Phase Diagrams

Structure-Property Relationship

Dr. G.M. Karthik

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 Phase Diagrams
Phase diagram: The relationship between phases in a system as a function of
pressure, temperature, and composition is depicted in maps.
• Phase diagrams are important to the engineer (design and process)
• Properties of materials are functions of their microstructures
• The development of the microstructure of an alloy is related to the
characteristics of its phase diagram
• Also provides information related to the melting temperature (casting),
solidus temperature, phase boundaries, etc.
Phases with minimum
Temperature free energy under
equilibrium conditions
Represent equilibrium relationships corresponding
to the minimum free energy state of the system –
Equilibrium diagram or phase diagrams
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Composition
 • Phases present

• Solute?
Phase Diagrams •
•
Phase compositions
Relative phase amounts
• Spatial distribution
• Solvent?
• Component?
• Phases?
• Solubility Limit?
• Phase boundary?
• Phase equilibrium?
• Polymorphic form or
allotropic form?
• Time required or Rate
of transformation?
• Equilibrium phases?
• Metastable Phases?
Phase: Physically distinct, mechanically separable, and chemically homogeneous
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 Hume-Rothery rules
Substitutional solid solutions:
In substitutional solid solutions, the atoms of the host element are replaced by the atoms of another
element.
- The atomic radius difference between the solute and the solvent atoms should not exceed 15%.
- The crystal structure of the solute and the solvent elements should be similar.
- The valency of the two elements should be similar or equal.
- The electronegativities of the solute and the solvent atoms should be similar.
Interstitial solid solutions:
In interstitial solid solutions, the atoms of an element occupy the interstitial site present in the host
element crystal structure.
- The atomic radius difference between the solute and the solvent atoms should be more than 15% such
that the solute atoms are smaller than the solvent atoms.
- The electronegativities of the solute and the solvent atoms should be similar.
- The valency of the two elements should be similar or equal.

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One-Component (OR UNARY) Phase Diagram

• For pure metals

Phase
boundaries • The composition is constant
• Temperature and Pressure
Triple point
are varied

Triple point:
• 273.16 K and 6.04x10-3 atm
Allotropes: multiple solid phases • Solid, liquid, and vapor phases are
simultaneously in equilibrium with one another
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 Binary Phase Diagrams
Binary phase diagram is one in which temperature and composition are variable
parameters, and pressure is held constant - normally 1 atm.
• When the components are more than 2, the phase diagram becomes complex – Most
engineering applications use binary diagrams with the major solute element.

• Binary Isomorphous Systems

• Binary Eutectic System
• Binary Eutectoid System
• Binary Peritectic System

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 Binary Isomorphous Systems
Isomorphous System: the elements have
complete liquid and solid solubility of the two
components.
Example: copper–nickel system
• Liquidous line
• Solidus line
• Undercooling
• Freezing range
Pure metal Alloy
L
L

L+α L+α
Temp. Temp.
Undercooling α
Freezing α
range
Time Time 7
Interpretation of Phase Diagrams
• Phases Present
• Phase composition (Tie Line)
• Phase Fraction (Lever Rule)
Weight fraction - Two-Phase
Regions

Volume fraction = ?
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 Gibbs Phase Rules
This rule represents a criterion for the number of phases that will coexist within a system at
equilibrium

P+F=C+N
F - number of degree of freedom
C - number of components
P - number of phases
N - number of noncompositional variables (e.g., temperature and pressure)

Because pressure is constant (1 atm), the parameter N is 1- the temperature is the only
noncompositional variable.

P+F=C+1

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 Gibbs Phase Rules
Phase (P):
• Gas (always single phase)
• Liquid (single or multiple phases)
• Solid (single or multiple phases)
Component (C):
• Independent chemical species in terms of which the composition of a system is specified.
• Steel – Fe and C are the chemical species (2 components)
Component Phase
Water (H2O) 1 1 (liquid)
Water + Ice 1 2 (L + S)
Water + salt (H2O+NaCl) 2 1 (L)
Steel (Fe+C) 2 2 (α+Fe3C) 10
 Gibbs Phase Rules
Degrees of Freedom (F):
• the number of degrees of freedom or the number of externally controlled variables (e.g.,
temperature, pressure, composition) that must be specified to completely define the state
of the system
• F is the number of variables that can be changed independently without altering the
number of phases that coexist at equilibrium

P+F=C+1

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 P+F=C+1 C=?

Single Phase P=?

To completely describe the

system with 1 phase and 2
components, 2 parameters are
required
(temperature and composition)

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 P+F=C+1 C=?

Two Phase P=?

L+α, L+β, and α+β phase regions

To completely describe the system

with 2 phases and 2 components,
one parameter is required
(temperature or composition)

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 P+F=C+1 C=?

Three Phases P=?

The compositions of all three

phases as well as the
temperature are Fixed

Invariant Reaction

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 Development of
Microstructures in
Isomorphous Systems
Non-Equilibrium Cooling
Conditions

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 Development of
Microstructures in
Isomorphous Systems
Equilibrium Cooling
Conditions

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Binary Eutectic Systems
• Three single-phase regions are
found on the diagram: α, β, liquid
• α phase is a solid solution rich in
copper; it has silver as the solute
(FCC structure)
• β-phase solid solution also has an,
but copper is the solute (FCC
structure)

• Solvus Line
• Maximum solubility limit

Eutectic Reaction

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 Development of
Microstructures in
Eutectic Systems
Equilibrium Cooling
Conditions

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 Development of
Microstructures in
Eutectic Systems
Equilibrium Cooling
Conditions

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 Development of
Microstructures in
Eutectic Systems
Equilibrium Cooling
Conditions

Eutectic Reaction

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 Development of
Microstructures in
Eutectic Systems
Equilibrium Cooling
Conditions

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Equilibrium Diagrams Having Intermediate Phases Or Compounds

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Eutectoid And Peritectic Reactions
Eutectoid Reaction

Peritectic Reaction

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 Congruent transformations
• Those for which there are no compositional alterations are said to be congruent
transformations
• Examples of congruent transformations include allotropic transformations and melting
of pure materials

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Iron Carbon Phase Diagram

Dr. G.M. Karthik

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Fe–Fe3C Phase Diagram

Second most used material in the world

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 Polymorphic or Allotropic Transformation
Pure iron, upon heating, experiences two
changes in crystal structure before it melts
From room temperature to 912 ℃
• The stable form, called ferrite
• α –iron
• BCC crystal structure.
Above 912 ℃ till 1394 ℃
• Ferrite experiences a polymorphic
transformation to austenite
• γ -iron
• FCC crystal structure
Above 1394 ℃ to melting point (1538 ℃)
• FCC austenite reverts to δ-ferrite
• δ-iron
• BCC crystal structure

Carbon is an interstitial impurity in iron and forms a solid solution with each of the phases δ, γ,27 α
 Critical Temperatures

Critical Temperatures:
The temperatures at which phase changes
occurs during heating (Ac) or cooling (Ar)
A0 : 210℃ - Curie temp. of cementite
A1: 727℃ - Eutectoid temperature
A2: 768℃ - Curie temp. of Ferrite (ferro to para)
A3: (γ+α)/γ phase boundary for hypoeutectoid
steels (changes with C content)
Acm: γ/(γ+Fe3C) phase boundary for
hypereutectoid steels (changes with C content)

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Fe–Fe3C Phase Diagram
Second highest used material in the world

Why are we calling Fe-

Fe3C phase diagram
instead of Fe-C diagram?

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 Why not Fe–C diagram?

• Cementite (Fe3C) is metastable and remain as

a compound at room temperature.
• Heated between 650 and 700 ℃ for several
years
• Fe3C will gradually transform stable form
carbon (graphite), which will remain upon
subsequent cooling to room temperature.
• Thus, the Fe–Fe3C phase diagram is not a true
equilibrium
• Fe3C is not an equilibrium compound.
• Decomposition rate of Fe3C is extremely
sluggish
• So, all the carbon in steel will be as Fe3C
instead of graphite

The maximum solubility of C in α-ferrite at room temperature is 0.008 wt%

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 Phases in Fe-Fe3C diagram
Phase Term Crystal Definition Temperature Composition Notes
structure range
α-Fe α-Ferrite BCC Interstitial < 910 ℃ Max. solubility of C ~ • C solubility is very less
solid solution 0.02 wt% at 727 ℃ • Small Interstitial void space (0.19 Ȧ) in
of C in BCC BCC Fe
Fe • C atoms (0.71 Ȧ) much larger than
the interstitial void space.
• Strong local strain field, max.
strengthening
γ-Fe Austenite FCC Interstitial 910 ℃ - 1394 Max. solubility of C ~ • large Interstitial void space (0.52 Ȧ) in
solid solution ℃ 2.11 wt% at 1147 ℃ FCC Fe
of C in FCC • Transforms to BCC δ-ferrite at 1394
Fe °C.
• Is not stable below the eutectoid
temperature (727 ° C) unless cooled
rapidly.
δ-Fe δ-Ferrite BCC Interstitial 1394 ℃ - Max. solubility of C ~ • High temperature phase
solid solution 1539 ℃ 0.1 wt% at 1493 ℃ • Stable at high temp. > 1394 °C
of C in BCC • Transform to liquid at ~1539 °C
Fe
Fe3C iron carbide Orthorho Intermetallic 1147 ℃ to RT With 25 at.% or 6.67 • Forms when solubility of C in α-ferrite
or mbic compound of wt% of C in Fe exceeded below 727℃
cementite Fe and C • Hard and Brittle intermetallic31phase
• Metastable phase
 Micrographs

Ferrite Austenite

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 Steels and Cast Iron

• Commercial Steels contain

carbon less than 1 wt%
• Commercial Cast Irons
contain carbon less than
4.5 wt%

Hypo Hyper
Steels Cast Iron
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 Invariant Reactions

Peritectic

Eutectic

Austenite

Ledeburite
Eutectoid

Pearlite

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 Invariant Reactions
Peritectic Reaction Fe-Fe3C alloy Eutectoid Reaction
Cooling
𝐿𝑖𝑞𝑢𝑖𝑑 + 𝑆𝑜𝑙𝑖𝑑1 Heating
⇔ 𝑆𝑜𝑙𝑖𝑑2 Cooling
0.5 - 0.18
𝑆𝑜𝑙𝑖𝑑 1 ⇔ 𝑆𝑜𝑙𝑖𝑑2 + 𝑆𝑜𝑙𝑖𝑑3
Austenite δ% =
Heating
at 1493 ℃ 𝐿+𝛿 ⇔𝛾 1493 δ L
0.5 - 0.1
Pearlite
Structure - BCC FCC at 727 ℃ 𝛾 ⇔ (α + 𝐹𝑒3𝐶)
wt.% of C
0.5 0.10 0.18 γ Structure FCC BCC Orth.
(Tie line) Peritectic
Fraction (wt%) reaction wt.% of C
18 82 100 0.77 0.02 6.67
(Liver rule) (Tie line)
Fraction (wt%)
100 89 11
Eutectic Reaction (Liver rule)
Cooling Fe-Fe3C alloy L
𝐿𝑖𝑞𝑢𝑖𝑑 Heating
⇔ 𝑆𝑜𝑙𝑖𝑑1 + 𝑆𝑜𝑙𝑖𝑑2 γ
Ledeburite L Eutectic Eutectoid
reaction γ+Fe3C
at 1147 ℃ 𝐿 ⇔ (𝛾 + 𝐹𝑒3𝐶) γ+ L
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reaction
1147℃ L+Fe3C
Structure - FCC Orth. 727℃
2.11 4.3 6.67
wt.% of C 0.02 0.77 6.67
4.3 2.11 6.67
(Tie line) Ledeburite: γ+Fe3C
Pearlite: α+Fe3C
Fraction (wt%)
100 52 48 3
(Liver rule)
36
37
 Microstructures of Eutectoid Steel
Pearlite
at 727 ℃ 𝛾 ⇔ (α + 𝐹𝑒3𝐶)

Fe3C

Ferrite

Pearlite: Alternating layers or lamellae of the two phases

38 (α and
Microstructures of Hypo Eutectoid Steel
Pearlite
at 727 ℃ 𝛾 ⇔ (α + 𝐹𝑒3𝐶)

Pearlite: Alternating layers or lamellae of the two phases

39 (α and
Microstructures of Hyper Eutectoid Steel
Pearlite
at 727 ℃ 𝛾 ⇔ (α + 𝐹𝑒3𝐶)

Pearlite: Alternating layers or lamellae of the two phases

40 (α and
41
 Effect of Alloying elements
Ferrite Stabilizers
• Some elements tend to stabilize the ferrite phase in preference to the austenite phase
• Many of these elements might have the same crystal structure as the ferrite (BCC)
• They tend to reduce the austenite area on the phase diagram

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 Effect of Alloying elements
Austenite Stabilizers
• Some elements tend to stabilize the Austenite phase in preference to the Ferrite phase
• Mn, Ni are the common austenite stabilizing elements
• They tend to enlarge the austenite area on the phase diagram.

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Influence of Alloying Elements on Eutectoid Temperature

Ferrite Stabilizers
• Raises the eutectoid temperature to
above 727 ℃.
• Ti amd Mo are most effective elements
Austenite Stabilizers
• Lowers the eutectoid temperature to
below 727 ℃
• Ni amd Mn are most effective elements

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Influence of Alloying Elements on Eutectoid Composition

Both Ferrite and Austenite

Stabilizers decreases the eutectoid
composition from 0.77 % C

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Transformation Diagram
Nucleation and Growth Stages

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 ISOTHERMAL
TRANSFORMATION DIAGRAM
Eutectoid Steel
Time-Temperature-Transformation (TTT) diagram

iron–iron carbide eutectoid

reaction Pearlite

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iron–carbon alloy of eutectoid composition
 Microstructures
Diffusion is temperature dependent, at high
temperature diffusion of carbon atoms is faster so
coarser pearlite.
~Eutectoid temp.

~540C

• Other compositions, the curves will have different configurations.

Coarse Pearlite Fine Pearlite • Condition that the temperature of the alloy is held constant throughout the
duration of the reaction – isothermal; isothermal transformation diagrams, or
time–temperature–transformation (or T–T–T) plots
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TTT for hypoeutectoid steel

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TTT for hypereutectoid steel

+C

+C

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 Bainite
Austenite can also undergo transformation to other constitutes - one of these is
called bainite
• Austenite transforms to bainite at a lower
temperature than the pearlite formation
temperature
• When austenite is cooled rapidly below the
nose of the C-curve and kept isothermally in a
constant temperature bath
• The microstructure of the Bainite is again
ferrite and cementite (as in pearlite), however,
they don’t have the lamellar morphology
• Bainite: Fine nonlamellar mixture of ferrite and
carbide.
• Bainite is a Diffusional transformation
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 Types of Bainite Upper Bainite

• Upper Bainite – 550 to 350 ℃

• Feathery-shaped ferrite
• Cementite plates at the boundaries
• Hardness: 40-50 HRC

• Lower Bainite – below 350 ℃ and above Ms

• Ferrite is a plate-like
• Inside the ferrite plates transition carbides such as ε-
carbides (Fe2.4C) precipitate
• The carbide are much finer than those of upper bainite.
• Hardness: 50-55 HRC

Ferrite forms first and then cementite nucleates

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53
 Martensite
• When austenite is cooled to the ambient temperature ranges – Martensite will form
• Below bainitic transformation range – the diffusion rate of carbon becomes so negligible
• Therefore, austenite transforms without a change in composition to Martensite
• Diffusionless transformation

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• The interstitial carbon occupies the octahedral voids of FCC
• Body center and 12 edge centers
• Vertical C-axis of the BCT unit cell (cube edge) contract by 20% and a1,a2 (half of face
diagonals – expand by 12%)
c/a ratio > 1
c/a = 1% at 0.2%C
c/a = 1.04 at 0.8%C

• Iron atoms move in a coordinated fashion by a fraction of 55

an
interatomic distance.
 Types of Martensite
• Martenite start (Ms) temperature – martensite starts to form (below the bainitic range)
• By nucleation of the martensite plates at the austenite boundaries
• The amount of martensite formed is a function of the temperature below the Ms temperature the
alloy is cooled.
• It is not dependent on time at the temperature – diffusionless transformation
• Martensite Finish (Mf) Temperature
• The temperature below which we have 100% martensite.
• In some alloys, it can be below 0°C
• So, sub-zero treatment might be required
• Retained Austenite – the austenite that is not transformed to martensite and remainedwhen

Ms (°C) = 561-474C-33Mn-17Ni-17Cr-21Mo

Both Ms and Mf decreases with the alloying elements – except for cobolt
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Lath Martensite – high temperature and low alloying elements

Plate martensite – low temperature and high alloying elements

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 Continuous Colling
Transformation
Diagram
Eutectoid steel

Continuous cooling can not result in bainite in carbon steels

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 Continuous Colling
Transformation
Diagram for
alloy steel

In alloy steels continuous cooling can result bainite

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60
Heat Treatment of Steels

Dr. G.M. Karthik

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Heat Treatment of Steels

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Different Heat
Treatments

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 Annealing
Upper critical
The term annealing refers to a heat treatment in which a temperature
material is exposed to an elevated temperature for an
extended time and then slowly cooled.
(1) Relieve stresses
(2) Increase ductility
(3) Produce a specific microstructure. A3 Acm
Three stages: (1) heating to the desired temperature, (2)
holding or “soaking” at that temperature, and (3) Slow cooling
to
room temperature.
Austenitization: heating the steel into the austenite range
Above A3 for Hypo eutectoid steels
Above A1 for Hyper eutectoid steels Lower
Need to provide sufficient time to form homogeneous critical
austenite temperature

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 Different Types of Annealing
Full Annealing - is a heat treatment that is used to negate the effects of cold work—that is, to soften and increase
the ductility of a previously strain-hardened metal. Above A3 for hypo and A1 for hyper eutectoid steels
Spheroidize Annealing –
• Medium- and high-carbon steels having a microstructure containing even coarse pearlite - too hard to
machine or plastically deform.
• Heat-treated or annealed to develop the spheroidite structure.
• The spheroidizing heat treatment, during which there is a coalescence of the Fe3C to form the spheroid
particles, can take place Spheroidizing
Pearlite

Recrystallize Annealing – done in the subcritical temperature 600-650 C (the cold rolled ferrite recrystallize)
Stress relief Annealing - done around 600 C, to relive the stresses developed during forming/welding/machining– only
recovery occurs no recrystallization
Process Annealing – heat treatment given to metal inbetween the forming operations to improve ductility – full
recrystallization is not ensured. 65
 Normalizing

Refining the grain structure and

improving the mechanical properties

Normalizing Annealing 66
 Quenching and Tempering
Cooling rate at the core of the section should reach critical cooling rate – full hardening
Hyper eutectoid steels – upper critical temperature is steep – annealing and hardening above A1 not above Acm

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 Tempering
to relive the residual stresses and reduce the
brittleness of martensite

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 Hardenability
The ability of a material to be hardened through-out the cross section

• Jominy distance
Jominy end Quench Test • Ideal critical quench diameter
• Quench media also plays a role

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Critical diameter is function of
- Composition
- Grain size
- Austenitizing treatment

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Quench Cracks

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Martempering and
Austempering

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 Case Hardening Techniques
Surface of steel is made hard and wear resistance, core of the steel remain soft and tough

• Induction hardening (mass production of uniform cross sections)

• Laser hardening (defocused spot – no melting, high speed, precise control, shallow hardening
• Flame Hardening (Large workpieces)

No melting only heating above the upper critical temperature followed by immediate quenching

If carbon content of the steel is sufficient high to form hard 100% martensite

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 • Carburizing
If carbon content of the steel is low to form hard 100%
• Cyaniding martensite – then the chemistry of the surface must be changed
• Carbonitriding by adding more carbon or nitrogen only on the surface
• Nitriding
Carburizing:
• The carbon content on the surface of the steel is enriched up to 0.8-1.0%.
• Carbon diffuses into the steel as a function of time at temperatures above AC1 temperature (920-950 ℃) – austenitic range?
• Source of carbon – solid, liquid, gas

Pack Carburizing: Source of carbon (solid)

Part is kept in a carburized box - 85% charcoal+15% energizers(BaCO3)
• The depth of penetration increases as the square root of time
• Direct quenching from the carburizing temperature is nor possible

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 Gas Carburizing
A mixture containing 5-15% methane (propane) in a neutral carrier gas is used

• The carbon potential of the gas concentration increases with methane concentration.
• If the diffusivity of carbon is slower than carbon release from the gas - soot formation on the surface
• Close control of the temperature and case depth is possible
• Post quenching can be done directly.
Post carburization heat treatment
Liquid Carburizing

Typical bath composition 8% NaCN, 82% BaCl2, 10% NaCl

Case Core+Case
Direct Core
Refining Refining
Quench Refining
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Cyaniding
• The steel is heated in a molten cyanide salt bath maintained at 950°C, followed by
water or oil quenching.
• Liquid of NaCN, with concentration varying from 30-97%
• Both Carbon and Nitrogen enters the steel

Carbonitriding (dry/gas cyaniding)

• Gas carburizing process modified by the addition of anhydrous ammonia.
• The decomposition of ammonia – release nitrogen which enters the steel.
• Gas mixture – 15% NH3, 5% CH4 and 80% neutral gas
• -Done at temperature 700-900 C.

76
Nitriding
• Nitriding is carried out in the ferrite region - 500-590 C
• No phase change occurs after nitriding
• Pure ammonia decomposes to yield nitrogen, which enters steel

• The solubility of nitrogen in ferrite is low, so it forms hard nitrides (Fe3N)

• Nitrides with some alloying elements (Al, Mo, Cr)
• Very hard case 1000-2000 VPN. (martensite hardness 830 VPN)
• It also improves the corrosion properties of the steel

Problem
• Formation of undesirable nitrides (Fe4N) – very hard and brittle outer layer of the case
• White layer – need to be removed by grading before to be use in the application
• Can be controlled by the correct ratio of NH3/H2 gas mixture during treatment
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