MatS 4212

Section 4 Ceramic Phase Diagrams

A. Fundamentals - definitions, one component

diagrams
B. Binary Phase Diagrams
1. Features
2. Applications
C. Ternary Phase Diagrams
1. Features
2. Isoplethal analysis
3. Applications
Reading: Barsoum, Chapter 8; Reading from Bergeron and Risbud
Introduction to Phase Equilibria in Ceramics (course packet)

Background: Callister, Chapter 9

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Fundamentals
Phase - any portion of a system that is physically and chemically
homogeneous within itself and bounded by a surface so that it is
mechanically separable.

Equilibrium - a condition in which the properties of a system do

not change with time.

The equilibrium state at constant temperature and pressure is one

that minimizes the Gibbs free energy

Chemical equilibrium requires that the chemical potentials (partial

molar Gibbs free energies) of all components are the same in all
phases present

A phase diagram is a map of chemical

equilibrium Adapted from Bergeron and Risbud, Introduction to
Phase Equilibria in Ceramics
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Gibbs Phase Rule

P+F=C+2

Phases

Degrees of Freedom Components - the number o

- the number of intensive components is the smallest
variables that may be number of independently
changed without variable constituents needed to
changing the number of express the compositions of al
phases phases.

Gibbs phase rule holds for systems at equilibri

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One component phase diagrams

Monoclinic Tetragonal Cubic Liquid

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
Two component phase diagrams MatS 4212

Condensed
phase rule
P+F=C+1

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
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Tmp (MgO) = 2800°C

Liquidus
Liquid (L)

Solidus

Solid
Tmp (NiO) = 2000°C
Solution (SS)

Phase Diagrams for Ceramists

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Isoplethal Analysis Example

7 40

8 62

8 84

3 92

Phase Diagrams for Ceramists

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Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
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48% Cr2O3

45
33

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
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55% Cr2O3

45

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
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P L+NiO

3N-V+L
Liquid
P
3N-V+NiO

3N-V+2N-V
2N-V+L
V2O5+L P

2N-V+N-V
E N-V+L

V2O5+N-V

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
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Liquid-Liquid
immiscibility

Polymorphi
c
Forms

50

Bergeron and Risbud, Introduction to

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Ternary Diagrams

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
 Primary phase MatS 4212
Liquidus surface space for C:
C is first
Primary phase
crystalline phase
area for C
to form on
cooling

Boundary line:
Isotherms for
intersection of c
liquidus surfac
two liquidus
T surfaces

b a

b c

Ternary Eutectic L = A(s) + B(s) + C(s)

Bergeron and Risbud, Introduction to
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C
Liquid Cooling
Solid Cooling Curve - 7’’ Curve -
compositional path for T1 compositional path
solid on cooling. 8’’
T2 taken by liquid on
Starts at C, ends at X cooling. Starts at
X T3
T4 X, ends at E.
4’
Boundary line - solid C in H 5’
c T5
T6 G
equilibrium with solid B and
liquid T7
6’
Primary 7’
E
8’
phase
fields b a

B F A
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Terms
Primary Phase Field - The primary phase field
of a crystalline material is the region on the ternary
diagram in which a melt will form the that crystalline A
phase first on cooling

Boundary Line - a line between two primary

phase fields that represents a liquid phase in
equilibrium with two solid phases.

Binary Join - a straight line connecting points

representing the compositions of two crystalline
phases in a ternary system.

Alkemade Line - a join connecting connecting

points representing the compositions of two
crystalline phases that have a common boundary
line (i.e., can be in equilibrium with each other).
B BC C
Alkemade Theorem - The intersection of a
boundary line (or boundary line extended) with its
corresponding Alkemade line (or Alkemade line
extended) represents a temperature maximum on Adapted from Bergeron and Risbud,
Introduction to Phase Equilibria in
that boundary line and a temperature minimum on Ceramics
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Terms There are 2 compatibility

Primary Phase Field - The primary phase field triangles: A-B-BC and A-
of a crystalline material is the region on the ternary
diagram in which a melt will form the that crystalline BC-C A
phase first on cooling

Boundary Line - a line between two primary

phase fields that represents a liquid phase in
equilibrium with two solid phases. E3
a E4
Binary Join - a straight line connecting points
representing the compositions of two crystalline
E2
phases in a ternary system. E1
Alkemade Line - a join connecting connecting b bc c
points representing the compositions of two
crystalline phases that have a common boundary
line (i.e., can be in equilibrium with each other).
B E6 BC E5 C
Alkemade Theorem - The intersection of a
boundary line (or boundary line extended) with its
corresponding Alkemade line (or Alkemade line
extended) represents a temperature maximum on Adapted from Bergeron and Risbud,
Introduction to Phase Equilibria in
that boundary line and a temperature minimum on Ceramics
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Draw in Alkamade lines

Draw arrows on
boundary lines
and identify the
invariant points

E1
E2

Bergeron and Risbud, Introduction to

Phase Equilibria in Ceramics
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Consider a composition X Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

What is the composition of melt X?

29%A, 7%B, 64%C

What is the primary phase region?

C
What is the liquidus temperature? X
~1130°C
What is the compatibility triangle?

A-AB-C

E1
E2
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Isoplethal study of X Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

Draw the cooling path for the liquid

composition.

At what temperature does the last

liquid solidify?
Temp of E1, ~650°C
X
What is the composition of the last
liquid to solidify?
E1 : 51% A, 23% B,
26%C
What solid phases will be
present when the last liquid
solidifies?
E1
A, AB and C E2
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Isoplethal study of X Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

Find the number of phases,

compositions of phases and
relative amounts after melt X is
cooled to 1000°C.
2 phases
X
L (40%A, 8%B, 52%C)
Solid C (100%C)

73% Liquid
27% C

E1
E2
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Isoplethal study of X Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

Find the number of phases,

compositions of phases and relative
amounts after melt X is cooled to
700°C.
3 phases
X
L (54%A, 15%B, 31%C)
C
A

Solid is 9%A and 91%C

43% Liquid
57% Solid E1
E2
- 57(0.09)=5% A
- 57(0.91)=52%C
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At the eutectic temperature

At the eutectic temperature, the eutectic reaction takes place:

L = C+ A + AB

All of the AB is created by eutectic solidification of the liquid.

Note: If we started with a melt with the eutectic composition

E1, then it would form all three solids (C, A, AB) as the
temperature dropped and the reaction completes.
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Cooling paths for X Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

Add the cooling path for the solid

phase(s) to the cooling path of the
liquid
Cooling path of solid

Cooling path of liquid

E1
E2
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Composition of X at Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

temperature just below

4.1
the eutectic temperature.
%A = 4.1/18.4 x 100 =
22%
2.6

%AB = 2.6/18.4 x 100 = X

14%

%C = 11.7/18.4 x 100 =
64%
11.7

E1
E2
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Isoplethal study of Y Bergeron and Risbud, Introduction to Phase
Equilibria in Ceramics

What is the compatibility

triangle?
C-AB-B
What is the primary phase?
AB

What is the invariant point

where the liquid
disappears?
E2
Draw the cooling curves for
the liquid and solid
compositions
E1
E2
Liquid
Solid
Y
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Incongruent melting
The compositions of AC and AB
do not intersect their primary
phase fields. These compounds
melt incongruently. Peritectics
appear in the diagram.
NOTE: The three edges of a
ternary diagram are three binary
c systems - we can find binary
P phase diagrams for these, for
example. An alkemade lines
that cuts across the diagram,
E however, is only a true binary
system if the alkemade line
P intersects the boundary line. So,
E E P for example, the alkemade line
a b C-AB cannot be drawn as a
binary phase diagram. In these
E P cases, we can not draw arrows
on the alkemade line. On actual
phase diagrams, arrows are
always drawn on the boundary
lines, but not always on the
alkemade lines.
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Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics

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Consider a composition X
What is the composition of melt X?
12% R, 55% G, 30% K
What is the primary phase region?
G
What is the liquidus temperature? E E
~1900°C
What is the compatibility triangle?
K3G7 - R - K P E
At what temperature does
the last liquid solidify?

~1350°C, Eutectic

P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Find the number of phases,

compositions of phases and
relative amounts after melt X is
cooled to 1800°C.
3 phases
E E
L(18%R, 32%K - point
1), G, K3G7
25% Solid (1....1’ tie line) E
P
75% Liquid

Solid is given by point

1’. It is 20%G, 80%
K 3G 7
1
(G....K3G7 Alkemade line)
0
X
so overall,
1’
5%G, P E
20% K3G7, Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Find the number of phases,

compositions of phases and
relative amounts after melt X is
cooled to 1775°C.

3 phases
E E
L(point 2),
G, K3G7
E
40% Solid (2.... K3G7 tie P
line)
60% Liquid

Solid is almost all 2

K3G7. The G has 1
0
been removed, X
resorbed during
1’
cooling. P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Find the number of phases,

compositions of phases and
relative amounts after melt X
is cooled to 1600°C.

2 phases E E
L(point 3), K3G7
E
63% Solid K3G7 (3.... K3G7 tie P
line)
37% Liquid 3

2
1
0
X

1’ P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Find the number of phases,
compositions of phases and
relative amounts after melt X
is cooled to 1385°C.

3 phases
L(point 4),
E E
K, K3G7
74% Solid (4.... K3G7 tie
line)
E
4
P
26% Liquid
3
Solid is almost all
K3G7. The K is just 2
starting to form. 1
0
X

1’ P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Find the number of phases,

compositions of phases and
relative amounts after melt X is
cooled to just above E.

3 phases
L(point 5), K, K3G7 E E

76% Solid (5....5’ tie

line) 5 E
24% Liquid P 4

Solid composition is 3
given by 5’. It is
~3%K, 97% K3G7.
2
(K3G7.... K Alkemade line) 1
0
X
So, overall there is
2%K, 74% K3G7 and 1’ P E
24%L 5’
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Cooling curves
Liquid
Solid
E E

5 E
P 4

2
1
0
X

1’ P E
5’
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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1.2
Final solid composition
%K = 1.2/18.2 x 100 = 6.6%

%K3G7 = 14.7/18.2 x 100 =

80.8%
E E
%R = 2.3/18.2 x 100 =12.6%
14.7
E
E
P

X 2.3

P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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E E

P E

Y Z

P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Cooling curve for liquid
Y Cooling curve for solid

E E

P E

Y Z

P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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Cooling curve for liquid
Y
Cooling curve for solid

Cooling curve for liquid

Z Cooling curve for solid

E E

P E

Y Z

P E
Bergeron and Risbud, Introduction to Phase Equilibria in Ceramics
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At the peritectic temperature

At the peritectic temperature, a peritectic reaction takes place:

L + G = K3G7 + R

For Y, all of the K3G7 is created by solidification of the liquid at this

temperature and in this case the liquid is completely consumed and
solidification is complete.

For Z, all of the G is reacted away at this temperature, but liquid

remains so that the liquid composition continues to change during
cooling until it reaches the ternary eutectic, where the final
solidification takes place.

Y and Z are in different compatibility triangles!

Note: If we started with a melt with the peritectic composition P, then on cooling
through the peritectic temperature it would form K3G7 and R, and there would be some
liquid left. The liquid composition would follow the boundary line to E, where final
solidification takes place. P is in the R - K3G7-K compatibility triangle.
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Phase Diagrams for Ceramists

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Phase Diagrams for Ceramists

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70%CaO,
10%SiO2,
20%Al2O3

Phase Diagrams for Ceramists

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70%CaO, 10%SiO2, 20%Al2O3

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70%CaO, 10%SiO2, 20%Al2O3

Find the
compatibility
triangle and the
ternary invariant
point
P at 1470°C

Last liquid
solidifies
here.
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70%CaO, 10%SiO2, 20%Al2O3

Liquidus
temperature?

~1980°C
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70%CaO, 10%SiO2, 20%Al2O3

Find phases,
composition,
relative amounts
at 1800°C
2 phases
L (12% SiO2, 66%CaO,
22%Al2O3)
CaO (solid)

87%L
13%CaO
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70%CaO, 10%SiO2, 20%Al2O3

Find phases,
composition,
relative amounts
at 1600°C

3 phases
L (10% SiO2, 62%CaO,
28%Al2O3)
CaO (solid)
3CaO• SiO2 (solid)

71% Liquid
29% Solid

62%CaO/38%Ca3SiO5 ------
18% CaO, 11% Ca SiO
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70%CaO, 10%SiO2, 20%Al2O3

What happens
on cooling to
1500°C?

Still 3
phases
L
CaO
3CaO• SiO2

more solid
forms

solid has
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70%CaO, 10%SiO2, 20%Al2O3

What happens
on cooling
through 1470°C?

Peritectic reaction,
all liquid disappears
Ca3Al2O6 forms
compatibility triangle MatS 4212

composition of interest
composition of ternary invariant
cooling path of liquid
cooling path of solid
 compatibility triangle MatS 4212

composition of interest
11% CaO
54%Ca3Al2O6
35%Ca3SiO5
0.9

4.5

3
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Analyze composition Y

Y
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composition of interest compatibility triangle

composition of ternary invariant
cooling path of liquid
cooling path of solid

Y
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Phase Diagrams for Ceramists

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First crystalline
phase to form on
Polymorphic
cooling?
transformation of
SiO2
Solid SiO2 in
Tridymite polymorph
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Soda-Lime-Silica
Glass
73% SiO2, 16%Na2O,
11%CaO

What is the temp

needed to form a
1000°C
glass melt?

If completely
crystallized on cooling
what 3 phases form?

Phase Diagrams for Ceramists

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Only a portion of this

phase diagram is
mapped out.
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Consider the
composition labeled
X

X
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Consider the
composition labeled
X
Find compatibility triangle and
ternary invariant where last liquid
solidifies.

X
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What combination of
oxides should be made to
create a melt of this
composition?

58% SiO2
15% Al2O3
27% K2O
How high a temperature
is needed to form the
melt?1400°C

X
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Consider cooling a melt of

composition X to 1200°C.

How many phases are

present? 2

What are their

compositions?
Solid Leucite
Liquid (60% SiO2, 12% Al2O3)

What are their relative X

amounts?
30% Leucite
70% Liquid
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Consider cooling a melt of

composition X to 811°C.

How many phases are

present? 3

What are their

compositions?
Solid Leucite
Solid K2O•2SiO2
Liquid (64% SiO2, 5% Al2O3)
What are their relative
amounts?
56% Solid X
(12% K2O•2SiO2
88%Leucite)
-49.2% Leucite
-6.8 % K2O•2SiO2
44% Liquid
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Consider cooling a melt of

composition X to 809°C.

How many phases are

present? 3

What are their

compositions?
Solid Leucite
Solid K2O•2SiO2
Solid Potash Feldspar
What are their relative
amounts?
37% Leucite X
29% K2O•2SiO2
34% Potash Feldspar
 MatS 4212
Section 4 – Ceramic Phase Diagrams [Chapter 8, Packet from Introduction to Phase Equilibria in
Ceramics]

A. One Component Systems

1.Equilibrium and phase rule
2.Temperature vs. pressure, labeling regions, polymorphic phase transformation

B. Binary Systems
1.Condensed phase rule
2.Features of ceramic phase diagrams – single phase - line compounds and solid solution regions;
two phase regions; solid solutions and solubility; liquidus and solidus; eutectic and peritectic
points and reactions; melting behavior (congruent vs. incongruent); polymorphic phase
transformation
3.Solid solutions – substitutional and interstitial, factors that affect the extent of solid solution
4.Isophethal analysis - use of tie line (compositions of phases) and lever rule (relative amounts of
phases), microstructure prediction
5.Applications of binary phase diagrams – solubility, melting behavior, determination of phases
present (compositions, relative amounts) at different temperatures and overall composition,
temperature at which a liquid will first form when a mixture is heated

C. Ternary Systems
1.Finding composition in a triangle of 3 components
2.Three dimensional representation of effect of composition and temperature, and liquidus
projection as a two dimensional representation
3.Features: Alkemade lines, compatibility triangles, primary phase fields, intermediate compounds,
ternary and binary eutectics and peritectics
4.Isoplethal analysis
5.Applications – same as binary for ternary systems; liquidus temperature prediction for glass
forming systems