Material Science and

Engineering – Module 3
Syllabus

Physical Metallurgy:
Nucleation and growth: Introduction to homogeneous and heterogeneous nucleation,
critical radius for nucleation.
Heat treatment: Annealing, Normalizing, hardening, Tempering, Nitriding, Cyaniding,
Induction Hardening and Flame Hardening, Recent advances in heat treat technology. TTT
diagram, Recovery-Recrystallization-Grain Growth. Strengthening mechanisms: Strain
hardening, Precipitation hardening (Solid-Solution Strengthening), Grain refinement.
1. Nucleation and growth
1.1Introduction

The pouring of molten metal into a relatively cool mould initiates the process of solidification wherein the phase
transformation from liquid to solid occurs. The mode of freezing has a twofold influence upon the final
properties of the casting; the metallographic structure acquired by the casting is determined during
solidification, besides structure the soundness of the casting also depends upon the solidification mechanism.

1.2Solidification curves

A solidification curve (or cooling curve) is a record of material temperature vs time, as it cools down from its
molten state to room temperature. It can be used to determine the phase transition temperatures of materials
(pure metals or alloys).
(i) Solidification in pure metals
Pure metals have a clearly defined melting or freezing point. i.e., it solidifies at a constant temperature. The
evolution of latent heat is associated with solidification and as a result temperature remains constant. An
equilibrium cooling of pure metal maybe assumed as shown in figure 4.9. It is also seen that if a pure metal is
cooled rapidly or otherwise when it is very pure it may cool with some amount of undercooling.

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 Fig. Cooling curve for pure metals
(ii) Solidification in alloys
Solidification in solid solution alloys occurs over a range of temperature as shown in Fig. below. In alloys the
amount of undercooling required is less as compared to pure metals and hence the nucleation occurs with ease.
A rapidly solidifying alloy may show considerable amount of undercooling owing to differential freezing.

Fig. Cooling curve for alloys

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1.3Mechanism of Solidification

1.3.1Crystallization of the melt

Crystal lattice represents a more closely packed state of matter than the liquid, thus freezing is associated with
volume contraction. Moreover, freezing results in reduced molecular motion leading to liberation of energy in
the form of latent heat of crystallization which affects the rate and mode of crystal growth. Crystallization from
the melt involves successive stages of nucleation and grain growth. The location and relative rates of these two
phenomena determines the final structure.

At the melting point the thermal fluctuations result in the formation of tiny particles of the product phase which
grow further by the transfer of atoms across its interface. The process of formation of the first stable tiny particle
is called nucleation and the process of increase in the size of these particles is called grain growth.
1.4Nucleation

Nucleation is the beginning of phase transformation. There can be two types of nucleation:
i.) Homogeneous nucleation and
ii.) Heterogeneous nucleation
i) Homogeneous nucleation:
This type of nucleation is observed when solids are formed within its own melt without the aid of any foreign
particles. It occurs in perfectly homogeneous materials such as pure metals. Homogeneous nucleation requires
some amount of under cooling and the nucleation of super cooled grains which depends on two factors, viz,
volume free energy and surface free energy.
a) Volume free energy (ΔfV): The free energy available from the solidification process and it depends upon
the volume of particle formed.
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∆fV = − 3��r3 ∆G

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where, ΔG is free energy change per unit volume (the –ve sign indicates that the free energy decreases and
energy is released as the system moves to a more stable state) and r is the radius of nuclei
b) Surface free energy (∆fS): The energy required to form a solid-liquid interface.
∆fS = γ4πr2
where, γ is interfacial free energy per unit area.
The combined effect of volume free energy and surface free energy gives us the net total free energy change, i.e,
∆f = ∆fV + ∆fS

• Figure shows the relationship between latent heat energy(∆fV) and surface energy (∆fS) with increase in the
radius of the nuclei.
• With the increase in radius of nucleus, ∆fV decreases, but ∆fS increases. The combined effect is the net free
energy change ∆f.
• As the radius of nucleus increases free energy also increases till critical radius ‘r’ but further increase in
particle radius free energy decreases and even becomes –ve (dotted line)
• In order for grain growth to takes place around a particle nucleus, it should have reached the critical radius
(r*). If not, there won’t be formation of any nuclei, or the nuclei already formed may again go to liquid
phase.
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ii) Heterogeneous Nucleation:

It takes place due to the influence of foreign particles (container or insoluble impurities); the presence of
impurities lower the liquid-solid interface energy and help in nucleation there by reducing the amount of super
cooling needed to actuate nucleation.
The basic requirements for heterogeneous nucleation’s are
a) Nucleating agents: the presence of foreign particles so that nucleation takes place easily b)
Low contact angle: a good wetting between the liquid metal and the foreign particles.
 Fig: Contact angle for Heterogeneous nucleation

With small contact angles, the interface has low surface energy and nucleation can occur at small amount of
under cooling.

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Once the initial nuclei are established two possibilities exist for further crystallization. i.e., more solid may be
deposited upon the first nuclei or fresh nucleation may occur, but growth might be expected to predominat over
further nucleation. Therefore, in this type of nucleation, surface energy barrier is lower because part of the
nucleus is in contact with another phase/surface (impurities). These sites reduce the required energy for
nucleation. Hence, occurs much more easily than homogeneous nucleation.
Difference between homogeneous and Heterogeneous nucleation:
Homogeneous nucleation Heterogeneous nucleation

Occurs in pure metals Occurs in alloys

Nucleation is by deposition of atoms from Nucleation is by the influence of foreign

particles
its own melt

Requires some amount of undercooling for Undercooling is less as compared to

nucleation. homogeneous nucleation.

Starts below the equilibrium freezing Starts comparatively at much higher temperature
temperature
 1.5 Effect of Cold plastic deformation on increasing the strength of metals (Strain
Hardening):

The dislocation density increases with increased cold deformation. New dislocations are created by the cold
deformation and must interact with those already existing. As the dislocation density increases with deformation,
it becomes more and more difficult for the dislocations to move through the existing “forest of dislocations,”
and thus the metal work or strain hardens with increased cold deformation.
Eg- When ductile metals such as copper, aluminum, and iron that have been annealed are cold-worked at room
temperature, they strain-harden because of the dislocation interaction just described. Fig. below shows how cold
working at room temperature increases the tensile strength of unalloyed copper from about 30 ksi (200 MPa) to
45 ksi (320 MPa) with 30% cold work. Associated with the increase in tensile strength, however, is a decrease in
elongation (ductility), as observed in Figure 6.43. With 30% cold work, the elongation of unalloyed copper
decreases from about 52% to 10% elongation.
Cold working or strain hardening is one of the most important methods for strengthening some metals. For
example, pure copper and aluminum can be strengthened significantly only by this method. Thus, cold-drawn
unalloyed copper wire can be produced with different strengths (within certain limitations) by varying the
amount

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of strain hardening (giving percentage of deformation).

 1.5.2Recovery and Recrystallization of plastically deformed metals:
The effect of plastic deformation on the mechanical properties and microstructural features of metals was
discussed. When metal-forming processes such as rolling, forging, extrusion, and others are performed cold
(working at room temperature), the work material has many dislocations and other defects, and the grains are
stretched and deformed; as a result, the worked metal is significantly stronger but less ductile. Many times the
reduced ductility of the cold-worked metal is undesirable, and a softer metal is required. To achieve this, the
cold-worked metal is heated in a furnace. If the metal is reheated to a sufficiently high temperature for a long
enough time, the cold-worked metal structure will go through a series of changes called (1) recovery, (2)
recrystallization, and (3) grain growth. Fig. shows these structural changes schematically as the temperature
of the metal is increased along with the corresponding changes in mechanical properties. This reheating
treatment that softens a cold-worked metal is called annealing, and the terms partial annealing and full
annealing are often used to refer to degrees of softening.

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When a metal is heavily cold-worked, much of the strain energy expended in the plastic deformation is stored in
the metal in the form of dislocations and other imperfections such as point defects. Thus a strain-hardened metal
has a higher internal energy than an unstrained one.
(1) Recovery:
When a cold-worked metal is heated in the recovery temperature range that is just below the recrystallization
temperature range, internal stresses in the metal are relieved. During recovery, sufficient thermal energy is
supplied to allow the dislocations to rearrange themselves into lower-energy configurations. Recovery of many
cold-worked metals (such as pure aluminum) produces a subgrain structure with low-angle grain boundaries.
The internal energy of the recovered metal is lower than that of the cold-worked state since many dislocations
are annihilated or moved into lower energy configurations by the recovery process. During recovery, the
strength of a cold-worked metal is reduced only slightly, but its ductility is usually significantly increased (Fig.)

(2) Recrystallization:
Upon heating a cold-worked metal to a sufficiently high temperature, new strain-free grains are nucleated in the
recovered metal structure and begin to grow, forming a recrystallized structure. After a long enough time at a

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temperature at which recrystallization takes place, the cold-worked structure is completely replaced with a
recrystallized grain structure.
Important factors that affect the recrystallization process in metals and alloys are:
(1) amount of prior deformation of the metal
(2) temperature
(3) time
(4) initial grain size
(5) composition of the metal or alloy.
The recrystallization of a metal can take place over a range of temperatures, and the range is dependent to some
extent on the above variables listed. Thus, one cannot refer to the recrystallization temperature of a metal in the
same sense as the melting temperature of a pure metal.
The following generalizations can be made about the recrystallization process:
1. A minimum amount of deformation of the metal is necessary for recrystallization to be possible. 2. The
smaller the degree of deformation (above the minimum), the higher the temperature needed to cause
recrystallization
3. Increasing the temperature for recrystallization decreases the time necessary to complete it. 4. The final grain
size depends mainly on the degree of deformation. The greater the degree of deformation, the lower the
annealing temperature for recrystallization and the smaller the recrystallized grain size. 5. The larger the original
grain size, the greater the amount of deformation required to produce an equivalent recrystallization
temperature.
6. The recrystallization temperature decreases with increasing purity of the metal.

(3) Grain growth:

Growth follows nucleation and it determines the final crystallographic structure of the solid. The mode of
growth depends upon the thermal conditions in the solidification zone and the constitution of the alloy. During
growth, the material is transferred by diffusion and the rate of transfer by diffusion can be analyzed by an
equation of Arrhenius type, as shown below;
Rate of transfer = constant × e - Q/RT
where, Q – Activation energy, R – Gas constant and T – absolute temperature
The growth is controlled by the rate of heat transfer from the casting. Since there is a temperature gradient
towards the casting surface, the growth occurs in a direction opposite to heat flow. For growth to occur more
atoms must join the solid than leave it and for this to happen the temperature of the interface must be slightly
below the

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equilibrium freezing temperature. This means some amount of undercooling must exist if the interface is to
advance.

In case of pure metals, the undercooling can be produced only by thermal means (thermal undercooling) but in
alloys the undercooling may be produced by the changes in temperature as well as composition which is termed
as constitutional undercooling.
▪ Pure metals – thermal undercooling
▪ Alloys – constitutional undercooling
The presence of undercooling alters the growth morphology (i.e., the advance of solidification front); a faster
advancing interface experiences a transition of the solidification front from planar to cellular and to dendritic
from at even higher rates.
1.5.3Grain structure
The grain structure is defined by the grain size, grain shape and its orientation. Grain size is a very important
factor in relation to strength, usefulness and other physical properties. A fine grained structure offers better
strength over a coarse grained structure but suffers low ductility.
The other advantages of a finer grained structure include
→ increased impact toughness
→ improved machining finishes
→ mitigate cracks and quenching distortions
The grain size in the final product phase depends on the relative rates of nucleation and growth. As each
nucleating particle becomes a grain in the final product; a high nucleation rate means a large number of grains,
moreover with low growth rate more time is available for further nucleation to take place in the parent phase.
Thus, with a high nucleation rate and low growth rate a fine grained structure can be obtained.
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Typical grain structure

A solidifying melt can assume any of the grain structures as shown in Fig. below.
In case of pure metals a columnar grain structure with the grains growing from the mould wall towards the
casting is observed with a thin layer of equiaxed grains near the mould due to chilling effect. On the other hand
alloys experience better undercooling as compared pure metals and hence they usually solidify with a
completely equiaxed structure.
The metals with minor alloying constituents may solidify with a grain structure intermediate to pure metals and
alloys. The solidification begins similar to pure metals with an equiaxed chill zone near mould walls and then
followed by a columnar zone; as the concentration of the solute in the remaining melt becomes richer the mode
of solidification switches to that of an alloy type due to increased undercooling and the remaining melt solidifies
as equiaxed crystals.

Grain refinement is a process of refining the grain structure to impart better properties. It is simply a technique
to control the grain size of the cast structure. Grain refinement aims at reduction or elimination of columnar
zone and increase in number of equiaxed grains.
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1.6 Precipitation Hardening / Age Hardening:

Age hardening is a hardening heat treatment that involves formation of precipitates of an impurity phase over a
prolonged time, which impedes the movement of dislocations throughout the lattice; the precipitates form from a
supersaturated solid solution i.e., when the solubility limit is exceeded. It is employed to enhance hardness of
mostly non-ferrous metals such as aluminium, magnesium, nickel, titanium and some steels. Unlike ferrous
metals, the non-ferrous metals are not amenable to conventional hardening by quenching so as to form

martensite.
The age hardening process involves;
a) Solutionizing: Solution heat treatment where all the solute atoms are dissolved to form a single-phase
solution.
b) Quenching: Rapid cooling across the solvus line to exceed the solubility limit. This leads to a
supersaturated solid solution that remains stable (metastable) due to the low temperatures, which prevent
diffusion. c) Aging: Precipitation heat treatment where the supersaturated solution is heated to an intermediate
temperature to induce precipitation and kept there for some time (aging).
During age hardening, nucleation occurs at a relatively high temperature (often just below the solubility limit)
so that the kinetic barrier of surface energy can be more easily overcome and the maximum number of
precipitate particles can form. These particles are then allowed to grow at lower temperature in a process called
aging. This is carried out under conditions of low solubility so that thermodynamics drive a greater total volume
of precipitate formation.
Phases of aging:

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The different phase observed during aging with respect to time and obtained hardness value are shown in Fig.
below;
Stage 1 – clustering of solute atoms takes place (under-aging)
Stage 2 – nucleation and growth of second phase particles until an equilibrium precipitate volume fraction
is reached (optimum- aging)
Stage 3 – coarsening of precipitates (over-aging)

Too little diffusion (under aging), and the particles will be too small to impede dislocations effectively; too much
(over aging), and they will be too large and dispersed to interact with the majority of dislocations. Hence, only
an optimum aging will impede dislocations efficiently to enhance hardness.

Example – Age hardening of Al-Cu alloy system

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The alloy when heated to 500°C forms solid solution; upon slow cooling the copper starts precipitating out of it
and forms an intermetallic compound cuprous aluminate (CuAl2). On the other hand, if the alloy is rapidly
cooled by quenching the microstructure would contain only solid solution which is supersaturated; this is an
unstable state and fine precipitate of CuAl2 comes out of over a long duration of time. These second phase
particles helps in impeding the dislocation motion by distorting the lattice, thus providing a hardening effect.

Age hardening usually takes place in metals which are partially soluble in each other having better solubility at
elevated temperature than an lower temperature.
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1.7 Heat Treatment

Heat treatment can be defined as a combination of heating and cooling operations carried out on a metal or alloy
in the solid state so as to produce a particular microstructure and properties. It effectively alters the size and
shape of the grains and also the type, extent and distribution of different phases. In this chapter the heat
treatment of steels is discussed in particular.
Stages of heat treatment:
 → Heating the specimen to a specific temperature
→ Holding the specimen at that temperature for a suitable duration
→ Cooling the specimen at a specific rate
Any heat treatment process can be represented graphically with temperature in y axis and time in x axis as
shown in Fig.
Heat treatment temperature, holding time and rate of heating and cooling are some of the heat treatment process
variable. The final properties defined by microstructure depends on these process variables like rate of heating,
rate of cooling or isothermal holding at required temperature.

Purpose of Heat treatment:

▪ To refine the grains
▪ To improve mechanical properties
▪ To relieve internal stresses
▪ To modify electrical and magnetic properties
▪ To improve machinability
▪ To increase resistance to wear and corrosion.

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1.7.1Annealing:
Annealing involves heating a material to temperature above transformation range, holding at this temperature
and finally cooling at very slow rate. The objects are ordinarily allowed to cool slowly in furnace, although they
may be removed from the furnace and cooled in some medium which reduces the rate of cooling. Annealing can
be final treatment or a preparatory step for further treatment.
Purpose:
 → To relieve internal stresses developed during solidification or any other mechanical working.
→ To improves ductility and toughness property.
→ To enhance machinability
→ To refine grain size (Coarse grain structure).
→ To facilitate cold working

Fig. Annealing of Steels

Types of Annealing:
1. Full Annealing
2. Spheroidizing Annealing
3. Recrystallization Annealing
4. Stress-relief Annealing

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Full Annealing:
Heating the steel above the upper critical temperature for hypo-eutectoid steels (A3) and above lower critical
temperature for hyper-eutectoid steel (A1) and holding them at that temperature for a certain time, based on size
and shape of the specimen; thereafter cooling them at a very slow rate (furnace cooled) is termed as full
annealing. During this effective grain refinement can be achieved for hypo-eutectoid steels but for hyper-
eutectoid steels the austenite undergoes grain growth when held at high temperature for long duration which on
cooling will transform to coarse lamellar pearlite surrounded by a network of proeutectoid cementite. The
cementite network being brittle results in poor machinability and impact properties of the heat treated steel, thus
annealing should never be a final heat treatment for hyper-eutectoid steels.
Full annealing is expensive due to the prolonged heat treatment.
Spheroidizing Annealing:
Heating the steel slightly above or below the lower critical temperature (A1) and holding it at the same
temperature for certain duration so that the lamellar cementite in the pearlite colonies tends to spheroidize and
reduce their surface area; this corresponds to the softest state of steel. It is then furnace cooled. This process is
suitable for increasing the machinability (suitable for hyper- eutectoid steels).
Recrystallization Annealing:
This process is carried out at subcritical temperature, i.e., at about 600 to 650°C in order to remove the strain
hardening effects due to cold working. During this process the cold worked ferrite recrystallizes; the grain size
of the recrystallized microstructure decreases with the degree of cold work (deformation). This process is
suitable for enhancing the ductility. (Note: Higher the degree of cold working, more will be the strain hardening
effects and accordingly the recrystallization temperature will be low)
Stress-relief Annealing:
A recovery process carried out at sub critical temperature of about 600°C for hypo-eutectoid steels. There is no
recrystallization taking place rather a mild atomic mobility to diminish the concentration of point defects and to
remove residual stress due to cold working or machining; there is a slight decrease in the hardness. This process
requires sufficiently long holding time.

1.7.2Normalizing
Heating the steel to about 40 – 50°C above the upper critical temperature (A3 and Am) and holding at that
temperature for a short duration followed by cooling in the still air to room temperature is termed as
normalizing. Normalizing results in a fine pearlitic structure.

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Purpose:
→ To refine the grain size of steel (Fine grain structure)
→ To improve machinability
→ To eliminate or break coarse pro-eutectoid ferrite network in hypo-eutectoid steels or eliminate or break
 coarse pro-eutectoid cementite network in hyper-eutectoid steels.
→ To improve mechanical properties (strength and hardness)
→ To modify and refine cast dendritic structure

Fig. Normalizing of steel

Difference between Annealing and Normalizing:
Annealing Normalizing

Generally, Furnace cooling (Slow cooling rate) Generally, Air cooling (Faster cooling rate)

Softness or ductility increases Hardness of specimen increases

Continues cooling with lower degree Continues cooling with higher degree
of supercooling of supercooling

Poor dispersion of ferrite and cementite Better dispersion of ferrite & cementite
in pearlite phase in pearlite

Microstructure contains less amount of pearlite Microstructure contains more amount

of pearlite

Prolonged heat treatment time and Treatment is cheaper

higher energy consumption make
treatment more expensive

Basic purpose is to soften the specimen Basic purpose is to improve machinability

Less internal stress More internal stress

Coarser grains Finer grains

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