Department of mechanical Engineering ATMECE

Module-2
SOLIDIFICATION

OBJECTIVES:
 To learn and understand the concepts of solidification

 Solid Solution and types

 Phase and phase equilibrium

 Nucleation and types of nucleation

 Crystal growth

 Phase diagrams
OUT COMES
The student should be able to understand the mechanism of solidification

Introduction
The solidification of metals and alloys is an important industrial process since most
metals are melted and then cast in to a semi finished or finished shape. When molten
metals are cast, solidification starts at the walls of the mould as it is being cooled.
The solidification of alloy takes place not at a specific temperature but over a range
of temperatures. While the alloy is in this range, it has a pasty form that consists of
solid, tree like structures called dendrites and liquid metals. The size and shape of
the dendrites depends on the cooling rate. The study of dendrites is important
because they influence compositional variations, porosity and segregation and
therefore properties.

Material Science 35 17ME32

Department of mechanical Engineering ATMECE

Component – is either pure metal and/or compounds of which an alloy is composed. The
components of a system may be elements, ions or compounds. They refer to the independent
chemical species that comprise the system.

System – it can either refer to a specific body of material under consideration or it may relate to
the series of possible alloys consisting of the same components but without regard to alloy
composition.

Solid solution – it consists of atoms of at least two different types where solute atoms occupy
either substitutional or interstitial positions in the solvent lattice and the crystal structure of the
solvent is maintained.

Solubility limit – for almost all alloy systems, at a specific temperature, a maximum of solute
atoms can dissolve in solvent phase to form a solid solution. The limit is known as solubility limit.
In general, solubility limit changes with temperature. If solute available is more than the solubility
limit that may lead to formation of different phase, either a solid solution or compound.

Phase equilibrium – it refers to the set of conditions where more than one phase may exist. It can
be reflected by constancy with time in the phase characteristics of a system. In most metallurgical and
materials systems, phase equilibrium involves just solid phases. However the state of equilibrium is
never completely achieved because of very slow rate of approach of equilibrium in solid systems. This
leads to non-equilibrium or meta-stable state, which may persist indefinitely and of course, has more
practical significance than equilibrium phases. An equilibrium state of solid system can be reflected in
terms of characteristics of the microstructure, phases present and their compositions, relative phase
amounts and their spatial arrangement or distribution.

Kinetics of nucleation and growth

Structural changes in metallic systems usually take place by nucleation and growth whether it is
just a phase change within one of the three states, or a simple structural rearrangement within a
single phase, or a phase transformation. An equilibrium phase diagram presents the phases and
phase changes expected under equilibrium conditions, but it provides no information about the
rates of transformation. Although changes in pressure, composition, or temperature can cause
phase transformations, it is temperature changes that are more important. From a micro structural
standpoint, the first process to accompany a phase transformation is nucleation (i.e. the formation
of very small particles or nuclei of the product phase from the parent phase) of the new phase
particles which are capable of growing. The second stage is growth, in which the nucleated
particles increase their size. The transformation reaches completion if growth of these new phase
particles is allowed to proceed until the equilibrium fraction is attained.
Both nucleation and growth require that the accompanying free energy change be negative.
Consequently, the super-heating or super-cooling that is necessary for a phase change is to be
expected. That is a transformation cannot tale place precisely at the equilibrium transformation

Material Science 36 17ME32

Department of mechanical Engineering ATMECE

temperature because at that temperature free energies of phases are equal. In addition to
temperature, two other factors that affect transformation rate – first, diffusion controlled
rearrangement of atoms because of compositional and/or crystal structural differences; second,
difficulty encountered in nucleating small particles via change in surface energy associated with
the interface. Diffusion limits both the nucleation and growth rates in many cases.
With the nucleation of new particle, new interface is created between the particle and liquid. This
interface will have positive energy that must be supplied during the transformation process. A
tiny particle has a large surface area to volume ratio and therefore be unstable. Thus energy of the
surface can effectively prevent the initial formation of a tiny particle. A particle said to have
nucleated when it becomes stable and will not disappear due to thermal fluctuations. After a
particle attained a critical size, it can grow further with a continuous decrease in energy. The
surface energy is no longer a dominant factor in the growth process.

Nucleation
Homogeneous nucleation, the probability of nucleation occurring at any given site is identical
to that at any other site within the volume of the parent phase. When a pure liquid metal is cooled
below its equilibrium freezing temperature to a sufficient degree, numerous homogeneous nuclei are
created by slow-moving atoms bonding together. Homogeneous nucleation usually requires a
considerable amount of under cooling (cooling a material below the equilibrium temperature for a
given transformation without the transformation occurring). Under cooling enhances the formation of
nuclei that eventually grow. If f is the free energy change accompanying the formation of a spherical
new phase particle,

where r is the radius of the particle, g is the Gibbs free energy change per unit volume and γ is
the surface energy of the interface.
Heterogeneous nucleation, the probability of nucleation occurring at certain preferred
sites is much greater than that at other sites. During solidification, inclusions of foreign particles
(inoculants), walls of container holding the liquid provide preferred sites. Irregularities in crystal
structure such as point defects and dislocations possess strain energy. In solid-solid transformation,
foreign inclusions, grain boundaries, interfaces, stacking faults and dislocations can act as preferred
sites for nucleation as the strain energy associated with them will be reduced. The released strain
energy can reduce the energy requirements for free energy change, f. Therefore, nucleation proceeds
with a smaller critical radius. A majority of reactions are initiated by some type of heterogeneous
nucleation which is common among the two types.

Material Science 37 17ME32

Department of mechanical Engineering ATMECE

Figure-: Schematic of heterogeneous nucleation.

Crystal Growth
Many transformations occur as a result of continuous formation of critical nuclei in the parent
phase and the subsequent growth of the particles. Growth is the increase in size of the particle
after it has nucleated i.e. growth kinetics become important once an embryo has exceeded the
critical size and become a stable nucleus. Growth may proceed in two
radically different manners. In one type of growth, individual atoms move independently from the
parent to the product phase, thus it is diffusion controlled and is thermally activated. In the other
type of growth that occurs in solid-solid transformations many atoms move cooperatively without
thermal assistance. Growth that is diffusion controlled is more common the other. Growth usually
occurs by the thermally activated jump of atoms from the parent phase to the product phase. The
unit step in the growth process thus consists of an atom leaving the parent phase and jumping
across the interface to join the product phase. At the equilibrium temperature, both phases have
the same free energy, hence the frequency of jumps from parent phase to product phase will be
equal to that from product phase to parent phase i.e. the net growth rate is zero. At lower
temperatures, product phase is expected to have lower free energy, and thus a net flow of atoms
from parent phase to product phase. This net flux of atoms results in interface motion i.e. growth
rate is taken as the rate of increase of a linear dimension of a growing particle. As a function of
temperature, the growth rate first increases with increasing degree of super cooling, but
eventually slows-down as thermal energy decreases. This is same as for nucleation; however the
maximum in the growth rate usually occurs at a higher temperature than the maximum in the
nucleation rate.

Solid Solution
When two metals are mixed together they form an alloy if one metal is soluble in the other one in
solid state. Therefore, an alloy is a solid solution of two or more metals.
Primarily there are two types of solid solutions -
Substitutional – Solute atoms occupy the regular lattice sites of the parent metal (solvent).
Substitutional solid solutions can be random (Cu-Ni) or ordered (Cu-Au).
Interstitial – Solute atoms occupy the interstitial
positions (Steel – C solute atoms in Fe) .

Material Science 38 17ME32

Department of mechanical Engineering ATMECE

Hume-Rothery Rules
Formation of substitutional solid solutions between two metals is governed by a set of rules
known as Hume-Rothery rules
  Size difference between the atoms of solute and the parent metal should be less than 15%.
 The electronegetivity difference between the metals should be small (minimum chemical
 affinity to each other).
 The solubility of a metal with higher valence in a solvent of lower valence is more
 compared to the reverse situation e.g. Zn is much more soluble in Cu than Cu in Zn.
 For complete solubility over the entire range of compositions the crystal structures of the
solute and the solvent must be the same.
Phase
A phase can be defined as a physically distinct and chemically homogeneous portion of a system
that has a particular chemical composition and structure.
Water in liquid or vapor state is single phase. Ice floating on water is an example two phase
system.
Gibbs Phase rule
The number of degrees of freedom, F (no. of independently variable factors), number of
components, C, and number of phases in equilibrium, P, are related by Gibbs phase rule as
F=C–P+2
Number of external factors = 2 (pressure and temperature).
For metallurgical system pressure has no appreciable effect on phase equilibrium and hence, F =
C–P+1
Phase Diagrams
One component system
The simplest phase diagram is the water which is a one component system. It is also known as
pressure-temperature or P-T diagram. Two phases exist along each of the three phase boundaries.
At low pressure (0.006 atm) and temperature (0.010C) all the three phases coexist at a point called
triple point.

Material Science 39 17ME32

Department of mechanical Engineering ATMECE

Binary Phase diagrams

A binary phase is a two component system. Binary phase diagrams are most commonly used in
alloy designing.
The simplest binary system is the Cu-Ni which exhibits complete solubility in liquid and solid
state.

• The line above which the alloy is liquid is called the liquidus line. At temperature just
below this line crystals of α solid solution start forming.
• The line below which solidification completes is called solidus line. Hence, only α solid
solution exists at any temperature below the solidus line.
• The intermediate region between liquidus and solidus lines is the two-phase region where
liquid and solid coexists.

Material Science 40 17ME32

Department of mechanical Engineering ATMECE

• It can be noted that the two metals are soluble in each other in the entire range of
compositions in both liquid and solid state. This kind of system is known as
‘Isomorphous’ system.
The Tie line
The composition of phases in the two-phase region is not same.
To find the composition of the individual phases in the two phase region, a horizontal line (XY),
called tie line, is drawn and its intercepts on the liquidus and solidus lines, Cl and Cs, are taken as
the composition of the liquid and solid respectively.

Lever rule
The relative fractions of the phases at a given temperature for an alloy composition Co is obtained
by the lever rule. This rule gives the fraction of a phase by the ratio of the lengths of the tie line
between Co and composition of the other phase to the total length of the tie line. For example,
fraction solid, fs is given by

Phase diagrams- Limited solubility

Not all metals are completely soluble in each other. Distinctions can be made between two types
of solid solutions with limited solubility – (i) Eutectic and (ii) Peritectic.
When the melting points of two metals are comparable, a eutectic system forms while a peritectic
results when melting points are significantly different.
A eutectic reaction is defined as the one which generates two solids from the liquid at a given
temperature and composition, L → α + β

Material Science 41 17ME32

Department of mechanical Engineering ATMECE

Peritectic is Liquid + Solid 1 → Solid 2 (L + α→β)

In both the cases three phases (two solids and a liquid) coexist and the degrees of freedom F = 2 –
3 + 1 = 0. This is known as invariant (F = 0) reaction or transformation.
Eutectic Phase diagram

Three phases (L+α+β) coexist at point E. This point is called eutectic point or composition. Left
of E is called hypoeutectic whereas right of E is called hypereutectic.
A eutectic composition solidifies as a eutectic mixture of αand β phases. The microstructure at
room temperature (RT) may consist of alternate layers or lamellae of α andβ.
In hypoeutectic alloys the α phase solidifies first and the microstructure at RT consists of this α
phase (called proeutecticα) and the eutectic (α+β) mixture. Similarly hypereutectic alloys consist
of proeutectic and the eutectic mixture. The melting point at the eutectic point is minimum. That’s
why Pb-Sn eutectic alloys are used as solders. Other eutectic systems are Ag-Cu, Al-Si, Al-Cu.
Peritectic Phase diagram
L +α→β. An alloy cooling slowly through the peritectic point, P, the α phase will crystallize first
just below the liquidus line. At the peritectic temperature, TP all of the liquid and α will convert
toβ. Any composition left of P will generate excess α and similarly compositions right of P will
give rise to an excess of liquid.
Peritectic systems – Pt - Ag, Ni - Re, Fe - Ge, Sn-Sb (babbit).

Phase diagrams with intermediate phases

Binary system can have two types of solid solutions/phases – terminal phases and intermediate
phases. Terminal phases occur near the pure metal ends, e.g. α and β phases in the eutectic
system. Intermediate phases occur inside the phase diagram and are separated by two-phase
regions. The Cu-Zn system contains both types of phases. α and η are terminal phases and β, γ,

Material Science 42 17ME32

Department of mechanical Engineering ATMECE
δand ε are intermediate phases. Intermediate phases form in ceramic phase diagrams also. For
example, in the Al2O3 – SiO2 system an intermediate phase called mullite (3Al2O3.2SiO2) is
formed.

Summary
The solidification of alloy takes place not at a specific temperature but over a range of
temperatures. While the alloy is in this range, it has a pasty form that consists of solid, tree like
structures called dendrites and liquid metals. Formation of substitutional solid solutions between
two metals is governed by a set of rules known as Hume-Rothery rules. The relative fractions
of the phases at a given temperature for an alloy composition are obtained by the lever rule. A
eutectic reaction is defined as the one which generates two solids from the liquid at a given
temperature and composition, L → α +β. Peritectic is Liquid + Solid 1 → Solid 2 (L +α→β)
In both the cases three phases (two solids and a liquid) coexist and the degrees of freedom F = 2 –
3 + 1 = 0. This is known as invariant (F = 0) reaction or transformation.
Self assessment questions
1. Define nucleation. Derive an expression for the critical size of the nucleus for
homogeneous nucleation.
2. State and explain Gibb’s phase rule. How it can be applied to a unary phase diagram?
Show that degrees of freedom at triple point are zero.
3. Describe the solidification mechanism in pure metal. Distinguish between homogeneous
and heterogeneous nucleation.
4. Discuss the factors worked out by Hume-Rothery that governs the formation of an ideal
solid solution.
5. What are the different types of solidification
6. Explain with neat sketches the different stages of mechanisms of solidification.
7. Define solid solution. Explain substitutional and interstitial solid solution.
8. Explain the factors governing the formation of substitutional solid solution.
9. With the help of cooling curves ex[lain the solidification of pure metal and binary eutectic
alloy
10. A binary alloy A-50% B contains at a particular temperature two solid phases α and β are
5% B and 95% B respectively. calculate the amount of α and β in the alloy.

Material Science 43 17ME32

Department of mechanical Engineering ATMECE

IRON CARBON DIAGRAM

OBJECTIVES:
 To construct equilibrium diagrams involving complete and partial solubility,

 To understand lever rule

 To understand Iron carbon equilibrium diagram description of phases,

 To know solidification of steels and cast irons invariant reactions.
Outcomes:
1. Student can better understand the phase diagrams those are important to design and
control of heat treating process and to obtain desirable microstructures.

Material Science 44 17ME32

Department of mechanical Engineering ATMECE

Introduction
A phase in a material is a region that differs in its microstructure and /or composition from
another region. Phase diagrams are graphical reprentations of what phases are present in a
materials system at various temperatures and pressures and compositions. Most phase diagrams
are constructed by using equilibrium conditions and used by engineers and scientists to
understand and predict many aspects of the behaviour of materials.
The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram In their simplest form, steels are alloys
of Iron (Fe) and Carbon (C). The Fe-C phase diagram is a fairly complex one, but we will only
consider the steel part of the diagram, up to around 7% Carbon.

Phases in Fe–Fe3C Phase Diagram α-

ferrite - solid solution of C in BCC Fe
• Stable form of iron at room temperature.
• The maximum solubility of C is 0.022 wt%
• Transforms to FCC γ-austenite at 912 °C
γ-austenite - solid solution of C in FCC Fe
• The maximum solubility of C is 2.14 wt %.
• Transforms to BCC δ-ferrite at 1395 °C
• Is not stable below the eutectic temperature
(727 ° C) unless cooled rapidly (Chapter 10)
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
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
Fe-C liquid solution
A few comments on Fe–Fe3C system
C is an interstitial impurity in Fe. It forms a solid solution with α, γ, δ phases of iron. Maximum
solubility in BCC α-ferrite is limited (max. 0.022 wt% at 727 °C) - BCC has relatively small

Material Science 45 17ME32

Department of mechanical Engineering ATMECE
interstitial positions. Maximum solubility in FCC austenite is 2.14 wt% at 1147 °C - FCC has
larger interstitial positions.
Mechanical properties: Cementite is very hard and brittle - can strengthen steels. Mechanical
properties also depend on the microstructure, that is, how ferrite and cementite are mixed.
Magnetic properties: α -ferrite is magnetic below 768 °C, austenite is non-magnetic
Classification.
Three types of ferrous alloys:
• Iron: less than 0.008 wt % C in α−ferrite at room T
• Steels: 0.008 - 2.14 wt % C (usually < 1 wt %) α-ferrite + Fe3C at room T
• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)
Eutectic and eutectoid reactions in Fe–Fe3C
Eutectoid: 0.76 wt %C, 727 °C γ(0.76 wt% C) ↔ α (0.022 wt% C) +
Fe3C Eutectic: 4.30 wt% C, 1147 °C L ↔ γ + Fe3C

Eutectoid: 0.76 wt %C, 727 °C

γ (0.76 wt% C) ↔ α (0.022 wt% C) +
Fe3C Eutectic: 4.30 wt% C, 1147 °C
L ↔ γ + Fe3C
Eutectic and eutectoid reactions are very important in heat treatment of steels
Development of Microstructure in Iron - Carbon alloys
Microstructure depends on composition (carbon content) and heat treatment.
In the discussion below we consider slow cooling in which equilibrium is maintained.

Material Science 46 17ME32

Department of mechanical Engineering ATMECE
Microstructure of eutectoid steel (II)
When alloy of eutectoid composition (0.76 wt % C) is cooled slowly it forms perlite, a lamellar
or layered structure of two phases: α-ferrite and cementite (Fe3C). The layers of alternating
phases in pearlite are formed for the same reason as layered structure of eutectic structures:
redistribution C atoms between ferrite (0.022 wt%) and cementite (6.7 wt%) by atomic diffusion.
Mechanically, pearlite has properties intermediate to soft, ductile ferrite and hard, brittle
cementite.
Microstructure of eutectoid steel (II)
In the micrograph, the dark areas are Fe3C layers, the light phase is α-ferrite

Microstructure of hypo eutectoid steel (I)

Compositions to the left of eutectoid (0.022 - 0.76 wt % C) hypo eutectoid alloys.
γ → α + γ → α + Fe3C

TTT Diagrams
 The family of S-shaped curves at different T is used to construct the TTT diagrams. The
TTT diagrams are for the isothermal (constant T) transformations (material is cooled
quickly to a given temperature before the transformation occurs, and then keep it at that
 temperature).
 At low temperatures, the transformation occurs sooner (it is controlled by the rate of
 nucleation) and grain growth (that is controlled by diffusion) is reduced.
 Slow diffusion at low temperatures leads to fine-grained microstructure with thin-layered
structure of pearlite (fine pearlite).

Material Science 47 17ME32

Department of mechanical Engineering ATMECE

 At higher temperatures, high diffusion rates allow for larger grain growth and formation
 of thick layered structure of pearlite (coarse pearlite).
 At compositions other than eutectoid, a proeutectoid phase (ferrite or cementite) coexist
 with pearlite.
 Additional curves for proeutectoid transformation must be included on TTT diagrams.

Formation of Bainite Microstructure (I)

If

Formation of Bainite Microstructure (II)

 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 the 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

Upper bainite Lower bainite

Spheroidite
• Annealing of pearlitic or bainitic microstructures at elevated temperatures just below eutectoid
(e.g. 24 h at 700 C) leads to the formation of new microstructure – spheroidite - spheres of
cementite in a ferrite matrix.
• Composition or relative amounts of ferrite and cementite are not changing in this
transformation; only shape of the cementite inclusions is changing.
• Transformation proceeds by C diffusion – needs high T.
• Driving force for the transformation - reduction in total ferrite - cementite boundary area

Material Science 48 17ME32

Department of mechanical Engineering ATMECE

Martensite (I)
• Martensite forms when austenite is rapidly cooled (quenched) to room T.
• It forms nearly instantaneously when the required low temperature is reached. The austenite-
martensite does not involve diffusion → no thermal activation is needed, this is called a thermal
transformation.
• Each atom displaces a small (sub-atomic) distance to transform FCC γ-Fe (austenite) to
martensite which has a Body Centered Tetragonal (BCT) unit cell (like BCC, but one unit cell
axis is longer than the other two).
• Martensite is metastable - can persist indefinitely at room temperature, but will transform to
equilibrium phases on annealing at an elevated temperature.
• Martensite can coexist with other phases and/or microstructures in Fe-C system
• Since martensite is metastable non-equilibrium phase, it does not appear in phase Fe-C phase
diagram

Summary
 A phase in a material is a region that differs in its microstructure and /or composition from
another region. Phase diagrams are graphical reprentations of what phases are present in a
materials system at various temperatures and pressures and compositions. Most phase
diagrams are constructed by using equilibrium conditions and used by engineers and
scientists to understand and predict many aspects of the behaviour of materials. The
different forms of iron and carbon are α-ferrite, γ-austenite, δ-ferrite. TTT diagrams are

Material Science 49 17ME32

Department of mechanical Engineering ATMECE
for the isothermal (constant T) transformations (material is cooled quickly to a given
temperature before the transformation occurs, and then keep it at that temperature).
Self assessment questions
1) Draw iron carbon equilibrium diagram and mark on it all salient temperatures,
composition and phases involved. Elaborate the invariant reactions.
2) Construct a phase diagram using the following data and label all the fields Melting
point of Ag = 961oC melting point of copper = 1083 C Eutectic temperature = 7800C
0
Eutectic composition = 28%Cu maximum solubility of Cu in Ag = 9% at 7800C
maximum solubility of Cu in Ag = 2% at 00C. Determine the following. Solidification
start and end of temperature for 30% Ag alloy, temperature at which a 15% Cu alloy has
50% liquid phase and 50% solid phase
3) What is a phase diagram?. Clearly explain the different predictions that can be made from
phase diagram.
4) Draw the iron carbon equilibrium diagram and label all the parts.
5) With the help of a iron carbon diagram explain cooling of steel with 0.6% carbon showing
the microstructure at different stages.
6) What is an invariant reaction? Write the following binary invariant reactions 1) Eutectoid
2) peritectic
7) Calculate the amount of proeutectoid ferrite, total ferrite and cementite in 0.6% C steel at
room temperature.
8) Draw the TTT diagram for eutectoid steel and explain the different microstructures
obtained at various cooling rates.
9) What is critical cooling rate?
10) Two metals A and B melt at 6000C and 4000C respectively. They do not form any
intermediate phase. The maximum solid solubility in each other is 4% down to 000C.an
eutectic reaction takes place at a composition of 65%A-35%B at 3000C. Draw the phase
diagram and label all regions. Find the temperature at which a 20% A-80%B alloy starts
and completes solidification. Find the temperature at which the same alloy is 50% solid
and 50% liquid.

Material Science 50 17ME32