STRUCTURAL ANALYSIS OF NANOMATERIALS

Lecture 05: Transformation of Phases

Dr. Kaushik Pal

Associate Professor
Dept. of Mech. & Indl. Engg.
Joint faculty: Centre of Nanotechnology
Why Do We Study Phase Transformation?

• The tensile strength of an Fe-C alloy of eutectoid composition can

be varied between 700-2000 MPa depending on the heat treatment
process adopted.
• This shows that the desirable mechanical properties of a material can
be obtained as a result of phase transformations using the right heat
treatment process.
• In order to design a heat treatment for some alloy with desired room
temperature properties, time and temperature dependencies of some
phase transformations can be represented on modified phase
diagrams.

ADVANCED COMPOSITE LAB 2

Phase Transformation:
Phase:
 Homogeneous portion of system that has uniform physical and chemical characteristics.
 It is physically distinct from other phases, chemically homogeneous and mechanically
separable portion of a system.
Phase Transformation:
 Process of formation of a new phase with a distinct physical or chemical character or a
different structure than parent phase.
 Change of one phase into another.
 Example:
 Water → Ice
 α- Fe (BCC) → γ- Fe (FCC)
 γ- Fe (FCC) → α- Fe (ferrite) + Cementite (involves change in composition)
 Ferromagnetic phase → Paramagnetic phase (based on a property)

ADVANCED COMPOSITE LAB 3

Classification of Phase Transformation:

Simple Diffusion Dependent Phase

Transformation

Classification of phase Complex Diffusion Dependent Phase

transformation Transformation

Diffusion Less Phase

Transformation

ADVANCED COMPOSITE LAB 4

Simple Diffusion Dependent Phase Transformation:
 No change in composition.
 No change in phases.
 Example: Melting/solidification of pure metals, grain
growth, recrystallization, allotropic transformations.
Complex Diffusion Dependent Phase Transformation:
 Changes in phase compositions.
 Changes in number of phases.
 Example: Eutectoid transformations.
Diffusion Less Phase Transformation:
 Produces metastable phase.
 Involves small displacements of all atoms in structure.
 Example: Martensitic transformation.

ADVANCED COMPOSITE LAB 5

Kinetics of Phase Transformation:
Kinetics: Study of reaction rates of phase transformation.
• Involve change in structure and composition.
Phase Transformation
• It’s the re-arrangement & re-distribution of atoms which requires diffusion.

Process of phase transformation involves

a) Nucleation:
 Involves the appearance of very small particles, or nuclei of new
phase which are capable of growing.
 Nucleus forms when Gibbs free energy, G, of system decreases.
ΔG = (-ve) negative
b) Growth:
 Increase in size of nucleus at the expense of parent phase.

ADVANCED COMPOSITE LAB 6

 Types of Nucleation

Homogeneous Heterogeneous
nucleation nucleation

 Nuclei of the new phase form uniformly  Nuclei form at structural

throughout the parent phase inhomogeneities, insoluble impurities,
grain boundaries, dislocations etc.
 Require supercooling (80-300 °C).
 Require slight supercooling (0.1-10 °C).

ADVANCED COMPOSITE LAB 7

Homogenous nucleation:
 It occurs when there are no special object inside a phase which can cause nucleation.
 It is also called as self nucleation.
 Requires super cooling or super heating for nucleation to occur.
 Probability of nucleation is same throughout the volume of the parent phase.

Example: When a pure liquid metal is cooled

slowly below its equilibrium freezing temperature
to a sufficient degree numerous homogeneous
nuclei are created by slow moving atom bonding
together in a crystalline form.

ADVANCED COMPOSITE LAB 8

Solidification of a metal:
 Above melting point Tm,
 (Liquid free energy) Gl < G s (Solid free energy).
 Free energy change for solidification, ΔG > 0.
 Below Tm, ΔG < 0 and nuclei of solid phase form.
 Two contributions to free energy change, volume free energy (ΔGv) and surface
free energy (γ), due to creation of a new surface.
𝟒
 Taking nucleus as a spherical particle of radius ‘r’; ΔG = 𝝅𝒓𝟑 ∆𝑮𝒗 + 𝟒𝝅𝒓𝟐 𝜸
𝟑

 Tiny particle of solid that forms first will be stable only when it achieves a
critical radius (r*). Below the critical radius it is unstable and is called embryo.
 Since this happens at the maximum of the ΔG vs. ‘r’ curve.
𝒅(∆𝑮) 𝟒
= 𝝅 ∆𝑮𝒗 𝟑𝒓𝟐 + 𝟒𝝅𝜸 𝟐𝒓 = 𝟎
𝒅𝒓 𝟑
𝟐𝜸 𝟏𝟔𝝅𝜸𝟑
 This yields, 𝒓∗ = and ∆𝑮∗ =
∆𝑮𝒗 𝟑 ∆𝑮𝒗 𝟐

ADVANCED COMPOSITE LAB 9

Heterogeneous nucleation:
 Nucleation occur at the interphase between two phases or at the grain boundary.
 Probability of nucleation is much higher at certain preferred sites such as mold wall,
inclusions, grain boundaries, compared to rest of the parent phase.
Example: Solidification of a liquid on an inclusion surface
o γSL - solid-liquid surface
 It has three interfacial energies that exist at two phase boundaries: o γSI - solid surface
o γIL - liquid surface
 θ is wetting angle formed between γSL and γSL vector.
 Surface tension force balance in the plane of flat surface is given by:
𝛄𝐈𝐋 = 𝛄𝐈𝐒 + 𝛄𝐒𝐋 𝐜𝐨𝐬𝛉
∗ 𝟐𝛄 ∗ 𝟏𝟔𝛑𝛄𝟑 𝐒𝐋
 With a similar approach it can be shown: 𝐫 = − 𝐒𝐋 and ∆𝐆 = 𝐒 𝛉
∆𝐆𝐯 𝟑∆𝐆𝐯𝟐

 The small value of θ ensures that the energy barrier (Δ G) is effectively lowered
in heterogeneous nucleation.

ADVANCED COMPOSITE LAB 10

Nucleation and Growth Kinetics:
• Growth: It is the increase in size of nucleus at the expense of parent phase.
• Growth rate (G) is determined by rate of diffusion, and its temperature dependence is same
as for diffusion coefficient.
𝑸
𝑮 = 𝑪 𝒆𝒙𝒑 −
𝒌𝑻
• Once the embryo exceeds the critical size r*, growth of nucleus
starts and nucleation continues simultaneously.
• Nucleation and growth rates are function of temperature.
• Nucleation rate increases with cooling rate and degree of
undercooling (ΔT = Tm – T).
• High nucleation rate and low growth gives finer grain size.

ADVANCED COMPOSITE LAB 11

Rate of Phase Transformation:
 Transformations follow a characteristic S-shaped, or sigmoidal curve.
 Modeled by the Avrami equation: 𝒚 = 𝟏 − 𝐞𝐱 𝐩 −𝒌𝒕𝒏
where k, n are time independent constants.
 Rate of phase transformation is the reciprocal of time for transformation to proceed halfway
to completion.
𝒓∗ = 𝟏 𝒕𝟎.𝟓 = 𝑨𝒆−𝑸/𝑹𝑻 → [Arrhenius expression]
where, R= gas constant, A=Arrhenius constant, Q= activation energy, T=temperature (K).
 Rate increases with temperature.
 Rate is often small, so equilibrium is not possible.

ADVANCED COMPOSITE LAB 12

Supercooling and Superheating:
 Crossing a phase boundary on composition-temperature phase diagram, phase transformation towards
equilibrium state is induced.
 But transition to equilibrium structure takes time and transformation is delayed.
 During cooling, transformation occur at temperatures less than predicted by phase diagram:
supercooling.
 During heating, transformation occur at temperatures greater than predicted by phase diagram:
superheating.
 Degree of supercooling/superheating increases with rate of cooling/heating.
 Driving force to nucleate increase as ΔT increases.  Metastable states can be formed as
Small
result of fast temperature change.
Small
supercooling
nucleation Few nuclei Large crystals  Microstructure is strongly affected
rate by cooling rate.
Rapid  Effect of time on phase
Large transformation is explained using
nucleation Many nuclei Small crystals
supercooling
rate Iron-carbon alloy.

ADVANCED COMPOSITE LAB 13

Degree of supercooling (Δt) values for several metals:

Metal ΔT (°C)
Antimony 135
Germanium 227
Silver 227
Gold 230
Copper 236
Iron 295
Nickel 319
Cobalt 330
Palladium 332

ADVANCED COMPOSITE LAB 14

Iron-Carbon Phase Diagram:
Five Phases in Fe-C system:
 α-ferrite:
• Interstitial solid solution of C in BCC iron.
• Maximum solubility of C is 0.025%.
• Exists from 273 °C to 910 °C.
 Austenite (γ):
• Interstitial solid solution of C in FCC iron.
• Maximum solubility of C is 2.1%.
• Exists from 910 °C – 1394 °C.
 δ-ferrite:
• Solid solution of C in BCC iron.
• Maximum solubility of C is 0.09%.
• Exist over temperature of 1394 °C – 1593 °C.
 Cementite, Fe3C:
• Intermetallic compound.
• C content in Fe3C is 6.67%.
 Liquid Fe-C solution.

ADVANCED COMPOSITE LAB 15

Critical temperatures in Fe-C system:
 Eutectoid temperature (727 °C) during heating and cooling is Ac1 and Ar1.
[where, A for arrêt (arrest), c for chauffage (heating) and r for refroidissement (cooling)].
 At normal rates of heating or cooling, Ac1 > Ar1.
 A2 at 768 °C is currie temperature above which Fe turns paramagnetic while heating.
 Temperatures corresponding to (𝜸 + 𝜶)/𝜸 and (𝜸 + 𝑭𝒆𝟑𝑪)/𝜸 phase boundaries are function of
carbon content, represented as A3 and Acm.
 Eutectic temperature is 1146 °C & Peritectic temperature is 1495 °C.

Classification of ferrous alloys based on carbon content:

 Iron: contains less than 0.008 wt % C in α-ferrite at room temperature.
 Steel: 0.008 - 2.14 wt % C (usually < 1 wt % ) α-ferrite + Fe3C at room temperature.
 Cast Iron: 2.14 - 6.7 wt % (usually < 4.5 wt %).

ADVANCED COMPOSITE LAB 16

Phase Transformation in Fe-C System: δ Ferrite
Peritectic reactions γ - iron Austenite
α Ferrite
It comprises of three invariant reactions as Eutectic reactions
Fe3C Cementite
Eutectoid reactions γ+ Fe3C Ledeburite
a) Peritectic reaction at 1495 °C: α+ Fe3C Pearlite
 L (0.53% C) + δ-ferrite (0.09% C) → γ-iron (austenite) (0.17% C).
b) Eutectic reaction at 1146 °C:
 L (4.3% C) → γ-iron (2.1 % C) + Fe3C (6.67% C).
 Eutectic mixture of austenite (γ) and cementite (Fe3C) is called Ledeburite.
 Compositions right and left of 4.3% are called hyper and hypoeutectic steels (Cast iron).
c) Eutectoid reaction at 727 °C:
 γ (0.8 % C) → α (0.025% C) + Fe3C (6.67% C).
 Eutectoid mixture of ferrite (α) and cementite (Fe3C) is called Pearlite.
 Compositions right and left of 0.8% are called hyper and hypoeutectoid steels.
 Compositions up to 2.1% C are steels and beyond this are cast iron.

ADVANCED COMPOSITE LAB 17

 Microstructures:
 Microstructure depends on composition (carbon content) and
heat treatment.
 Eutectoid steel (0.8% C) will have 100% pearlite (p) at room
temperature (RT).
 Pearlite formed under equilibrium conditions consists of
alternate lamellas of ferrite and Fe3C.
 Hypoeutectoid steels → α + p.
 Hypereutectoid steels → Fe3C + p.
 Hypoeutectic cast irons consist of γ + ledeburite (Le) below
eutectic temperature and p + Fe3C + Le at room temperature
as the γ transforms to Fe3C and p at eutectoid temperature.
 Hypereutectic cast irons will have a structure of Fe3C + Le.

ADVANCED COMPOSITE LAB 18

Isothermal Transformation Diagram:
 Gives relation between temperature and time for phase formation.
 Also known as Temperature-time-transformation (T-T-T)
diagram.
 Normal cooling rate forms pearlite (P), higher cooling rate forms
bainite (B).
 Size of pearlite or bainite depends on transformation temperature.
 Martensite (M) forms when steel is cooled below martensite start
(Ms) temp at much higher cooling rate so that nose of T-T-T curve
(shown dotted) is avoided (the long blue arrow).
 Diffusion rates below Ms is so low that γ → M transformation is a
diffusion less process (C content remains same).
 Crystal structure changes from FCC (γ) to body centered
tetragonal (BCT).

ADVANCED COMPOSITE LAB 19

T-T-T diagram for eutectoid Fe-C alloy:
Pearlite:
 Thickness of ferrite and cementite layers in pearlite is ~ 8:1.
 Absolute layer thickness depends on temperature of
transformation.
 Higher the temperature, thicker the layers.
 Family of S-shaped curves at different T, constructs TTT diagrams.
 TTT diagrams are for isothermal transformations.
 At low temperature, transformation occurs early and grain growth
is reduced.
 At compositions other than eutectoid, a proeutectoid phase (ferrite
or cementite) coexist with pearlite.
Coarse pearlite → formed at higher temperature → relatively soft
Fine pearlite → formed at lower temperature → relatively hard

ADVANCED COMPOSITE LAB 20

Formation of Bainite Microstructure:
 If transformation temperature is low enough (≤540 °C) bainite
rather than fine pearlite forms.
 For T ~ 300-540 °C, upper bainite consists of needles of ferrite
separated by long cementite particles.
 For T ~ 200-300 °C, lower bainite consists of thin plates of ferrite
containing very fine rods or blades of cementite.
 In bainite region, transformation rate is controlled by
microstructure growth (diffusion) rather than nucleation.
 Since diffusion is slow at low temperatures, this phase has a very
fine (microscopic) microstructure.
 Pearlite and bainite transformations are competitive;
transformation between pearlite and bainite not possible without
first reheating to form austenite

ADVANCED COMPOSITE LAB 21

Spheroidite:
 Annealing of pearlitic or bainitic microstructures at
elevated temperatures just below eutectoid leads to
the formation of new microstructure: spheroidite.

 Spheroidite are spheres of cementite in ferrite

matrix.

 Composition or relative amounts of ferrite and

cementite are not changing in this transformation.

 Only shape of cementite inclusions is changing.

 Transformation proceeds by composition diffusion, needs high temperature.

 Driving force for the transformation - reduction in total ferrite - cementite boundary area

ADVANCED COMPOSITE LAB 22

Martensite:
 Martensite forms when austenite is rapidly cooled (quenched) to room
temperature.
 Austenite-martensite does not involve diffusion, no thermal activation is
needed, this is called an athermal transformation.
 Martensite grains nucleate and grow at a very rapid rate, the velocity of
sound within the austenite matrix.
 Transformation of FCC to BCT (body-centered tetragonal).

 Martensite:
 Metastable.
 Coexist with other phases in Fe-C system.
 Non-equilibrium single phase.
 Occurs instantaneously i.e. time dependent.

ADVANCED COMPOSITE LAB 23

 Austenite to Martensite → 4.3 % volume increase.

ADVANCED COMPOSITE LAB 24

Continuous Cooling Transformation (C-C-T) Diagram:
 C-C-T curve (Blue) is shifted to right of T-T-T (dashed)
curve as C-C-T occurs at lower temperature and longer
time compared isothermal holding.
 Bainite does not form in steels during continuous cooling
and C-C-T curve ceases just below the nose.
 Microstructure (fine or coarse) depends on cooling rate.
(Higher the cooling rate finer is the microstructure).
 Finer size pearlite is called sorbite and very fine size
pearlite is troostite.
 Critical cooling rate is one at which cooling curve just
touches the nose of C-C-T curve.
 Cooling rate higher than critical rate is needed to form
martensite.

ADVANCED COMPOSITE LAB 25

Tempered Martensite:
 Martensite is brittle, needs to be modified for practical applications.
 It is done by heating it to 250-650 °C for some time (tempering) which produces
tempered martensite.
𝑴𝒂𝒓𝒕𝒆𝒏𝒔𝒊𝒕𝒆 𝑩𝑪𝑻, 𝒔𝒊𝒏𝒈𝒍𝒆 𝒑𝒉𝒂𝒔𝒆 → 𝑻𝒆𝒎𝒑𝒆𝒓𝒆𝒅𝒎𝒂𝒓𝒕𝒆𝒏𝒔𝒊𝒕𝒆 (𝜶 + 𝑭𝒆𝟑𝑪 𝒑𝒉𝒂𝒔𝒆𝒔)
 Tempered martensite: fine-grained-dispersed cementite grains in ferrite matrix.

 It is less strong as compared to regular martensite.

 Has enhanced ductility (ferrite phase is ductile).
 Mechanical properties depend upon: cementite particle
size: fewer, larger particles means less boundary area and
softer, more ductile material - eventual limit is spheroidite.
 Particle size increases with higher tempering temperature
and longer time (more C diffusion) - therefore softer, more
ductile material.

ADVANCED COMPOSITE LAB 26

Possible Austenite Transformations:

Solid lines: diffusional transformations

Dashed lines: diffusion less martensite
transformations

ADVANCED COMPOSITE LAB 27

Microstructures and Mechanical Properties for Iron-Carbon Alloys:
Microconstituent Phases present Arrangement of phases Mechanical properties
Spheroidite α Ferrite + Fe3 C Relatively small Fe3 C sphere like Soft and ductile
particles in an α-ferrite matrix

Coarse pearlite α Ferrite + Fe3 C Alternating layers of α-ferrite and Harder and stronger than spheroidite,
Fe3C that are relatively thick not ductile as spheroidite.

Fine Pearlite α Ferrite + Fe3 C Alternating layers of α-ferrite and Harder and stronger than coarse
Fe3C that are relatively thin pearlite, not ductile as coarse pearlite.
Bainite α Ferrite + Fe3 C Very fine and elongated particles of Hardness and strength greater than fine
Fe3 C in an α-ferrite matrix pearlite; hardness less than martensite:
ductility greater than martensite.
Tempered α Ferrite + Fe3 C Very small Fe3 C sphere like particles Strong, not hard as martensite, but
martensite in an α-ferrite matrix much more ductile than martensite.

Martensite Body centered tetragonal, Needle shape grains Very hard and very brittle.
single phase

ADVANCED COMPOSITE LAB 28

Summary:

 Phase transformation is the process of formation of a new phase.

 It involves two process as nucleation and growth.
 Avrami equation is used for the calculation of degree of progress of
transformation phase, which is a function of time.
 During cooling, transformations occur at temperatures less than predicted by
phase diagram called as supercooling.
 TTT diagram is called temperature-time-transformation plot.
 Depending on the type of transition, it shows various type of complexity.

ADVANCED COMPOSITE LAB 29

ADVANCED COMPOSITE LAB 30