AB formation

•  Under rapid cooling

conditions AB may
not nucleate
•  and liquidus lines
are extended (as
shown)
•  So eutectic occurs at
a lower temperature

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 GLASS FORMATION

Na2O-CaO-SiO2 phase
diagram

Glass Forming region

26
 Crystal Nucleation in a Soda-Lime Glass
TTT Curves

For typical/
normal cooling
No
rates no
crystallization crystallization nucleation of
crystals occurs
in glass systems
27