EQUILIBRIUM PHASE DIAGRAMS

ANANDH SUBRAMANIAM
Materials Science and Engineering
INDIAN INSTITUTE OF TECHNOLOGY KANPUR
Kanpur- 110016
Ph: (+91) (512) 259 7215, Lab: (+91) (512) 259 7147
anandh@iitk.ac.in
http://home.iitk.ac.in/~anandh/
MATERIALS SCIENCE
19 Oct 2015
& AALearner
Learners Guide
Learners Guide
ENGINEERING http://home.iitk.ac.in/~anandh/E-book.htm
AN INTRODUCTORY E-BOOK

Alloy Phase Equilibria, A. Prince, Elsevier Publishing Company, Amsterdam (1966)

Phase Diagrams
Phase diagrams are an important tool in the armory of an materials scientist
In the simplest sense a phase diagram demarcates regions of existence of various phases.
This is similar to a map which demarcates regions based on political, geographical,
ecological etc. criteria.
Phase diagrams are maps*
Thorough understanding of phase diagrams is a must for all materials scientists
Phase diagrams are also referred to as EQUILIBRIUM PHASE DIAGRAMS
This usage requires special attention: though the term used is Equilibrium, in practical
terms the equilibrium is NOT GLOBAL EQUILIBRIUM but MICROSTRUCTURAL
LEVEL EQUILIBRIUM (explanation of the same will be considered later)
This implies that any microstructural information overlaid on a phase diagram is for
convenience and not implied by the phase diagram.
The fact that Phase Diagrams represent Microstructural Level equilibrium is often not
stressed upon.

* there are many other maps that a material scientist will encounter like creep mechanism maps, various kinds of materials selection maps etc.
 Broadly two kinds of phase diagrams can be differentiated* those involving time and
those which do not involve time (special care must be taken in understanding the former
class- those involving time).
In this chapter we shall deal with the phase diagrams not involving time.
This type can be further sub-classified into:
Those with composition as a variable (e.g. T vs %Cu)
Those without composition as a variable (e.g. P vs T)
Temperature-Composition diagrams (i.e. axes are T and composition) are extensively used in
materials science and will be considered in detail in this chapter. Also, we shall restrict
ourselves to structural phases (i.e. phases not defined in terms of a physical property)**
Time-Temperature-Transformations (TTT) diagrams and Continuous-Cooling-
Transformation (CCT) diagrams involve time. These diagrams are usually designed to
have an overlay of Microstructural information (including microstructural evolution).
These diagrams will be considered in the chapter on Phase Transformations.

* this is from a convenience in understanding point of view

** we have seen before that phases can be defined based either on a geometrical entity or a physical property (sometimes phases based on a
physical property are overlaid on a structural phase diagram- e.g. in a Fe-cementite phase diagram ferromagnetic phase and curie
temperatures are overlaid)
Let us start with some basic definitions:

DEFINITIONS

Components of a system

Independent chemical species which comprise the system:

These could be: Elements, Ions, Compounds
E.g.
Au-Cu system : Components Au, Cu (elements)
Ice-water system : Component H2O (compound)
Al2O3 Cr2O3 system : Components Al2O3, Cr2O3
Note that
components need not
be only elements

This is important to note that components need not be just elements!!

Phase This is the typical textbook definition which one would see!!

Physically distinct, chemically homogenous and mechanically separable region of a

system (e.g. gas, crystal, amorphous...).

Gases
Gaseous state always a single phase
mixed at atomic or molecular level Three immiscible liquids
Liquids
Liquid solution is a single phase
e.g. NaCl in H2O
Liquid mixture consists of two or more phases
e.g. Oil in water (no mixing at the atomic/molecular level)
Solids
In general due to several compositions and crystals structures many phases are possible
For the same composition different crystal structures represent different phases.
E.g. Fe (BCC) and Fe (FCC) are different phases
For the same crystal structure different compositions represent different phases.
E.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases
What kinds of Phases exist?

We have already seen the official definition of a phase:

Physically distinct, chemically homogenous and mechanically separable region of a
system.
However, the term phase is used in diverse contexts and we list below some of these.

Based on state Gas, Liquid, Solid

Based on atomic order Amorphous, Quasicrystalline, Crystalline
Based on Band structure Insulating, Semi-conducting, Semi-metallic, Metallic
Based on Property Paraelectric, Ferromagnetic, Superconducting, ..
Based on Stability Stable, Metastable, (also- Neutral, unstable)
Also sometimes- Based on Size/geometry of an entity Nanocrystalline, mesoporous,
layered,
Phase transformation
Phase Transformation is the change of one phase into another.
E.g.: Water Ice
- Fe (BCC) - Fe (FCC)
- Fe (FCC) - Fe (ferrite) + Cementite (this involves change in composition)
Ferromagnetic phase Paramagnetic phase (based on a property)

Grain

The single crystalline part of polycrystalline metal separated by similar entities by a

grain boundary

Microstructure An alternate definition based on magnification

(Phases + defects + residual stress) & their distributions

Structures requiring magnifications in the region of 100 to 1000 times

OR
The distribution of phases and defects in a material

Again this is a typical textbook definition which has been included for!!
Phase diagram
Map demarcating regions of stability of various phases.
or
Map that gives relationship between phases in equilibrium in a system as a
function of T, P and composition (the restricted form of the definition sometime considered in materials textbooks)

Variables / Axis of phase diagrams

The axes can be:
Thermodynamic (T, P, V),
Other possibilities include magnetic field intensity (H), electric field (E) etc.
Kinetic (t) or
Composition variables (C, %x) (composition is usually measure in weight%, atom% or mole fraction)
In single component systems (unary systems) the usual variables are T & P
In phase diagrams used in materials science the usual variables are:T & %x
In the study of phase transformation kinetics Time Temperature Transformation
(TTT) diagrams or Continuous Cooling Transformation (CCT) diagrams are also
used where the axis are T & t
 Important points about phase diagrams (Revision + extra points)

Phase diagrams are also called Equilibrium Phase Diagrams.

Though not explicitly stated the word Equilibrium in this context usually means
Microstructural level equilibrium and NOT Global Equilibrium.
Microstructural level equilibrium implies that microstructures are allowed to
exist and the system is not in the global energy minimum state.
This statement also implies that:
Micro-constituents* can be included in phase diagrams
Certain phases (like cementite in the Fe-C system) maybe included in phase
diagrams, which are not strictly equilibrium phases (cementite will decompose to
graphite and ferrite given sufficient thermal activation and time)
Various defects are tolerated in the product obtained. These include defects
like dislocations, excess vacancies, internal interfaces (interphase boundaries,
grain boundaries) etc.
Often cooling lines/paths are overlaid on phase diagrams- strictly speaking this
is not allowed. When this is done, it is implied that the cooling rate is very slow
and the system is in ~equilibrium during the entire process.
(Sometimes, even fast cooling paths are also overlaid on phase diagrams!)

* will be defined later

 The GIBBS PHASE RULE
The phase rule connects the Degrees of Freedom, the number of Components in a system
and the number of Phases present in a system via a simple equation.
To understand the phase rule one must understand the variables in the system along with
the degrees of freedom.
We start with a general definition of the phrase: degrees of freedom

Degrees of Freedom: A general definition

In response to a stimulus the ways in which the system can respond corresponds to the
degrees of freedom of the system

For a system in equilibrium F=CP+2 F Degrees of Freedom

or C Number of Components
The phase rule FC+P=2 P Number of Phases

The Phase rule is best understood by considering examples from actual phase diagrams as
shown in some of the coming slides
Variables in a Phase Diagram
C No. of Components
P No. of Phases
F No. of degrees of Freedom
Variables in the system =
Composition variables + Thermodynamic variables
Composition of a phase specified by (C 1) variables
(e.g. If the composition is expressed in %ages then the total is 100% there is one equation
connecting the composition variables and we need to specify only (C1) composition variables)
No. of variables required to specify the composition of all Phases: P(C 1)
(as there are P phases and each phase needs the specification of (C1) variables)
Thermodynamic variables = P + T (usually considered) = 2
(at constant Pressure (e.g. atmospheric pressure) the thermodynamic variable becomes 1)
Total no. of variables in the system = P(C 1) + 2
F < no. of variables F < P(C 1) + 2
A way of understanding the Gibbs Phase Rule: F = C P + 2
The degrees of freedom can be thought of as the difference between what you (can) control
and what the system controls

F = C+2 P

Degrees of Freedom = What you can control What the system controls

Can control the no. of System decided how many

components added and P & T phases to produce given the
conditions
Single component phase diagrams (Unary)
Let us start with the simplest system possible: the unary system wherein there is just one
component.
Though there are many possibilities even in unary phase diagrams (in terms of the axis and
phases) , we shall only consider a T-P unary phase diagram.
Let us consider the Fe unary phase diagram as an illustrative example.
Apart from the liquid and gaseous phases many solid phases are possible based on crystal
structure. (Diagram on next page).
Note that the units of x-axis are in GPa (i.e. high pressures are needed in the solid state and
liquid state to see any changes to stability regions of the phases).
The Gibbs phase rule here is: F = C P + 2. (2 is for T & P).
Note that how the phase fields of the open structure (BCC- one in the low T regime () and
one in the high T regime ()) diminish at higher pressures. In fact - phase field completely
vanishes at high pressures.
The variables in the phase diagram are: T & P (no composition variables here!).
Along the 2 phase co-existence lines the DOF (F) is 1 i.e. we can chose either T or P
and the other will be automatically fixed.
The 3 phase co-existence points are invariant points with F = 0. (Invariant point implies
they are fixed for a given system).
 F=CP+2

Gas Single phase regions

F=11+2=2
T and P can both be varied while still
being in the single phase region

Liquid
Temperature (C)

Two phase coexistence lines

F=12+2=1
(BCC) we have only one independent variable
(we can chose one of the two variables (T
or P) and the other is automatically
1535 fixed by the phase diagram)
1410
(FCC)
Triple points:
3 phase coexistence
(BCC) (HCP) F=13+2=0
triple points are fixed points of a
phase diagram (we cannot chose T or P)

Pressure (GPa)
The maximum number of phases which can
Note the P is in GPa coexist in a unary P-T phase diagram is 3
Very High pressures are required for things to happen in the solid state
 Understanding aspects of the iron unary phase diagram

The degrees of freedom for regions, lines and points in the figure are marked in the diagram
shown before
The effect of P on the phase stability of various phases is discussed in the diagram below
It also becomes clear that when we say iron is BCC at RT, we mean at atmospheric pressure
(as evident from the diagram at higher pressures iron can become HCP)

This line slopes upward as at constant T if we increase the P the

Gas gas will liquefy as liquid has lower volume (similarly the reader
should draw horizontal lines to understand the effect of pressure
Increase P and gas will
liquefy on crossing phase on the stability of various phases- and rationalize the same).
Liquid boundary
Temperature (C)

Phase fields of non-close packed structures

(BCC) shrink under higher pressure

Phase fields of close packed structures expand

(FCC) under higher pressure

These lines slope downward as: Under

(HCP) higher pressure the phase with higher
(BCC) packing fraction (lower volume) is
preferred

Pressure (GPa)
Usually (P = 1 atm) the high temperature phase is the
loose packed structure and the RT structure is close packed.
How come we find BCC phase at RT in iron?
Binary Phase Diagrams

Binary implies that there are two components.

Pressure changes often have little effect on the equilibrium of solid phases (unless
ofcourse we apply huge pressures).
Hence, binary phase diagrams are usually drawn at 1 atmosphere pressure.
The Gibbs phase rule is reduced to:
Variables are reduced to: F = C P + 1. (1 is for T).
T & Composition (these are the usual variables in Materials Phase Diagrams)

Phase rule for condensed phases F=CP+1

For T

In the next page we consider the possible binary phase diagrams. These have been
classified based on:
Complete Solubility in both liquid & solid states
Complete Solubility in both liquid state, but limited solubility in the solid state
Limited Solubility in both liquid & solid states.
Overview of Possible Binary Phase diagrams
Liquid
Liquid State
State Solid
Solid State
State analogue
analogue

Complete Solubility in both liquid & Isomorphous Solid state analogue of

solid states Isomorphous
Isomorphous with ordering

Isomorphous with
phase separation

Eutectic Eutectoid
Complete Solubility in both liquid state,
but limited solubility in the solid state
Peritectic Peritectoid

Monotectic Monotectoid
Limited Solubility in both liquid & solid
states
Syntectic
What are the variables/DOF in a binary phase diagram?

We have already seen that the reduced phase rule at 1Atm pressure is: F = C P + 1.
The one on RHS above is T.
The other two variables are:
Composition of the liquid (CL) and composition (CS) of the solid.
In a fully solid state reaction:
Composition of one solid (CS1) and composition of the other solid (CS2).
The compositions are defined with respect to one of the components (say B):
CLB, CSB

The Degrees of Freedom (DOF, F) are defined with respect to these variables.
System with complete solid & liquid solubility: ISOMORPHOUS SYSTEM
Let us start with an isomorphous system with complete liquid and solid solubility Pure
components melt at a single temperature, while alloys in the isomorphous system melt
over a range of temperatures*. I.e. for a given composition solid and liquid will coexist
over a range of temperatures when heated.
Model Isomorphous phase diagram
We mention some important points here (may be/have been reiterated elsewhere!):
Such a phase diagram forms when there is complete solid and liquid solubility.
The solid mentioned is crystalline.
The solid + liquid region is not a semi-solid (like partly molten wax or silicate glass). It is a
crystal of well defined composition in equilibrium with a liquid of well defined
composition.
Both the solid and the liquid and the solid (except pure A and pure B) have both A and B
components in them.
A and B components could be pure elements (like in the Ag-Au, Au-Pd, Au-Ni, Ge-Si) or
compounds (like Al2O3-Cr2O3).
At low temperatures the picture may not be
ideal as presented in the diagram below and we Liquid (solution)
may have phase separation (Au-Ni system) or
have compound formation (for some
compositions) (Au-Pd system). These cases will Solid + Liquid

T
be considered later.
Each solid, with a different composition is a
Note that between two single
different phase. The area marked solid in the phase regions there is a two
phase diagram is a phase field. phase region (for the alloy) Solid (solution)
(except for special cases)
If heated further the liquid will vaporize, this part
of the phase diagram is usually not shown in the
diagrams considered. A %B B
Now let us map the variables and degrees of freedom in varions regions of the isomorphous phase diagram
C=1 F=CP+1
P=2
F=0 Variables T, CLB 2 C=2
P = 1 (liquid)
M.P. of A F=2
Liquid
For pure components all
Variables T and Composition can
transformation
temperatures (BCC to T, CLB, CSB 3 both be varied while still

T
FCC, etc.) are fixed (i.e. being in the single phase
zero F) region
Solid + Liquid
in the two phase region, if
we fix T (and hence exhaust C=2
our DOF), the composition of P=2
liquid and solid in equilibrium F=1
are automatically fixed (i.e. we
have no choice over them).
Alternately we can use our
DOF to chose CL then T
Solid M.P. of B
and CS are automatically Disordered (substitutional) solid solutions
fixed.
C=2
Variables T, CSB 2
P=1
F=2

A B
%B F=2P
F=2P F= 3 P
For alloys
For pure components at any T
Gibbs free energy vs composition plot at various temperatures: Isomorphous system
As we know at constant T and P the Gibbs free energy determines the stability of a phase. Hence, a
phase diagram can be constructed from G-composition (Gmixing-C) curves at various temperatures.
For an isomorphous system we need to chose 5 sample temperatures: (i) T1 > TA, (ii) T2=TA, (iii)
TA>T3>TB, (iv) T4=TB, (v) T5<TB.

For compositions
between X1 and X2
the common tangent
construction gives
the free energy of
G of L lower than for all
the L+ mixture
G of L lower than for all
compositions and hence L is stable compositions except for pure A.

How
How to get G
to get G
versus
versus composition
composition
curves
curves
Click
Click here
here to
to know ..
know more
more

5
 Isomorphous Phase Diagram: an example
A and B must satisfy Hume-Rothery rules for the formation of extended solid solution.

Examples of systems forming isomorphous systems: Cu-Ni, Ag-Au, Ge-Si, Al2O3-Cr2O3.

Note the liquidus (the line separting L & L+S regions) and solidus (the line separating L+S
and S regions) lines in the figure.

2200
Liquidus
L+S
T (C)

2100

S
2000 Solidus
Note that the components in
this case are compounds

Al2O3 10 30 50 70 90 Cr2O3
%Cr2O3 Schematics
 ISOMORPHOUS PHASE DIG.

Points to be noted:
Pure components (A,B) melt at a single temperature. (General) Alloys melt over a range of
temperatures (we will see some special cases soon).
Isomorphous phase diagrams form when there is complete solid and liquid solubility.
Complete solid solubility implies that the crystal structure of the two components have to be
same and Hume-Rothery rules have to be followed.
In some systems (e.g. Au-Ni system) there might be phase separation in the solid state (i.e.
the complete solid solubility criterion may not be followed) these will be considered later
in this chapter as a variation of the isomorphous system (with complete solubility in the
solid and the liquid state).
Click here to know more about HUME ROTHERY RULES

Both the liquid and solid contain the components A and B.

In Binary phase diagrams between two single phase regions there will be a two phase
region In the isomorphous diagram between the liquid and solid state there is the
(Liquid + Solid) state.
The Liquid + Solid state is NOT a semi-solid state it is a solid of fixed composition
and structure, in equilibrium with a liquid of fixed composition.
In the single phase region the composition of the alloy is the composition.
In the two phase region the composition of the two phases is different and is NOT the
nominal composition of the alloy (but, is given by the lever rule). Lever rule is considered next.
Tie line and Lever Rule
Given a temperature and composition- how do we find the fraction of the phases present along with the composition?

Say the composition C0 is cooled slowly (equilibrium)

At T0 there is L + S equilibrium
Solid (crystal) of composition C1 coexists with liquid of composition C2

We draw a horizontal line (called the Tie

Line) at the temperature of interest (say T0).
Tie line is XY.
Note that tie lines can be drawn only in the
two phase coexistence regions (fields). Though
they may be extended to mark the temperature.
To find the fractions of solid and liquid we
use the lever rule.
 We draw a horizontal line (called the Tie Line) at the temperature of interest (say T0).
The portion of the horizontal line in the two phase region is akin to a lever with the
fulcrum at the nominal composition (C0).
The opposite arms of the lever are proportional to the fraction of the solid and liquid
phases present (this is the lever rule).

At T0
Note: strictly speaking The fraction of liquid (fl) is (C0 C1)
cooling curves cannot be
overlaid on phase diagrams
The fraction of solid (fs) is (C2 C0)
Cooling C0 C1 C2 C0
fliquid at T0 f solid
Arm of the lever
Arm of the lever C2 C1 atT0
C2 C1
proportional to L
the liquid proportional to
the solid

Tie line
T0 Note that tie line is drawn within the two phase
L+S region and is horizontal.
Fulcrum of the lever
T

S
A C1 C0 C2 B
%B
Expanded version

At T0
The fraction of liquid (fl) is proportional to (C0 C1) AC
The fraction of solid (fs) is proportional to (C2 C0) CB

Arm of the lever

proportional to Arm of the lever
the liquid proportional to
the solid
Extended tie line AC C0 C1
C fliquid
T0 AB C2 C1
A B
CB C2 C0
Fulcrum of the lever f solid
AB C2 C1

C1 C0 C2
Points to be noted

For a composition C0
At T0 Both the liquid and the solid phases contain both the components A and B
To reiterate: The state is NOT semi-solid but a mixture of a solid of a definite composition (C1) with a
liquid of definite composition (C2)
If the alloy is slowly cooled (maintaining ~equilibrium) then in the two phase region (liquid + solid
region) the composition of
the solid will move along the brown line and the composition of the liquid will move along the blue line.
The composition of the solid and liquid are changing as we cool!
Isomorphous Phase Diagrams Note that
Ag & Au are so similar that the phase diagram
becomes a thin lens (i.e. any alloy of Au & Ag melts
over a small range of temperatures as if it were
nearly a pure metal!!).
Any composition melts above the linear interpolated
melting point.

Note here that there is solid solubility, but it is not complete at

Any composition melts low temperatures (below the peak of the 1 + 2 phase field
above the linearly dome)
interpolated melting point (we will have to say more about that soon)

Below T1 (820C) for some range of compositions the solid T1

solubility of Au in Ni (and vice-versa) is limited.
Extensions of the simple isomorphous system: Congruently melting alloys
We have seen that a pure metal melts at a single temperature (Why?!!).
An alloy typically melts over a range of temperatures. However, there are special compositions which
can melt at a single temperature like a pure metal. One of these is the congruent melting composition-
in a variation of the isomorphous phase diagram. Some systems show this type of behaviour.
Intermediate compounds also have this feature as we shall see later.

Case A Elevation in MP Variables T, CLB, CSB 3 Depression in MP Case B

C=2
P=2
F = 1?? (see below)

Congruently melting alloys just like a pure metal

Is the DOF 1? No: in requiring that CLB = CSB we have exhausted the degree of freedom. Hence T
is automatically fixed DOF is actually zero! Tie line has shrunk to a point!
Extensions of the simple isomorphous system: What does this imply w.r.t the solid state phases?

Elevation in the MP means that the solid state is more stable (crudely speaking the
ordered state is more stable) ordering reaction is seen at low T.
Depression in MP means the liquid state (disordered) is more stable phase separation
is seen at low T. (Phase separation can be thought of as the opposite of ordering. Ordering (compound formation) occurs for
ve values of Hmix, while phase separation is favoured by +ve values of Hmix.

AB bonds stronger than AA and BB bonds AA and BB bonds stronger than AB bonds
Solid stabilized Ordered solid formation Liquid stabilized Phase separation in the solid
state
Case A Case B

E.g. Au-Ni
Examples of isomorphous systems with phase
separation and compound formation

Au-Ni: model system to

understand phase separation

Au-Pt system with phase

separation at low temperatures

Au-Pd system
with 3
compounds
Phase separation in a AlCrFeNi alloy (with composition
Al28.5Cr27.3Fe24.9Ni19.3) into two BCC phases
Congruent transformations
We have seen two congruent transformations (transformations which occur without
change in composition). The list is as below.
Melting point minimum
Melting point maximum
Order disorder transformation
Formation of an intermediate phase

Melting point maximum

Formation of an intermediate phase

Order disorder transformation

Eutectic Phase Diagram
Very few systems exhibit an isomorphous phase diagram (usually the solid solubility of one
component in another is limited).
Often the solid solubility is severely limited- though the solid solubility is never zero (due to
entropic reasons).
In a simple eutectic system (binary), there is one composition at which the liquid freezes to
two solids at a single temperature. This is in some sense similar to a pure solid which freezes
at a single temperature (unlike a pure substance the freezing produces a two solid phases-
both of which contain both the components).
The term EUTECTIC means Easy Melting The alloy of eutectic composition freezes at a
lower temperature than the melting points of the constituent components.
This has important implications e.g. the Pb-Sn* eutectic alloy melts at 183C, which is
lower than the melting points of both Pb (327C) and Sn (232C) can be used for
soldering purposes (as we want to input least amount of heat to solder two materials).
In the next page we consider the Pb-Sn eutectic phase diagram.
As noted before the components need not be only elements. E.g. in the A-Cu system a
eutectic reaction is seen between (Solid solution of Cu in Al) and (Al2Cu- a compound).

* Actually - eutectic alloy (or (Pb)-(Sn) eutectic alloy)

 327C Liquidus
L
300

T (C)
Eutectic reaction
L+
Solidus 232C

200 +L L+
D E 183C F

Teutectic = TE
100 Solvus
TE +

18% 97%
62%
Pb 10 30 50 70 90 Sn
%Sn
CE Ceutectic = CE CE
Eutectic reaction (the proper L Cool

way of writing the reaction) 62% Sn 183 C 18% Sn 97% Sn
CE CE CE
Note that Pb is CCP, while Sn at RT is Tetragonal (tI4, I41amd) therefore complete solid solubility across compositions
is ruled out!!
Note the following points:
and are terminal solid solutions (usually terminal solid solutions are given symbols ( and )); i.e. is a solid solution of
B (Sn) in A (Pb).
(In some systems the terminal solid solubility may be very limited: e.g. the Bi-Cd system).
has the same crystal structure as that of A (Pb in the example below) and has the same crystal
structure as B (Sn in the example below).
Typically, in eutectic systems the solid solubility increases with temperature till the eutectic point (i.e.
we have a sloping solvus line). In many situations the solubility of component B in A (and vice-
versa) may be very small.
The Liquidus, Solidus and Solvus lines are as marked in the figure below.

327C Liquidus
L
300 Eutectic reaction
L+
Solidus 232C
T (C)

200 +L L+
183C

100 +
Solvus
18% 62% 97%
Pb 10 30 50 70 90 Sn
%Sn
 At the eutectic point E (fig. below) 3 phases co-exist: L, &
The number of components in a binary phase diagram is 2 the number of degrees of freedom F = 0.
This implies that the Eutectic point is an Invariant Point for a given system it occurs at a fixed
composition and temperature.
For a binary system the line DF is a horizontal line.
Any composition lying between D and F will show eutectic solidification at least in part (for
composition E the whole liquid will solidify by the eutectic reaction as shown later).
The percentage of and produced by eutectic solidification at E is found by considering DF* as a
E
lever with fulcrum at E. D F

L
300 Eutectic reaction
L+

200 +L E
L+
D F
T (C)

C=2
P=3
100 F=0 +
* Actually just below DF
as tie lines are drawn in a
Increasing solubility of B in A with T two phase region
%B
A 10 30 50 70 90 B
Examples of Eutectic microstructures As pointed out before microstructural information is often overlaid on phase
diagrams. These represent microstructures which evolve on slow cooling.
(Al)

Al-Al2Cu lamellar eutectic

Al2Cu
Pb-Sn lamellar eutectic (note that one of the
2 m

Sn components is a compound!)

Though we label the microstructure

as Pb-Sn lamellar eutectic it is
actually a - eutectic.

Composition plot across lamellae

Pb
 C2

C1 C4

The solidification
sequence of C4 will be
similar to C2 except
that the proeutectic
phase will be

C3

Pb-Sn eutectic
Funda Check What is meant by microstructural level equilibrium?

let us understand the concept using an example considered before.

During the eutectic reaction (during slow cooling) a lamellar micro constituent is obtained.
Fig.1: Al-Al2Cu eutectic

This results in a huge amount of interfacial area between the two

phases (Al, Al2Cu), which will result in a high value of interfacial
energy.
2 m

The equilibrium state would correspond to the schematic as shown below.

Polyhedral crystals

Since we tolerate the microstructure as in Fig.1 (and do not take the system to the global
energy minimum state), the equilibrium considered in typical phase diagrams are
microstructural level equilibrium.
Peritectic Phase Diagram
Like the eutectic system, the peritectic reaction is found in systems with complete liquid
solubility but limited solid solubility.
In the peritectic reaction the liquid (L) reacts with one solid () to produce another solid ().
L + .
Since the solid forms at the interface between the L and the , further reaction is
dependent on solid state diffusion. Needless to say this becomes the rate limiting step and
hence it is difficult to equilibrate Peritectic reactions (as compared to say eutectic
reactions). Figure below.
In some peritectic reactions (e.g. the Pt-Ag system- next page), the (pure) phase is not
stable below the peritectic temperature (TP = 1186C for Pt-Ag system) and splits into a
mixture of ( + ) just below TP.
 Melting points of the components
Pt-Ag Peritectic system
vastly different.
Pt-Ag is perhaps not a good
example of a peritectic system
Peritectic reaction obvious looking at the phase
L+ field (not stable below the
peritectic composition).

TP

Note that below TP pure is not
stable and splits into ( + )

CP CP CPL

L Cool
Formal way of writing
the peritectic reaction
66.3% Ag 10.5% Ag 1186 C 42.4% Ag
CPL CP CP
Funda Check

Components need not be only elements- they can be compounds like Al2O3, Cr2O3.
Phase diagrams usually do not correspond to the global energy minimum- hence often
microstructures are tolerated in phase diagrams.
Phase diagrams give information on stable phases expected for a given set of
thermodynamic parameters (like T, P). E.g. for a given composition, T and P the phase
diagram will indicate the stable phase(s) (and their fractions).
Phase diagrams do not contain microstructural information- they are often overlaid on
phase diagrams for convenience.
Metastable phases like cementite are often included in phase diagrams. This is to extend
the practical utility of phase diagrams.
Strictly speaking cooling curves (curves where T changes) should not be overlaid on
phase diagrams. (Again this is done to extend the practical utility of phase diagrams assuming that the cooling is slow).
Precipitation
Precipitation Hardening
The presence of dislocations weakens the crystal leading to easy plastic deformation.
Putting hindrance to dislocation motion increases the strength of the crystal.
Fine precipitates dispersed in the matrix provide such an impediment.
Strength of Al 100 MPa
Strength of Duralumin with proper heat treatment (Al + 4% Cu + other alloying elements)
500 MPa.

Philosophy behind the process steps in Precipitation Hardening

If a high temperature solid solution is slowly cooled, then coarse (large sized) equilibrium
precipitates are produced. These precipitates have a large distance between them. These
precipitates have incoherent boundaries with the matrix (incoherent precipitates).
Such (coarse) precipitates, which have a large inter-precipitate distance, are not the best
in terms of the increase in the hardness.
Hence, we device a 3 step process to obtain a fine distribution of precipitates, which have a
low inter-precipitate distance, to obtain a good increase in hardness.

r
tte
g oo
d Be
t Multi-step process used to
No
obtain a fine distribution of
Coarse incoherent
precipitates (with small
precipitates, with large
inter-precipitate distance)
inter-precipitate distance
Al-Cu phase diagram: the sloping solvus line and the design of heat treatments

The Al-Cu system is a model system to understand precipitation hardening (typical

composition chosen is Al-4 wt.% Cu).
Primary requirement (for precipitation hardening) is the presence of a sloping solvus line
(i.e. high solubility at high temperatures and decreasing solubility with decreasing
temperature). In the Al rich end, compositions marked with a shaded box can only be used
for precipitation hardening.

Sloping Solvus line:

high T high solubility
low T low solubility of Cu in Al

Al
Cu
 +
Slow equilibrium cooling gives rise to coarse
precipitates which is not good in impeding
+ dislocation motion.*

( FCC ) ( FCC ) CuAl2 (Tetragonal )

slow cool
4 % Cu 0.5 % Cu 52 % Cu
550 o C RT RT

4 % Cu

*Also refer section on Double Ended Frank-Read Source in the chapter on plasticity: max = Gb/L
Heat treatment steps to obtain a fine distribution of precipitates
To obtain a fine distribution of precipitates the cycle A B C is used

Note: Treatments A, B, C are for the same composition

Assume that we start with a material having coarse
B
equilibrium precipitates (which has been obtained by prior slow cooling of the
sample).

A A: We heat the sample to the single phase region () in

C
the phase diagram (550C).
B: We quench (fast cooling) the sample in water to
+ obtain a metastable supersaturated solid solution (the amount
of Cu in the sample is more than that allowed at room temperature according to the
phase diagram).

4 % Cu C: We reheat the sample to relatively low temperature

(~180C/200C) get a fine distribution of precipitates. We
have noted before that at low temperatures nucleation is dominant over growth.

A Heat (to 550oC) solid solution

Supersaturated solution
B Quench (to RT)
Increased vacancy concentration
C Age (reheat to 200oC) fine precipitates
 100oC Schematic curves
Real experimental curves
are in later slides
Hardness

180oC

20oC

Log(t)

Higher temperature less time of aging to obtain peak hardness

Lower temperature increased peak hardness
optimization between time and hardness required

Note: Schematic curves shown- real curves considered later

 180oC Peak-aged

Hardness
Dispersion of Coarsening
fine precipitates of precipitates
(closely spaced) with increased
inter-precipitate spacing

Underaged Overaged
Not zero of
hardness scale
Log(t)
Region of precipitation
Region of solid solution hardening
strengthening Hardness is higher than that of Al (but little/some solid solution
(no precipitation hardening) strengthening)
 180oC Peak-aged

In

)
-c

es
Hardness
o he

n
zo
re
nt

P
(p

(G
re
c

nt
ip

re
ita
he
te
s )
Co

Section of GP zone parallel to (200) plane

Log(t)
CRSS Increase

Particle
shearing
Particle
By-pass
r f (t )
1 1
r 2
r
Particle radius (r)
GP Zones

Cu rich zones fully coherent with the matrix low interfacial energy
(Equilibrium phase has a complex tetragonal crystal structure which has incoherent
interfaces)
Zones minimize their strain energy by choosing disc-shape to the elastically soft <100>
directions in the FCC matrix
The driving force (Gv Gs) is less but the barrier to nucleation is much less (G*)
2 atomic layers thick, 10nm in diameter with a spacing of ~10nm
The zones seem to be homogenously nucleated (excess vacancies seem to play an
important role in their nucleation)
 Selected area diffraction (SAD) pattern, showing
streaks arising from the zones.

5nm

Bright field TEM micrograph of an Al-4% Cu alloy

(solutionized and aged) GP zones.

5nm
Atomic image of Cu layers in Al matrix