Unit-2

Phase Diagram
 Contents

Equilibrium Diagram:
Importance of Equilibrium diagram,
Gibbs’s Phase Rule,
Solid Solution & their types,
Hume Rothery's rules,
Types of phase diagram,
Isomorphism, Eutectic, Peritectic and Eutectoid Reaction,
Importance of lever rule.
Iron carbon equilibrium Diagram:
Phases in the Fe–C system
Transformation Reactions,
Critical Temperatures and their significance,
The TTT diagram,
CCT diagram.
 Phase Diagrams

• A phase diagram is a graphical representation of the phases that are

present in a material at various temperatures and pressures and
compositions.

• It usually describes the equilibrium conditions.

• Sometimes non-equilibrium conditions are also shown when well

known.
 Importance of Phase diagram
Important information, useful in materials development and selection,
obtainable from a phase diagram:
 It shows phases present at different compositions and temperatures
under slow cooling (equilibrium) conditions.
 It indicates equilibrium solid solubility of one element/compound in
another.
 It suggests temperature at which an alloy starts to solidify and the
range of solidification.
 It signals the temperature at which different phases start to melt.
 Amount of each phase in a two-phase mixture can be obtained.
 Definitions/Terms related with Phase Diagram
• System - A part of universe under study is called system.

• Phase - A phase is a homogenous, physically distinct and mechanically

separable portion of the material/system with a given chemical
composition and structure (a and b).

• Variable - A particular phase exists under various conditions of

temperature, pressure and concentration. These parameters are called
as the variables of the phase.

• Components - The elements or compounds that are present in the

system are called as components. E.g.- Al and Cu in Cu-Al system.
 Gibbs phase rule
 In a system under a set of/equilibrium conditions, number of phases(P)
exist can be related to the number of components(C) and degrees of
freedom(F) by Gibbs phase rule.
 Thermodynamically derived Gibbs phase rule is expressed as
P+F=C+2
 Degrees of freedom refers to the number of independent variables
(e.g.: pressure, temperature) that can be varied independently without
changing the number of phases existing in the system.
 In practical conditions for metallurgical and materials systems,
pressure can be treated as a constant (1atm.).
 Thus Condensed Gibbs phase rule is written as:
P+F=C+1
In the above rule 1 represents any one variable out of the remaining two
i.e. temperature and pressure.
 Solid Solution-
• It is an alloy in which the atoms of solute are distributed in the solvent
and has the same structure as that of the solvent.
• Solid solutions have different compositions with similar structure.
• There are two types of solid solutions:
1) Substitutional solid solution:
2)Interstitial solid solution:
 Substitutional Solid Solution–
• Solute atoms occupy the regular lattice sites of the parent metal
(solvent).
• Substitutional solid solutions can be Ordered / Regular (Cu-Au) or
Disordered /Random (Cu-Ni).

Random substitutional Ordered substitutional Solvent atom Solute atom

• Complete regularity is possible only when the two metals are mixed in
some proportions like 1:1 , 3:3 etc.
• Substitutional solid solutions formation is favored if atomic sizes of two
metals are nearly equal.
• Ordered substitutional solution alloys in general are hard than Random
substitutional alloys.
 Interstitial solid solution-
• Solute atoms occupy the interstitial positions (Steel – C solute atoms
in Fe) .
• This type of solid solution formation is favoured when the atomic size
of solute atom is very small as compared to atomic size of solvent.

Interstitial solid solution

 Intermediate Phases
• As the name suggest intermediate structures formed between two
metals are neither the parent metals nor like an alloy.
Intermetallic compounds -
• If two elements have high difference in electronegetivity, they tend to
from a system called intermetallic compound.
• Intermetallic compounds like Mg2Si, Cu2S are cubic whereas NiAs, CuSn
are hexagonal.
Sigma phase
• Sigma phase has a very complex crystal structure and is very brittle.
• This phase can act as a source of embrittlement in some alloys such as
steels.
Metal carbides and nitrides
• Metals which have high chemical affinity for carbon and nitrogen form
carbides and nitrides such as VC, VN, TiC, TiN.
• They can act as source of hardening in many alloys
 Hume-Rothery’s rules of solid solubility-
• In formation of solid solution, the solubility limit in the solvent is
governed by certain factors. These factors are known as Hume
Rothery’s rules of solid solubility.

1) Atomic size factors - Solid solution formation is favourable when the

difference in atomic size between the two atoms is < ~15%, otherwise
solubility is limited.
2) Chemical affinity factor - The greater the chemical affinity of two metals,
the more restricted is their solid solubility and greater the tendency of
formation of compound.
3) Relative valency factor - Lower valency metal have good solubility for
the higher valency metal.
4) Crystal structure - Metals having same crystal structure will have
greater solubility.
 Lever rule-
• The weight percentages of the phases in any 2 phase region for given
alloy at any temperature can be calculated by using the lever rule.
• Let us consider an isomorphous system of two metals A and B.

Fig- A typical isomorohous phase diagram

• Consider an isomorphous system of two metals A & B as shown in fig.
• Let Z be the composition of the alloy under consideration & T be the
temperature at which the amounts of phases are to be found out.
• Let amount of solid be (S) and hence amount of liquid(L) will be 1-S, if
total amount is assumed to be 1.
• Then to find equilibrium relative amounts of phases by lever rule - A
tie-line is constructed across the two phase region at the temperature
of the alloy to intersect the region boundaries.

Phase percent = opposite arm of lever x 100

total length of the tie line

Therefore amount of solid S = (Arm length CF)/(Arm length CD)

= (Opposite arm length)/(Total length of arm)
Hence amount of liquid L = 1-S
 Types of phase diagram
1. Isomorphism: Complete Solubility in both liquid & solid states
example: Cu-Ni, Ag-Au, Ge-Si, Al2O3-Cr2O3.

Figure: Isomorphism System

2.Eutectic : Complete Solubility in both liquid state, but limited
solubility in the solid state
Example: Pb-Sn, Cu –Al etc

Figure: Eutectic System

2. Eutectic: 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 183°C, which is lower than the
melting points of both Pb (327 °C) and Sn (232°C)
→can be used for soldering purposes (as we want to input
east amount of heat to solder two materials). .
3. Peritectic : Like the eutectic system, the peritectic reaction is found
in systems with complete liquid solubility but limited solid solubility.
Example: Fe-C, Cu-Zn, Al-Ti, Pt-Ag system etc
4.Eutectoid Reactions:
- occurs from one solid phase to two new solid
phases.
- Upon cooling, a solid phase transforms into two
other solid phases (γ↔α + β) in the example
below)
- example: Fe-C, Cu-Sn, Cu-Al, Zn-Al, Al-Mn etc
 Iron carbon equilibrium diagram
• In their simplest form, steels are alloys of Iron (Fe) and Carbon
(C), in which carbon content is between 0.008and 2.0 percent.
• Commercial steels always contains some amount of other
elements. If these elements are accidentally present without any
intension, they are called impurities, however if they added
purposely they are called as alloying element.
• Steels with other element in small amounts are called plain
carbon steels and their structures and properties can be
discussed with the help of Fe-C equilibrium diagram.
• In certain cases, some of the elements are intentionally added to
steels to increase some of the required properties. These steels
are called alloy steels.
Iron carbon equilibrium diagram
Iron carbon equilibrium diagram
 Phases in Fe–Fe3C Phase Diagram

i) α‐ferrite‐solid solution of C in BCC Fe

Stable form of iron at room temperature.
The maximum solubility of C is 0.025 wt% at 727 °C
Transforms to FCC γ-austenite at 912 °C

ii) γ-austenite - solid solution of C in FCC Fe

The maximum solubility of C is 2.14 wt % at 1147
Transforms to BCC δ-ferrite at 1395 °C
Is not stable below the eutectic temperature (727 ° C) unless
cooled rapidly.
 Phases in Fe–Fe3C Phase Diagram (contd….)

iii) δ-ferrite solid solution of C in BCC Fe

The same structure as α-ferrite
Stable only at high T, above 1394 °C
Melts at 1538 °C

iv) Fe3C (iron carbide or cementite)

This intermetallic compound is metastable, it remains as a
compound
indefinitely at room T, but decomposes (very slowly, within
several years)
into α-Fe and C (graphite) at 650 - 700 °C.
 Phase transformations reactions
• Fe-C binary system contains three different Phase
transformations reactions as-
i) Peritectic transformation
ii) Eutectic transformation
iii) Eutectoid transformation
 Peritectic transformation
In general Peritectic transformation is denoted as –
S1 + L Constant Temp. S2

Where S1 & S2 = two different solids

L = liquid.

Peritectic reaction at 1492 C in equilibrium diagram is given as -

δ (o.1% C) + L ( o.55% C) 1492 γ-iron (o.18% C)

For Hypoperitectic steels the transformation can be written as

δ + L 1492 γ+δ

For Hyperperitectic steels the transformation can be written as

δ + L 1492 γ+L
 Eutectic transformation
In general Eutectic transformation is denoted as –
L Constant Temp. S1 + S2
Where S1, S2 = different solids
L = liquid.

Eutectic transformation at 1147 C in equilibrium diagram is given as -

L ( 4.3%C) 1147 γ (2.0%C) + Fe3C (6.675%C)

 Eutectoid transformation
In general Eutectoid transformation is denoted as –
S1 Constant Temp. S2 + S3
Where S1, S2 & S3 = different solids

Eutectoid transformation at 727 C in equilibrium diagram is given as

–

γ (0.8% C) 727 α (0.025%C) + Fe3C (6.67% C)

 Critical temperatures
These are the temperatures at which the phase changes occur during heating and
cooling.
Critical temperatures in Fe-Fe3C Equilibrium diagram are represented as-

A0 - Cementite changes from ferromagnetic to paramagnetic.

- Indicated by A0 at 210 C.

A1- Denotes the temperature at which pearlite transforms to austenite.

- Transformation occur at constant temperature 727 C, called as
Eutectoid Temperature.
- This temp. also known as lower critical temp.

A2 - Indicates the temperature at which ferromagnetic ferrite becomes

paramagnetic.
- Transformation occur at 768 C , called as Curie temp.
 Critical temperatures (contd….)
A3 -Temp.at which last trace of free ferrite gets dissolved to form 100%
austenite.
- It decreases from 910 C at 0% C to 727 C At 0.8 C.
- Known as upper critical temp for ferrite.

Acm - The temp. at which last trace of free cementite gets dissolved to
form 100 % austenite.
- It increases from 727 C to 1147 C with increase in carbon from 0.8
to 2.0 %.
- Also known as upper critical temperature for cementite.
 TTT Diagram

• T (Time) T(Temperature) T(Transformation) diagram is a plot of temperature

versus time for a steel alloy of definite composition.

• It is used to determine when transformations begin and end for an isothermal

(constant temperature) heat treatment of a previously austenitized alloy.

• These diagrams indicate the phases existing in steels at various temperatures

and time, hence useful in heat treatment of steels.

• With the help of these diagram proper cooling cycle can be selected to obtain
desired transformation product.
 Determination of TTT diagram-
• For the given steel, TTT diagram can be experimentally determined as below-
i) Heat large no of steel pieces of a suitable size in austenitic region. Throughout
the experiment, the austenitizing temp. must be kept constant.
ii) Soak this samples for sufficient time, to obtain homogeneous austenite.
iii) Transfer all these samples quickly into a salt bath kept in another furnace at
some constant temp. between A1 and Ms.
iv) Remove these samples one by one at fixed interval of time and quench them in
brine or cold water, due to this untransformed austenite transformed to
martensite.
v) Study these samples metallographically and find out time of start of that
particular transformation and end of transformation.
vi) Similar studies are conducted at different temperatures, and time of start and
end of transformation are determined.
vii) The obtained times at different isothermal transformation temp. are plotted on
temp Vs time graph and smooth curves are drawn through these points.
 TTT diagram- (contd….)
• Typical TTT diagram of eutectoid, hypoeutectoid and hypereutectoid steels are shown in
fig –

TTT diagram of Eutectoid steel

a) Hypoeutectoid steel ( 0.35% C) b) Hypereutectoid steel (1.1% C)
 CCT(Continuous Cooling Transformation )Diagrams

 Isothermal TTT diagram are not the most practical due to rapidly cooling and
constant maintenance at an elevated temperature.

 Most heat treatments for steels involve the continuous cooling of a specimen to
room temperature.

 For continuous cooling, of steel from high temp. to low temp. the time required for
a reaction to begin and end is delayed due to this –

 The isothermal curves/ TTT curves are shifted to right and also downwards
require longer times and lower temperatures, i.e. pearlite and bainite
transformations occur at lower temp. and require longer time for completion.
Fig- Continuous Cooling Transformation (CCT) curve for eutectoid steel.
 Possible Transformations

Martensite
T Martensite
Strength

Ductility

Bainite
Fine pearlite
Coarse pearlite
Spheroidite
General Trends