MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

Solidifcaton
CHAPTER-2
Solidifcaton: Meaning, degree of super cooling, homogeneous and
heterogeneous nucleation, mechanism of solidification –nucleation and
crystal growth, dendritic growth. [03]

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MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

MME-2104, MATERIALS SCIENCE & METALLURGY [ 3 0 0 3]

1. K.M Gupta (2012) “ Material science, Metallurgy and Engineering

Materials, Umesh Publication, New Delhi.
2. Lakhtin Yu., (1985). "Engineering Physical metallurgy and heat
treatment”, MIR Publishers, Moscow
3. William D. Callister (2007), “Materials Science and Engineering” , John
Wiley & Sons
4. Avner S.H. (2004), “Introduction to Physical Metallurgy ", 3rd Edition,
McGraw Hill.New Delhi
5. Arzamasov, (1989) " Material Science ", MIR Publishers,Moscow.
6. Raghavan V,(1989) “Material Science and Engineering”, 4th Edition,
Prentice Hall of India, Delhi

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 MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

Chapter 2: Solidifcaton
Introducton:
The solidification of metals and alloys is an important industrial process since most of the
metals are melted and then cast into a semi finished or finished shape. Solidification is one
of the most important phase transformations in materials, and its proper understanding is
essential in control of many fabricating processes. The transformation of a metal or alloy
from its liquid state to the solid state is often known as primary crystallization or simply
solidification.
Defniton of Solidifcaton:
The transformation of metals and alloys from liquid state to solid state (crystalline state) is
called solidification or crystallization.
To understand the concept of solidification, let us first understand the melting process. Then
let us understand the process of solidification.
Meltng or Fusion of Metals:
Consider a pure metal being melted from room

Temperature
temperature. When the melting temperature is
C
reached, the solid metal starts melting, but at Melting Temp.
constant temperature. This can be understood by L
considering the graph of temperature versus time L+S
A B
as shown in figure 3.1. The process of melting takes
place at constant temperature as the heat added is Latent heat
utilized in breaking the bonds of the solid crystal Super heat
S
structure.
The heat that is added to the metal to convert all
the solid metal into liquid state is called the “Latent O Time
heat of fusion”. AB represents the constant Fig. 3.1 Melting process
temperature line. The heat that is further added to the metal in the molten metal is called
Temperature

the “Super heat”. C

Freezing or Solidifcaton or Crystallizaton of metals: L

Solidification is the reverse of melting. The pure
metal in its molten state first gives up its D L+S E
Temperature

superheat upon cooling. When the temperature Latent heat

drops to the freezing (solidification) temperature, S
the solidification process starts. The metal starts C Super heat
to give out its latent heat at constant freezing F
Freezing temp.
temperature. This continues until all the metal in
L Time
the liquid state is converted into the solid state.
Fig This
Further the metal in the solid state is cooled to room temperature. 3.2 The
typesolidification process
of curve (graph)
T D
as shown in figure 3.2, i.e., temperature taken on1the Y axis versusL the
+ S time taken on the X
axis is called as the “Cooling Curve”
Cooling curve for pure metal and alloy T2 E

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F
Time
Fig 3.3 (b) Cooling curve for an
 MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

Temperature

D L+S E
TS

F
The solidification of a pure metal takesTimeplace at a constant temperature T S as shown in figure
Fig(a).
3.3 3.3The
(a) Cooling curveline
solidification for aDEpure
is horizontal on the cooling curve for a pure metal which
metal
means that solidification begins and ends at the same temperature T S. Whereas, the
solidification of an alloy takes place over a range of temperature T 1 to T2 as shown in figure
3.3 (b). The solidification line DE is inclined on the cooling curve for an alloy which means
that solidification begins at temperature T1 and ends at temperature T2.
The solidification of metal can be divided into:
(a) Nucleaton of minute crystals – The formation of stable nuclei in the liquid melt.
(b) Growth of nuclei into crystals and formaton of grain structure.
Nucle Crystals
i or
Grains

Liquid
metal Grain
boundaries

Fig 3.4 Stages in the solidification process

Undercooling/Supercooling: Cause of initaton of Solidifcaton:

The solidification is initiated and proceeds due to conversion of matter to a more stable
thermodynamic condition with less free energy or thermodynamic potential.
At any given temperature, the total energy content (H) of a system is divided between free
energy (F) and bound energy (TS).
 H = F + TS -------- (3.1)
Free energy (F) is defined as the isothermally available energy. i.e., under certain conditions,
the free energy can be released from the system with no accompanying change in

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 MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

temperature of system. Free energy is reversibly changed upon changes in temperatures,

allotropic transformations, fusion (melting), etc.
Bound energy (TS) is expressed as product of the absolute temperature (T) and the entropy
(S). It exists as the kinetic energy of the random motions of the atoms within the system and
as potential energy of the atoms arrangement relative to each other.
 Total heat energy, H = F + TS
Or Free energy, F = H – TS = (E + PV) - TS
Where, H = E + PV ------- (3.2)
E = Internal Energy, P = Pressure, V = Volume, T = Absolute temperature, S = Entropy.
So solidification proceeds when the solid crystals are more stable i.e., when the solid crystals
are having less free energy content compared to the liquid metal.

Relatonship of free energy with temperature:

The free energy of a phase decreases with temperature. The variation of Free energy of
liquid and solid states of a metal with temperature is shown in figure 3.4. At temperature T S,
the liquid and solid phases are having the same free energy content which means that solid
and liquid phases co-exist at temperature T S for infinite period of time. Hence, the
temperature TS is known as the equilibrium temperature of solidification or melting.
The solidification does not begin at this temperature. It proceeds only when there is a
difference in free energy contents of solid
and liquid phases, that too when the free
Free Energy, F

energy content of solid state is lesser than

that of the liquid state.
From the free energy diagram (fig 3.5) it can
F
be noted that at temperatures lesser than
TS, free energy content of solid phase is
lesser than that of liquid phase. Hence,
solidification starts and proceeds only when
the metal is supercooled to the supercool
temperature TK below the equilibrium FS
T FL
temperature TS. The amount of
temperature by which the metal is
TK TS
supercooled (difference between TS & TK, Temperature, T
i.e., T = TS – TK) is called the “Degree of Fig 3.5 Variation of free energy of a
Temperature

C
metal with temperature
Supercooling” or “Degree of Undercooling”
 Degree of Supercooling = T = TS – TK L

TS D L+S E
TK
D1
The actual cooling curve: S

F
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Time
Fig. 3.6 Cooling curve with
supercooling shown on it
 MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

The cooling curve which was shown earlier in figure 3.2 has to Supercooling
represent the “Supercooling” or “Undercooling” on it. Figure 3.6
shows that the liquid metal must be supercooled below T S upto the point D1 (temperature
TK) for the solidification to initiate. Once the nuclei are formed, the heat released increases
the temperature of the liquid metal from T K to TS as represented by the portion of the curve
D1D. Then the solidification proceeds at constant temperature T S (represented by line DE)
where the latent heat released is used in building bonds between atoms. At point E, the
solidification is complete and the line EF represents the cooling of the solid phase formed.

Mechanism of Solidifcaton in metals and alloys:

As mentioned earlier, solidification of liquid metal takes place in two stages:
(a) Nucleation of minute crystals
(b) Growth of these crystals into grains and formation of grain boundaries.
(a) Nucleaton of minute crystals:
The molten metal in the liquid state Liquid
is in a highly unstable state. It metal Nucle
possesses high energy (kinetic i
energy) and the atoms are in a state
Temperature

C Crystals
of vigorous random motion. The
or
high velocity motion of the atoms Grains
does not allow them to respond to L
the attractive forces between D
TS L+S E
themselves, i.e., the forces causing
TK
their motion are prominent. As the D1
metal cools (temperature falls), the S
atoms lose their energy and their F
motion becomes less vigorous. Now
the attractive forces become Time
prominent and the atoms collide Fig. 3.7 Cooling curve with undercooling
with each other forming small and solidification stages shown on
it
clusters of atoms. Usually 2 to 3
atoms come together to form a cluster. Such a cluster of atoms is called an “Embryo” or
“Chance aggregate”. Sometimes the embryo formed may again disassociate and dissolve
into the melt. Once the embryo reaches a particular size (critical size), it will not disassociate
and is called as the “Nucleus”. This phenomenon of formation of a stable nucleus is called as
“Nucleation”. Simultaneously a number of such nuclei are formed at random locations in the
liquid melt. If more number of nuclei are initially formed, the final grain structure will be fine
and if less number of nuclei are formed initially, the final grain structure will be coarse or
medium.
Crystal Growth & formaton of grain boundaries:

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 MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

Once the nuclei are formed, the molten metal around the nuclei begin to solidify. During
solidification, the metal continuously releases the latent heat which it had acquired during
melting. The heat released is absorbed by the surrounding molten metal which will in turn
release it to the surrounding environment for the solidification process to continue.
Depending upon the crystal structure of the metal undergoing solidification, the atoms will
arrange themselves around the nucleus in 3 dimensions (X, Y & Z directions). The unit cells
get added in 3 dimensions forming a structure similar to branching of tree as shown in figure
3.10 (a) to (b). Such a structure is called the “Dendritc Structure” and such growth of the
crystal is called as the “Dendritc Growth”.
Towards the end of the solidification process, only a small amount of the liquid is remaining.
The big dendrite trees meet each other at their extremities. The last atoms in between the
crystals take up compromise positions. Such atoms are weakly bonded with the crystals.
Such atoms form the “Grain Boundaries” or the “Crystal Boundaries”. The grain boundary
width will range over a few atomic dimensions.

Fig 3.10
Fig 3.10
(a)
(b)

Nucleaton types: Nucleation in metals and alloys may occur by two mechanisms:
(i) Homogeneous Nucleaton & (ii) Heterogeneous Nucleaton
Comparison between Homogeneous and Heterogeneous Nucleaton:
Homogeneous Nucleaton Heterogeneous Nucleaton
1. Nucleation takes place without the 1. Nucleation takes place in the presence
presence (help) of any impurity atoms. of impurity atoms.
Fig 3.10
2. It is an ideal case of nucleation and 2. It is found in actual Fig practice
3.10 and occurs
(c) Fig 3.10 (a)
occurs in pure metal solidification. to (d) Three dimensional dendritic growth
(d)
in all metals and alloys.
3. Nucleation may be initiated at any site 3. Nucleation is initiated on substrate
within the liquid melt simultaneously. (impurity) surfaces. i.e., its initiation is
not simultaneous.
4. This require higher degree of 4. This requires lower degree of
suprecooling supercooling
5. It is a slower process and hence larger 5. It is a faster process and hence smaller
grain size is seen after solidification. (finer) grain size is seen after

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MME-2104 (Material Science and Metallurgy) Chp-2 (Solidification)

solidification.
6. Critical size of the nucleus required is 6. Critical size of the nucleus required is
larger. smaller.

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