MODULE -2.

Mechanism of Crystallization

Prof. Mansi Lakhani

 PHASE TRANSFORMATION
PHASE
TRANSFORMATION

THERMODYNAMICS KINETICS
CONCEPT CONCEPT
viz. changes in phases viz. rate at which
wrt temp and pressure transformation takes place
(Phase diagrams) (Nucleation and Growth)

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Phase transformation can be liquid to
solid, solid to solid, etc.

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KINETICS OF PHASE TRANSFORMATION

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 NUCLEATION
Formation of new phase from the parent phase.
1. Homogenous nucleation
2. Heterogeneous nucleation
For the homogeneous type, nuclei of the new phase form uniformly throughout the
parent phase, whereas for the heterogeneous type, nuclei form preferentially at
structural inhomogeneity, such as container surfaces, insoluble impurities, grain
boundaries, dislocations, etc.

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Change in Free energy vs Nucleus
radius plot

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GROWTH

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GROWTH

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OVERALL TRANSFORMATION RATE

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 MODULE -2.2

Classification of alloy based

on Phases & Phase Diagrams

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BASIC TERMINOLOGY for Phase
diagram
FOR SOLID SOLUTION:
• Component are pure metals
and/or compounds of which an
alloy is composed. For
example, in a copper-zinc
brass, copper and zinc are
components.

• Solvent represents element or

compound that is present in the
greatest amount.

• Solute is used to denote

element or compound in a
minor concentration.

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 SOLUBILITY LIMIT
There is a maximum concentration of solute atoms that may dissolve in the
solvent to form a solid solution, this is called a solubility limit.
Example: Sugar and water.

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 PHASE
• A phase may be defined as a homogeneous portion of a system that has
uniform physical and chemical characteristics.
• Every pure material is considered to be a phase; so also is every solid,
liquid, and gaseous solution.
• For example, the sugar–water syrup solution just discussed is one phase,
and solid sugar is another. Each has different physical properties (one is a
liquid, the other is a solid);
• Furthermore, each is different chemically (i.e., has a different chemical
composition); one is virtually pure sugar, the other is a solution of H2O
and C12H22O11.
• Much of the information about the control of the phase structure of a
particular system is conveniently and concisely displayed in what is called
a phase diagram, also often termed an equilibrium diagram.

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ONE COMPONENT PHASE DIAGRAM

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 BINARY PHASE DIAGRAM
Phase diagram in which temperature and
composition are variable parameters, and pressure
is held constant—normally 1 atm, and the study is
restricted to Binary alloys only.

Binary phase diagrams are maps that represent the

relationships between temperature and the
compositions and quantities of phases at
equilibrium, which influence the microstructure of
an alloy.
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BINARY ISOMORPHOUS SYSTEMS

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 BINARY ISOMORPHOUS SYSTEMS
• The liquid L is a homogeneous liquid solution composed of
both copper and nickel.
• The α phase is a substitutional solid solution consisting of
both Cu and Ni atoms, and having an FCC crystal structure.
• At temperatures below about 1080C, copper and nickel are
mutually soluble in each other in the solid state for all
compositions.
• This complete solubility is explained by the fact that both Cu
and Ni have the same crystal structure (FCC), nearly identical
atomic radii and electro negativities, and similar valences.
• The copper–nickel system is termed isomorphous because of
this complete liquid and solid solubility of the two
components. Prof. Mansi Lakhani
INTERPRETETION OF PHASE DIAGRAM
For a binary system of known composition and
temperature that is at equilibrium, at least three
kinds of information are available:

(1) the phases that are present,

(2) the compositions of these phases, and
(3) the percentages or fractions of the phases.

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 Phases Present
At point A, only α phase is present.

At point B, both α and liquid phases are present.

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 Composition of the phases
For point A (single phase region),
α-phase has 60% wt. Ni and 40% wt. Cu.

For Point B, as it is double phase region, use Tie-

line rule.
Composition of Liquid and α phase would be:
CL = 32% wt. Ni and 68% wt. Cu.
Cα = 42% wt. Ni and 58% wt. Cu.

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Percentages or fractions of the phases
For point A – 100% α is present (single phase
region)
For point B – Use lever arm rule.

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BINARY EUTECTIC PHASE DIAGRAM

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 EUCTECTIC REACTION

This reaction is known as Invariant Reaction, because it can occur at given temperature
and for given composition only.

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For 40% Sn and 60% Pb, at 150 C,
Determine 1. Phases, 2. Composition of Phases and 3.
Percentage/fraction of phases.

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Iron – Iron Carbide Phase Diagram

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IRON-IRON CARBIDE DIAGRAM

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Ferrite & Austenite

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Eutectoid Steel

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Hypo-Eutectoid steel

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Hyper-Eutectoid steel

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Pearlite

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At 0.38% carbon, Pro-eutectoid ferrite
& Pearlite

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At 1.4 % carbon, Pro-eutectoid
cementite & Pearlite

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 MODULE 2.3

TRANSFORMATION
DIAGRAMS

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 Limitations of Fe-C diagram
• Though the Fe-C equilibrium diagram is very useful, it does not provide
information about the transformation of austenite to any structure other
than equilibrium structures, nor does it provide any details about the
influence of cooling rates on the formation of different structures.
• In other words, Fe-C diagram does not explain the decomposition of
austenite under non-equilibrium conditions or conditions involving faster
rates of cooling than equilibrium cooling.

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 Time-Temperature-Transformation
Diagram
• It shows what structures can be expected after various rates
of cooling.
• It graphically describes the cooling rate required for the
transformation of austenite to pearlite, bainite or martensite.
• TTT diagram also gives the temperature at which such
transformations take place.

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Phase vs TTT Diagram

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 Transformation Diagram
There are two main types of transformation
diagrams that are helpful in selecting the
optimum steel and processing route to achieve a
given set of properties. These are:
1. Time-temperature transformation (TTT)
diagrams
2. Continuous cooling transformation (CCT)
diagrams

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 TTT diagram
• Indicates the amount of transformation at a constant
temperature.
• Samples are austenitised and then cooled rapidly to
a lower temperature and held at that temperature
whilst the amount of transformation is measured.
• A large number of experiments are required to build
up a complete TTT diagram.

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 TTT diagram for eutectoid steel
Steps to follow for preparing TTT diagram:
• Prepare samples in required shape and size
• Place the samples in a furnace or molten salt bath in the austenitic temperature
that is at around 780°C (727 + 50°C apprx.). Specimen should be held at this
constant temperature to make complete austenitic structure in the sample.
• These specimens are divided into groups and quickly transferred to an incubation
bath which is maintained at constant temperature below 727°C.
• After predermined time intervals individual specimens are removed from their
baths and quenched into water.
• The microstructure is then examined to see the extent to which the transformation
had taken place at holding temperature.

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Phase transformations in TTT diagram
• Pearlite forms above the nose—that is, over the temperature
range of about 540 to 727°C.
• for isothermal treatments at temperatures between about
215 and 540°C Bainite is the transformation product.
• Below 215°C temperature, the austenite changes or
transforms to martensite.

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 PEARLITE
• At temperatures just below the eutectoid, relatively thick layers of both
the ferrite and Fe3C phases are produced; this microstructure is called
coarse pearlite.
• The thin layered structure produced in the vicinity of 540°C is termed fine
pearlite.

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 BAINITE
• Bainite consists (like pearlite) of a ferrite matrix in which particles of
cementite are embedded. The individual particles are much finer than in
pearlite.
• The appearance of bainite may vary between
– feathery mass of fine cementite and ferrite for bainite formed around
480°C and
– dark acicular (needle shaped) crystals for bainite formed in the region of
around 410°C).

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 MARTENSITE
• At the foot of the TTT diagram, there are two lines Ms (215°C
) and Mf (50°C).
• Martensite is an interstitial supersaturated solid solution of
carbon in iron having a bodycentered tetragonal lattice.
• Martensite is very hard, strong and brittle.

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 Austenite to various structure
depending on cooling rate (TTT curve)

Austenite

Slow Moderate Rapid

cooling Cooling Cooling

Pearlite Bainite Martensite

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 Practical difficulties in plotting TTT
diagram
• In Austenite to Pearlite transformation in which, it is impossible to change
the temperature from 727°C to 500°C in zero time and from 500°C to room
temperature in zero time.
• Same case is with all other transformations, that is from austenite to
bainite, austenite to martensite.
• Specimen size should be kept small and special care should be taken
during their rapid transfer between baths.

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 Continues Cooling Transformation
Diagram
Steps for plotting CCT diagram:
• Prepare samples
• Heat specimens at 780°C temperature in the furnace
• Hold the specimen at 780°C for complete austenitic
transformation.
• After pre-determined time intervals, individual specimen is
removed from furnace and cooled upto room temperature by
various continuous cooling rates.
• Mark corresponding transformation start and end point,
which will give two separate curves one by joining

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• In CCT diagram instead of holding at constant
temperature, the specimen is continuously
cooled.

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Effect of Cooling Rate on the Formation of
Different Reaction Products

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Effect of Cooling Rate on the Formation of
Different Reaction Products

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Effect of Cooling Rate on the Formation of
Different Reaction Products

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Effect of Cooling Rate on the Formation of
Different Reaction Products
• Very slow cooling rate (furnace cooling),will result in
coarse pearlite with low hardness.
• Air cooling produces fine pearlite.
• In water quenching, entire substance remains
austentic until the Ms line is reached, and changes to
martensite between the Ms and Mf lines.
• It is possible to form 100% pearlite or 100%
martensite by continuous cooling, but it is not
possible to form 100% Bainite.

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Cooling Curves On TTT & CCT Diagram

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Austenite to various structure depending on cooling
rate (continuous cooling)

Austenite

Slow Moderate Rapid

cooling Cooling Cooling

Coarse Fine
Martensite
Pearlite Pearlite
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 Critical Cooling Rate
• If the cooling curve is tangent to the nose of TTT curve, the
cooling rate associated with this cooling curve is Critical
Cooling Rate (CCR) for this steel.
• Any cooling rate equal to or faster than CCR will form only
martensite.

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GRAPHITIZATION OF CAST IRON /
CLASSIFICATION OF CAST IRON

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 CAST IRON
• Generically, cast irons are a class of ferrous alloys with
carbon contents above 2.14 wt%; in practice, however,
most cast irons contain between 3.0 and 4.5 wt% C and,
in addition, other alloying elements.
• A reexamination of the iron–iron carbide phase diagram
reveals that alloys within this composition range
become completely liquid at temperatures between
approximately 1150 and 1300C which is considerably
lower than for steels.
• Thus, they are easily melted and amenable to casting.
Furthermore, some cast irons are very brittle, and
casting is the most convenient fabrication technique.

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CLASSIFICATION OF CAST IRON

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 GREY CAST IRON
• The carbon and silicon contents of gray cast irons vary between 2.5 and
4.0 wt and 1.0 and 3.0 wt%, respectively. For most of these cast irons, the
graphite exists in the form of flakes (similar to corn flakes), which are
normally surrounded by an ferrite or pearlite matrix.
• Because of these graphite flakes, a fractured surface takes on a gray
appearance, hence its name.
• Mechanically, gray iron is comparatively weak and brittle in tension as a
consequence of its microstructure; the tips of the graphite flakes are sharp
and pointed, and may serve as points of stress concentration when an
external tensile stress is applied. Strength and ductility are much higher
under compressive loads.
• They are very effective in damping vibrational energy.
• Base structures for machines and heavy equipment that are exposed to
vibrations are frequently constructed of this material

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FERRITIC GRAY CAST IRON

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PEARLITIC GRAY CAST IRON

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AAPLICATION OF GRAY C.I

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 NODULAR / DUCTILE CAST IRON
• Adding a small amount of magnesium and/or cerium to the gray iron before
casting produces a distinctly different microstructure and set of mechanical
properties. Graphite still forms, but as nodules or sphere like particles
instead of flakes. The resulting alloy is called nodular or ductile iron.
• The matrix phase surrounding these particles is either pearlite or ferrite.
• Nodular C.I are stronger and much more ductile than gray iron.
• Typical applications for this material include valves, pump bodies,
crankshafts, gears, and other automotive and machine components.

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FERRITIC NODULAR GRAY CAST IRON

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PEARLITIC NODULAR CAST IRON

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APPLICATION OF DUCTILE C.I

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 WHITE CAST IRON
• For low-silicon cast irons (containing less than 1.0 wt% Si) and rapid
cooling rates, most of the carbon exists as cementite instead of graphite.
• A fracture surface of this alloy has a white appearance, and thus it is termed
white cast iron.
• As a consequence of large amounts of the cementite phase, white iron is
extremely hard but also very brittle, to the point of being virtually
unmachinable.
• Its use is limited to applications that necessitate a very hard and wear-
resistant surface, and without a high degree of ductility—for example, as
rollers in rolling mills. Generally, white iron is used as an intermediary in
the production of yet another cast iron, malleable iron.

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WHITE CAST IRON

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 MALLEABLE CAST ITON
• Heating white iron at temperatures between 800ᴼC and 900ᴼC for a
prolonged time period and in a neutral atmosphere causes a decomposition
of the cementite, forming graphite, which exists in the form of clusters or
rosettes surrounded by a ferrite or pearlite matrix, depending on cooling
rate. This type is known as Malleable cast iron.
• The microstructure is similar to that for nodular iron, which accounts for
relatively high strength and appreciable ductility or malleability.
• Applications include connecting rods, transmission gears, and differential
cases for the automotive industry, and also flanges, pipe fittings, and valve
parts for railroad, marine, and other heavy-duty services.

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MALLEABLE CAST IRON

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APPLICATION OF MALLEABLE C.I

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Identify the type of Cast Iron based on Microstructure as shown below:

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