Phase diagrams.

1
 Components and phases
• Each material can be characterized by it’s elemental
composition and by it’s phase content. Phase content
defines the structure of the material. Structure of the
material determines it’s properties.

:Example :Phase content

Compositio β (lighter
n of the
phase) Ag
alloy
79.1 wt%
Silver – 20.9 α (darker
wt% Copper phase) Cu

2
 :Definition

• Phase is a homogeneous portion of a

system that has specific atomic
structure, physical and chemical
characteristics. If more than one phase
is present in a given system, each
phase will have its own distinct
properties and a boundary separating
the phases.
3
Phase content depends on T & Composition (co) of the
material.
. Phase diagram represents this dependence
• Changing T can change # of phases: path A to B
• Changing Co can change # of phases: path B to C

B
C

4
 Types of solid phases.
1) Solid solutions:

Interstitial Solid Superlattice: solute Substitutional Solid

Solution: atoms with
a small atomic radii
dissolve in the lattice
(they occupy
interstitial positions).
Usually interstitial
atoms are: N, C, H,
B. In such solution
there is a limit of a
5
solubility.
atoms occupy only Solution: in this solid
particular positions in solution solute atoms
the lattice, creating substitute the solvent
additional order – atoms on random
superlattice. These positions. Limit of
phases called – solubility in such
ordered phases. case depends on
several conditions
(Hume – Rothery
rules).
 Solubility
Solubility - The amount of one component (solute) that
can be completely dissolved in a second component
(solvent) without creating a second phase. The
solublity is the main characteristic of solid solution.
 Unlimited solubility - When the amount of
solute that can be dissolved in a solvent
without creating a second phase is unlimited.
 Limited solubility - When only a some
maximum amount of a solute can be dissolved
in a solvent. This amount is called “solubility
limit”.

6
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herein under license.

Illustration: (a) Water exists in three states (phases):

gas, liquid, and solid. (b) Water and alcohol have
unlimited solubility. (c) Salt and water have limited
solubility. (d) Oil and water have no solubility.
7
 :Example of the Solubility Limit
• Solubility Limit: T
Max concentration for α
which only a solution
occurs. α +
β
• Ex: Phase Diagram:
Pb-Sn System
Question: What is the
solubility limit of Sn in Pb at 100°C? 5 wt% Sn
Answer: 5 wt% Sn.
If Comp < 5 wt% Sn: α (Pb)
If Comp > 5 wt% Sn: α (Pb) + β (Sn) coexist

• Solubility limit increases with T:

e.g., if T = 150°C, solubility limit = 10wt% Sn.
8
 Hume-Rothery rules for solid
solubility:
- Size factor – when the difference between
the atomic diameter of the solvent and the
solute atoms is more than 15%, the
solubility is limited (due to high level of
distortions in the lattice).
- Crystal structure factor – if the crystal
structure of the two components is
identical, solubility will be higher.
- Valence factor – atoms with higher valence
(those atoms that contribute more
electrons) usually dissolve better than those
atoms that have lower valence (atoms that
contribute less electrons).
- Electronegativity factor – if solute and
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solvent stand close in the line of the
 :Examples

• rat Cu =1.278Å, rat Ni =1.243Å, both have FCC structure. These

elements stand very close in the periodical table: ZNi =28,
ZCu =29.
• rat Pb =3.5Å, rat Sn =2.81Å. Pb has FCC structure, Sn has
tetragonal structure. ZPb =82, ZSn =50, both stand in the IV
column in the periodical table.
10
 Phase equilibria
• Phases can be stable (in equilibrium state) or metastable
(non equilibrium). Phase is stable if it’s structure and
characteristics do not change with time.
• Equilibrium is best described in terms of a thermodynamic
quantity called the free energy (G). Free energy is a
function of the internal energy of a system and also function
of the entropy of the system (the degree of randomness or
disorder of the atoms in the structure). A system is at
equilibrium if its free energy is at a minimum under some
specified combination of T (temperature), P (pressure) and
C (composition).
:Examples

G G Intermetallic
At a specific T phase with
narrow
Phase with range of
wide range of stability
stability
11
%C in wt %C in wt
 Definitions:
 Binary phase diagram - A phase diagram for a
system with two components.
 Ternary phase diagram - A phase diagram for a
system with three components.
 Isomorphous phase diagram - A phase diagram in
which components display unlimited solid solubility.
 Liquidus temperature - The temperature at which
the first solid begins to form during solidification.
 Solidus temperature - The temperature below
which all liquid has completely solidified.

12
 Examples of binary b) Peritectic phase
:phase diagrams diagram
c) Complex phase
diagram

Solid solution

a
a) Isomorphous phase
diagram

c
13
 :Ternary Phase Diagrams
•Phase diagrams are
also constructed for
systems with more
than 2 components.
•Usually these
diagrams are
presented at
constant pressure
and at constant
temperature. Image
on the right present
U-Fe-Al phase
diagram at 850°C.

14
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15
phase
ternary

the left.
diagram
• Hypothetical

presented on
 :Binary Phase Diagrams
• Binary phase diagrams represent the
relationships between temperature and
compositions, showing the phases existing at
equilibrium. (Pressure is held constant – normally 1
atm.) In phase diagrams solubility limits are clearly
seen.
• Changes in the phases existing in the alloy and/or
phase quantity will influence the microstructure of
an alloy.
• Microstructure is subject of direct microscopic
observations, using optical or electron
microscopes. In metal alloys, microstructure is
characterized by the phases present, their
proportions, and the manner in which they are
distributed or arranged.
16
 b) Solid solution range
of B in A is wider than
solid solution range of
A in B.
c) Mg2Pb is an
intermediate phase.
Existence of valence
Solid solution
compound shortens
the range of solid
a b solution.

a) Cu and Ni are mutually

soluble in each other in
the solid state for all
compositions.
(rat Cu =1.27Å, rat Ni =1.24Å,
both FCC, same valence
and close
electronegativities.)

c
17
• This SEM image shows the lamellar eutectic
structure in the alloy Al77wt%-Cu33wt%. The
interlamellar spacing is about one micron.
18 back2
 :Intermediate Phases
• For some systems intermediate compounds rather than solid
solutions may be found on the phase diagram and these
compounds have distinct chemical formulas and crystal
structures; for metal-metal systems they are called
intermetallic compounds (bonded by metallic bonds).

19
 Intermediate Phases:
a) Valence Compounds
• Valence compounds are
created when the two
components stands far away
from each other in the
periodical table.
• Valence compounds are
bonded by ionic or covalent
bonds.
• Valence compounds can be
either strictly stoichiometric
(Mg2Pb previously) or to have
some range of stability (γ and
δ on the figure).
• Valence compounds are brittle
and have poor electrical
conductivity.
20
 Intermediate Phases:
b) Interstitial Compounds
• When concentration of interstitial atoms (C,B,N) is
more than solubility limit, interstitial compounds are
created: Fe3C, TaC, TiN, WC, MnN (ratC=0.77Å,
ratN=0.74Å, ratB=0.80Å).
• These compounds are very stable, they have high
hardness and high melting temperature.
• According to G. Hägg, when r < 0.59 ,
R
composition of interstitial compounds is: MX, M2X,
M4X or MX2.
• Homogeneity range of interstitial compounds can
be quite wide.
21
 Binary Isomorphous Phase
:Diagram
F T>1453°

F
T=1290°

Cs CL
F
liquid
T<1085°
• System is:
--binary i.e., 2 components: Cu and Ni. solid
--isomorphous i.e., complete solubility of one Cu Ni
component in another; α phase field
extends
22 from 0 to 100wt% Ni.
 The cooling curve for an isomorphous
alloy during solidification
T

1453

time
T

1085

23 time
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The cooling curve for an isomorphous alloy during

solidification. We assume that cooling rates are small so
as to allow thermal equilibrium to take place. The
changes in slope of the cooling curve indicate the
liquidus
24 and solidus temperatures, in this case for a Cu-
40% Ni alloy.
 For known composition
and temperature at least
3 kinds of information
are available:
1) the phases that are
Tie line present,
2) the composition of these
phases (according to the
left and right points of the
tie line),
CL CS
3) the percentage or
fractions of the phases.
25
 :Lever Rule
• C0 – initial concentration of the
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used

c0 component in the alloy.

• Cs – concentration of solid
phase
• CL – concentration of liquid
herein under license.

phase.
• ML=weight of the liquid phase
• Ms=weight of the solid phase
cLML+csMs=c0(ML+Ms)
(cL-c0)ML+(cs-c0)Ms=0
M L cS − c0
= Lever rule
M S c0 − cL ‫חוק מנוף‬
cS − c0
ML =
cS − c L
c0 − cL
26 MS =
cS − c L
Microstructures developed during equilibrium
:cooling
Zoom in of the area in the red square

• Consider Co = 35wt%Ni.
27
• Equilibrium cooling
 :Non-Equilibrium Cooling
• C changes during solidification
process. First α to solidify has C0 = 46wt%Ni.
• Cu-Ni case:
Last α to solidify has Cα = 35wt%Ni.
• Fast rate of • Slow rate of
cooling: cooling:
Cored structure Equilibrium structure
Uniform Cα:
First α to solidfy:
46wt%Ni 35wt%Ni
Last α to solidfy:
< 35wt%Ni

28
 Binary Eutectic Phase Diagram
Eutectic: is a specific mixture of two phases that
simultaneously crystallize from molten solution at
specific concentration and at specific temperature,
which is the lowest temperature of crystallization
/melting (Greek “eutektos”- meaning “easily melted”).
Usually eutectic exhibits lamellar microstructure.
Eutectic alloy – the mixture freezes as one at a single
temperature
When an alloy of non eutectic
composition freezes one phase
crystallizes at one temperature and
the other phase crystallizes at a
different temperature

29
 Example of Binary Eutectic
:Phase Diagram
• Point E called eutectic
point and it is an
invariant point, which is
designated by the
composition ce and
temperature Te.
• Eutectic reaction
occurs upon cooling the
liquid with composition
ce as it changes
temperature in passing
through Te; this reaction
may be written as
following
30
L→α +β
 :Cooling curves for eutectic diagram
T Cooling curve of
alloy with
composition C:
b c
779°C

time

Cooling curve of
T alloy with
composition b:

T 920
Cooling curve of
pure component Cu 779

1090 time

31 Compare with Cooling curves for isomorphous alloys

time
 T1

Relation
between free
energy curves T2
of each phase
and phase
:diagram T3

T3
T2

32 T1
 :The microstructure developed in eutectic binary system

33
 Photomicrograph of Pb-
Sn alloy with 50wt%Pb.
The microstructure is
composed of a primary
Pb rich (α prime) (large
dark regions) within a
lamelar eutectic structure
consisting of a Sn rich β
phase (light layers) and a
Pb rich (α phase) (dark
layers.)X400.

34
:Hypoeutectic & Hypereutectic alloys
T(°C)
300 L

L +α
200 α L +β (Pb-Sn
TE β
α +β System)
100

Co Co
hypoeutectichypereutectic
0 Co, wt% Sn
0 20 40 60 80 100
18.3 eutectic 97.8
61.9
hypoeutectic: Co=50wt%Sn hypereutectic: (illustration only)

eutectic: Co=61.9wt%Sn
α β
α β
α α β β
α β
α β
175µm 160µm
eutectic micro-constituent
35
 Calculation of amount of phases in the
:eutectic systems
In eutectic: M α = cβ − cE
Mβ cE − cα
• Inside the eutectic
C0 structure:
cβ − c E
%α =
cβ − cα
Cα CE Cβ
• If c0 is the initial
concentration:
cE − c0
%α prime =
cE − cα
c0 − cα
%eutectic =
cE − cα
36
 :Binary Peritectic Systems
α
C0 L Peritectic reaction:
L+α →β
L
Upon cooling from the
liquid phase, primary α is
formed (green particles).
β phase is the product of
the peritectic reaction
β
between α and liquid.
The β phase grows as
sheath around the
particles of the α phase.

37
 e peritectic
point
e phase
η phase
Liquid
eutectic
point
Sn

• This microstructure is obtained via a peritectic reaction

(L+e → η ) in 21%wt Cu- 61%wt Sn alloy.
• The peritectic reaction rarely goes to completion, since
the formation of η around the e phase separates it from
the liquid and inhibits further growth. Eventually, the
remaining liquid transforms by a eutectic reaction to η
and
38 Sn.
:Congruent Phase Transformations
Those transformations for which all
phases concerned have the same
composition throughout the
transformation are called
congruent transformations. For
incongruent transformations, at
least one of the phases will
experience a change in
composition.
Examples: melting of pure materials
and melting of the γ phase on the
left image – are congruent;
peritectic, eutectic reactions and
melting of an alloy that belongs to
an isomorphous system represent
incongruent transformations.
39
 :The Gibbs Phase Rule
• Gibbs phase rule represents a criterion for the number of
phases that coexist within a system at equillibrium. It defines
the relationship between number of degrees of freedom and
number of phases and number of components. Degree of
freedom is a number of thermodynamic free variables (composition,
temperature, pressure) which can be changed.
• P+F=C+N, where P-number of phases present, F-number of
degrees of freedom or the number of externally controlled
variables (e.g. temperature, pressure, composition), C-
number of components in the system (example 2 for binary
system), N-number of noncompositional variables (e.g.
pressure, temperature). When pressure is constant:
• F=C+1-P (since N=1, temperature is the only variable which is
noncompositional).

40
 :Short summary
For each phase diagram:
• Tie lines on the diagram give the compositions of the
phases in a two-phase field;
• The lever rule applies to find the amount of each
phase;
• Gibbs phase rule applies.
For example: in binary systems at a constant pressure,
three phases can only co-exist at a fixed temperature,
and their compositions are fixed. (These points are
called triple points or invariant points. Eutectic and
peritectic points are examples of such points.)

41
 Fe-C Phase Diagram
:Pure Iron
Upon heating pure iron experiences 2
changes in crystal structure:

At room temperature it exists as ferrite

(Fe-α ,BCC structure)

At 912°C a polymorphic transformation

occurs: ferrite → austenite (Fe-γ ,FCC
structure)

At 1394°C austenite transforms to a BCC

phase called δ ferrite.
42
:Iron-Carbon (Fe-C) Phase Diagram
• Pure iron: 3 solid
phases
– BCC ferrite (α )
– FCC Austenite (γ )
– BCC δ
• Beyond 6.7% C
cementite (Fe3C)
• Eutectic: 4.3% C
– L  γ + Fe3C
– (L  solid + solid)
• Eutectoid: 0.8% C
– γ  α + Fe3C
– (solid  solid +
solid) .Part of the Fe-C phase diagram

43
 Fe

44
wt.% C
 Fe-C Phase Diagram: Eutectoid Point
Schematic
representation of
the microstructures
for an iron-carbon Pearlite
alloy of eutectoid microstructure:
composition above
Just below the
and below the
eutectoid eutectoid point
temperature.

Schematic
representation of the
formation of pearlite
from austenite;
direction of carbon
diffusion indicated
by arrows

45
 Eutectoid Point: calculations
• Just below the
eutectoid point:

• Wα = (6.7-0.8)/(6.7-
0.02) = 88%

• WFe3C = (0.8-0.02)/(6.7-
0.02) = 12%

46
 :Hypoeutectoid Steel

Proeutectoid α (α prime ):
α phase formed at T > Teutectoid

47
 µ m 10

This is the image of two-phase structure (alpha-Fe + Pearlite)

48 formed in Fe-0.4wt%C alloy
 :Hypereutectoid Steel

49
• Steel : Fe-1wt%C
This secondary electron SEM image shows the cementite
delineating prior austenite grain boundaries with a thin layer.
The majority of the area being taken by the pearlite eutectoid. Each
pearlite cell has a different orientation; the dark phase is a ferrite
phase.
50
 Example: calculations of the
amounts according to lever rule

51
52
53
 :Steel With Alloying Elements
• Teutectoid changes: • Ceutectoid changes:

C eutectoid (wt%C)
0.8
T Eutectoid (°C)

1200 Ti Si
Mo W 0.6 Ni
1000 Cr
Cr 0.4
Si
800 Mn
Mn 0.2 W
Ti Mo
600 Ni
0
0 4 8 12 0 4 8 12
wt. % of alloying elements wt. % of alloying elements

54
 Example: stainless steel.
At first, let us review Fe-Ni and Fe-Cr binary phase
diagrams:

Fe

55
 Vertical section of Fe-Cr-C
%. diagram for 0.1C wt

• This figure shows that an excessive amount of chromium

can eliminate austenite at all temperatures, making it
impossible to achieve a γ to α transition.
• Without carbon, the limit beyond which austenite no
longer forms is about 13.5 wt% chromium. However,
additions of carbon help stabilize the austenite and
therefore increase this limit.
56
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The effect of 6%
manganese on the
stability ranges of
the phases in the
eutectoid portion of
the Fe-Fe3C phase
diagram.

57
 :Summary
Make sure you understand language and
concepts:
• Austenite •Lever rule
• Cementite •Liquidus line
• Component •Metastable
• Congruent transformation •Microstructure
• Equilibrium •Pearlite
• Eutectic phase/reaction/structure •Peritectic reaction
• Eutectoid reaction •Phase
• Ferrite •Phase diagram
• Hypereutectoid alloy •Primary phase
• Hypoeutectoid alloy •Solidus line
• Intermetallic compound •Solubility limit
• Isomorphous •System
•Tie line

58