Universidad

Carlos III de Madrid

www.uc3m.es

Aerospace Materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BASIC CONCEPTS
Component

Chemical substance or compound with fixed composition that can form part of a
phase or alloy.
alloy Examples: Aluminium (Al)
(Al), Alumina (Al2O3).
)

Phase

Chemically and structurally homogeneous area that forms part of the

microstructure.
i
t
t
C
Could
ld b
be fformed
db
by one or various
i
components.
t Examples:
E
l
Ferrite (solid solution Fe-C with BCC structure) austenite (solid solution Fe-C
with FCC structure), calcium carbonate (CaCO3)

Mi
Microconstituent
tit
t

Each one of different structures that

can be observed
on a polished surface
of the material.
Can be formed by one
or various phases

1: Ferrite
2 and 3: pearlite (ferrite + cementite)

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

DEFINITION OF EQUILIBRIUM PHASE DIAGRAM

Equilibrium diagram :
Map of the phases in thermodynamic equilibrium that are present in a
system of materials at different pressures, temperatures and compositions.
There is no liquid CO2 at Troom and
ambient pressure.
Gradient of P/T > 0, as it is in almost all
substances.
b t
Triple-point: gas, liquid and solid are at
equilibrium.
At T below the triple point CO2 can
sublime: gas solid (dry ice)

Phase diagram of CO2

Above Tc = 32 C and Pc =73 atm supercritical

CO2 fluid (used to extract caffeine from coffee)

Dry ice or card ice: solid CO2

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Universidad
Carlos III de Madrid
www.uc3m.es

Aerospace Materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

UNARY OR ONE COMPONENT PHASE DIAGRAM : P-T

Phase diagram of water

Dpt. Materials Sci. and Eng. and Chem. Eng.

Cooling curve for water

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

UNARY OR ONE COMPONENT PHASE DIAGRAM : P-T

Pure Iron

Different phases coexist at triple point

point.
Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Universidad
Carlos III de Madrid
www.uc3m.es

Aerospace Materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY ISOMORPHOUS PHASE DIAGRAMS

COOLING CURVES

Used to determine phase transition temperature.

T
Temperature
t
and
d time
ti
data
d t off cooling
li
molten
lt
metal
t l is
i
recorded and plotted.

Thermal arrest : heat lost = heat supplied by solidifying metal

Alloys
All
solidify
lidif over a range off temperature
t
t
(no
(
thermal
th
l
arrest)
Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY ISOMORPHOUS PHASE DIAGRAMS

SYSTEMS OF 2 COMPONENTS WITH COMPLETE SOLID SOLUBILITY

Design of a phase diagram from the cooling curves

100%B
0%A

80%B
20%A

20%B
80%A

0%B
100%A

Dpt. Materials Sci. and Eng. and Chem. Eng.

50%B
50%A

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY ISOMORPHOUS PHASE DIAGRAMS

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY ISOMORPHOUS PHASE DIAGRAMS

Complete Solid Solubility
Polycrystalline single
phase material.
Its microstructure is not
different from that of
the pure metal.
When solute is added,
Tm is modified

Complete solubility in
solid state.

Liquid

The alloy does not

solidify at a constant
temperature but at a
range of temperatures
Liquid
q
and Solid

Solid

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Universidad
Carlos III de Madrid
www.uc3m.es

Aerospace Materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

GIBBS PHASE RULE

F=CP+N
F = Degrees of freedom (No. of independent
variables available to the system)
C =No.
No of components
P =No. of phases
N=No. of noncompositional variables (e.g.
pressure and temperature)

For routine processing of materials

materials,
we can consider the pressure to be
fixed at 1atm:
=> F = C P + 1

F = 1- 2 + 2 = 1

F = 11- 2 + 2 = 1

Tem
mperature

F=CP+2

F = 2- 2 + 1 = 1

F = 1- 1 + 2 = 2

F = 1- 2 + 2 = 1
F = 1- 3 + 2 = 0

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

C
Composition
iti
Aerospace Materials I

Universidad
Carlos III de Madrid
www.uc3m.es

Aerospace Materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

TIE LINE AND LEVER RULE

Determination of Phase composition: Tie line

Determination of Phase Amounts: Lever rule

Phase composition:

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Intersections of the tie line

with phase boundaries

Composition of the
respective phases is given
by the composition axis

Aerospace Materials I

Topic 4: Phase diagrams

TIE LINE AND LEVER RULE

LEVER RULE
Determination of Phase Amounts

The fraction of each phase is

computed by taking the length
of the tie line from the overall
alloy composition to the phase
boundary of the other phase,
and diving by the total line
length

WL

C C0
S

R S C C L

C CL
R
0
R S C C L

C
CL

WL= fraction of liquid phase

W= fraction of phase
Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Universidad
Carlos III de Madrid
www.uc3m.es

Aerospace Materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

NON-EQUILIBRIUM SOLIDIFICATION
Non-equilibrium solidification

Microstructures of
heterogeneous composition
are produced
MICROsegregation (or
cored structure)

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

NON-EQUILIBRIUM SOLIDIFICATION
Non-equilibrium solidification

Microsegrgation (or coring) can be eliminated with

homogenization heat treatment at T below solidus
(Example: TTT< T7). During heat treatment solid state
diffusion occurs

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Universidad
Carlos III de Madrid
www.uc3m.es

Aerospace materials I

TOPIC 4. Phase Diagrams I

Basic concepts:
Component, phase, micro constituent.

Unary
y or one component
p
p
phase diagrams.
g
Binary isomorphous phase diagrams.
Gibbs Phase Rule.
Tie line and lever rule.
Non equilibrium solidification.
solidification
Binary eutectic systems.

Dpt. Materials Sci. and Eng. and Chemical Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY EUTECTIC SYSTEMS

SYSTEMS OF 2 COMPONENTS WITH PARTIAL SOLID SOLUBILITY AND AN INVARIANT EUTECTIC
REACTION

Eutectic
temperature

Eutectic composition
Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY EUTECTIC SYSTEMS

INVARIANT REACTIONS: They are produced at a fixed composition and
temperature for a given system, and the result also remains fixed
In a system of two partially soluble components a solidification reaction is produced at a
fixed composition and temperature with a profile of temperature gradient similar to pure
solids.

Cooling curve at eutectic Temperature

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Eutectic reaction
L +
+

Aerospace Materials I

Topic 4: Phase diagrams

BINARY EUTECTIC SYSTEMS

Eutectic reaction and microstructure

Eutectic product

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY EUTECTIC SYSTEMS

a) Sn-50%In
b) Al-13%Si
c) Al-33%Cu
d) Mg-37%Sn

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY EUTECTIC SYSTEMS

Hypo-Eutectic composition

Hypo Eutectic cooling curve

Hypo-Eutectic

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

BINARY EUTECTIC SYSTEMS

Hyper-Eutectic compositions

Hyper-Eutectic cooling curve

Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I

Topic 4: Phase diagrams

LEVER RULE IN BINARY EUTECTIC PHASE DIAGRAMS

Q
W '
PQ
QR
W
PQ R
P
We WL
PQ
W

P
PQ R

We = fraction eutectic microconstituent

WL = fraction of liquid phase
W = fraction of phase (primary )
W = total fraction of (p
(primary
y + in eutectic))
W =f raction of phase (total)
Dpt. Materials Sci. and Eng. and Chem. Eng.

UC3M

Aerospace Materials I