International Journal of Engineering Technology Science and Research

IJETSR
www.ijetsr.com
ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

Solidification Process of Pure Metal

Ramachander Jatoth1, G. Veerendra Naik 2

1
Assistant Professes Dept of Mechanical Engineering, Sri Venkateswara Engineering College, Suryapet, India.
2
Assistant Professes Dept Of Mechanical Engineering, Sri Venkateswara Engineering College, Suryapet,
India.

ABSTRACT
This paper reviews methods which have been proposed solidification process in the casting. Pure metals in its solid state
have low strength and good ductility. It can be formed into any shape. It can be rolled down to thin sheet (Aluminium
foil) or drawn into extremely fine wires (copper wires used as electrical conductors). It is crystalline but it is not so
apparent from its external shape as in the cases of several inorganic solids. The distance between atoms is of the order of
0.1nm. It can diffract X‐rays having wavelength of similar order. Its crystal structure can be determined from diffraction
patterns. On heating it melts at a fixed temperature. This is associated with the loss of its crystalline nature. On cooling it
becomes solid again.
Keywords: Cooling Curve, Phase Rule, Concept of Free Energy, Entropy, Surface Energy (grain boundary) & Under
Cooling, Nucleation & Growth, Homogeneous & Heterogeneous Nucleation, Directional Solidification.

INTRODUCTION
The transformation is basic to such technological applications as ingot casting, foundry casting, continuous
casting, single-crystal growth for semiconductors, and directionally solidified composite alloys. It is the
objective of this chapter to develop some of the basic concepts of solidification, and apply these to the
practical processes of ingot casting, continuous casting and fusion welding.
Pure metals in its solid state have low strength and good ductility. It can be formed into any shape. It can be
rolled down to thin sheet (Aluminium foil) or drawn into extremely fine wires (copper wires used as electrical
conductors). It is crystalline but it is not so apparent from its external shape as in the cases of several inorganic
solids. The distance between atoms is of the order of 0.1nm. It can diffract X‐rays having wavelength of
similar order. Its crystal structure can be determined from diffraction patterns. On heating it melts at a fixed
temperature. This is associated with the loss of its crystalline nature. On cooling it becomes solid again. This
module gives an overview of the process of solidification and answers some of the questions listed here. What
are the factors that would determine its final structure? Does the transformation take place at its melting point
during solidification? What is the role played by super cooling or under cooling?

COOLING CURVE
The best way to monitor the process of solidification is to measure its temperature by a thermocouple. Figure
1 gives a plot of temperature (T) as a function of time (t). It shows that temperature keeps dropping
continuously till it reaches a temperature when cooling stops till the liquid gets transformed totally into solid.
Thereafter temperature keeps dropping again.
As shows cooling curve of pure metal as it cools from liquid state. Gibb’s phase rule gives a simple
relationship between numbers of phases (P), number of component (C), and degree of freedom (F) for a given
system. This is stated as P+F = C+2. Note that C = 1 since it is a pure metal & P = 1 since there is only one
phase above Tm (melting point). Therefore F = 2. It means this state can have 2 controllable variables. These
are temperature and pressure.

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 International Journal of Engineering Technology Science and Research
IJETSR
www.ijetsr.com
ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

Fig 1: cooling curve of pure metal

Cooling curve for a pure metal showing possible under cooling.

• The transformation temperature, as shown on the equilibrium diagram, represents the point at which the
free energy of the solid phase is equal to that of the liquid phase.
• Thus, we may consider the transition, as given in a phase diagram, to occur when the free energy change,
ΔGV, is infinitesimally small and negative, i.e. when a small but positive driving force exists due to under
cooling.

SOLIDIFICATION OF A PURE METAL

 During solidification, the liquid changes in to solid during cooling.
 The energy of liquid is less than that of the solid above the melting point. Hence liquid is stable above the
melting point.
 Below the melting point, the energy of liquid becomes more than that of the solid.
 Hence below the melting point, the solid becomes more stable than the liquid.
 Therefore at the melting point, liquid gets converted in to solid during cooling.
 This transformation of liquid into solid below melting point is known as solidification.

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 International Journal of Engineering Technology Science and Research
IJETSR
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ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

GIBB’S PHASE RULE (P+F = C+2)

The degree of freedom that determines the number of control parameters (like temperature, volume, pressure,
composition) for any closed system follows Gibbs phase rule as stated in the caption of fig1. Above the
melting point this is equal to 2. Clearly these variables here are the temperature and pressure. The cooling
curve given above has been obtained at atmospheric pressure which is of course fixed. Therefore what the
phase rule tells us is that the liquid state is stable over a range of temperature. In other words to define the
state of liquid apart from pressure you need to define another variable that is temperature. Let us apply this to
the state where both liquid and solid can co‐exist. Here P = 2 and C = 1. From phase rule F = 1. This state can
have only one variable which in this case is pressure. This means in the case of a pure metal liquid & solid can
coexist only at a definite temperature which happens to be its melting point. As long as the solidification
process continues both liquid and solid must coexist. Therefore temperature has to remain constant. In other
words at a given pressure all pure metals or substance melts or solidifies at a fixed temperature called melting
point. This however can vary with pressure.

PHASE DIAGRAM OF PURE METAL

Phase diagram of a pure metal or a substance is a graphical representation of the domain in which a given
state is stable. For example it gives the range of temperature and pressure over which it exists as solid (S),
liquid (L) or gas G). Figure 2 gives a typical phase diagram of a pure metal.
A schematic phase diagram of a pure metal indicating the pressure temperature domain where it can exist as
solid, liquid or gas. The line indicates boundary between two phases. On any point on the line two phases are
equally stable. There is a point where three lines meet. This is a critical point (triple point) where three phases
can coexist. Apply phase rule. This gives F=0 meaning that it has no degree of freedom. Three phases can
coexist only at a fixed temperature & pressure. For water the triple point is at 0.006atmosphere 0.01°C. The
caption of fig 2 describes the main features of the phase diagram. It has a horizontal line drawn at 1
atmosphere pressure. It intersects the S/L boundary at its melting point and L/G boundary at its boiling point.
The slopes of these lines are positive indicating that both melting and boiling points increase with increasing
pressure.

Fig 3: A schematic phase diagram of a pure metal

GIBB’S FREE ENERGY (G)

Gibb’s free energy (G) is a measure of the stability of a phase at a given temperature and pressure. The lower
the free energy higher is its stability. At a given temperature (T) this is defined in terms of molar enthalpy (H)
and molar entropy (S) of a particular phase as follows:
G = H – T S --------------------- (1)
This can be written in differential form in terms of pressure (P) & temperature (T), the two common variables
for most transformation processes, as:

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ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

dG = V dP – S dT --------------------- (2)
The equation 2 is valid both for solid and liquid. Let us write these explicitly for the two using subscript S (for
solid) & L (for liquid). Figure 3 gives a schematic plot showing how free energy varies with temperature for
the two phases at 1 atmosphere pressure. The point where the two lines intersect denotes the melting point at
1atm.
dGL = VL dP – SL dT for liquid -------------------- (3)
dGS = VS dP – SS dT for liquid -------------------- (4)

Fig 3: A sketch showing how G varies as a function of T for solid (S) and liquid phase (L).

The two intersect at melting point Tm. Below this temperature solid is stable whereas above Tm liquid is
stable. At any temperature the difference between the two is the driving force for the transformation. At the
melting point the free energy of solid and liquid should be the same. Equating equation 3 & 4 and subsequent
rearrangement of the terms one gets the following expression:

∆ ∆
= = (∆ )= ∆
------------------------ (5)

Apply this to ice making. When water becomes ice there is an increase in volume and it is accompanied by
release of heat. Therefore ∆ − is positive; whereas ∆ − is negative. Consequently (dP/dT) or the
slope of the line denoting L‐S equilibrium should be negative signifying that at higher pressure ice forms at
lower temperature. This is exploited during ice skating. Ice melts because its freezing point drops under
pressure that is exerted by the skater. The thin layer of molten ice (water) that forms provides the lubricant
required for skating.

PHASE DIAGRAM OF PURE IRON

Iron can exist in more than one crystalline form. Melting point of pure iron is 1539°C. If it is cooled from its
molten state it first solidifies in the form a bcc phase. This form of iron is known as ferrite. As the temperature
goes down at 1400°C it transforms from phase to FCC phase. This is commonly known as iron or austenite.
Later at 910°C it again transforms into BCC crystal known as ferrite. Each of these transformations is
associated with a change in volume and enthalpy. The cooling curve is therefore is expected to show steps
(see fig 4) or discontinuities at these three temperatures. A step indicates coexistence of two phases. The phase
diagram of pure iron is shown in fig 5. This shows the effect of pressure on the temperatures at which
transformation of iron from one crystalline from to another takes place.

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IJETSR
www.ijetsr.com
ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

Fig 4: Cooling curve for pure iron showing three steps representing following transformations:

L = at 1539°C
L + γ = at 1400°C
L + α = at 910°C
The dashed vertical line in figure 5 has been drawn at 1atmospheric pressure. It intersects the boundaries
between alpha and gamma at 910°C. Alpha (α) (BCC) gamma (γ) (FCC) transformation is accompanied by
contraction. Therefore the slope of the line is negative. This suggests that at higher pressure transformation
would take place at a lower temperature. As against this the lines representing gamma delta or delta liquid
have positive slopes. At 1atmosphere pressure gamma delta transformation takes place at 1400C whereas delta
liquid transformation takes place at 1539C. Both of these are accompanied by expansion therefore the slopes
of the two lines are positive.

Fig 5: A sketch showing the phase diagram of pure iron. This gives the stability of α, γ, δ, L & G phases in
various temperature pressure domains.

PHASE DIAGRAM OF PURE METAL

The cooling curve of a pure metal as shown in fig 1 is indeed an idealization of the solidification process. In
reality the transformation from liquid to solid state begins only after it has cooled below its melting point.
Figure 6 shows a sketch of real cooling curve. Once the process initiates the latent heat that is released by the
metal raises the temperature back to its melting point. Thereafter the temperature remains constant till the
solidification is complete.

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IJETSR
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ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

Fig 6: A sketch showing real cooling curve. Along with this G versus T plot of the solid and liquid phases
have been shown. At a temperature lower than its melting point GS < GL signifying S is more stable than L.

When a solid forms in a pool of liquid a new surface is created (see fig 7). This has a finite energy. It is seen
from fig 6 that GS < GL when solidification begins. This difference in free energy acts as the driving force for
solidification. Once this is large enough for a stable nucleus of solid to form the process of solidification
begins. Until then unstable nuclei may appear and disappear again and again. Soon after a stable nucleus
forms it keeps growing. Thus the process of solidification can be visualized as one of nucleation and growth.

Fig 7: A sketch showing a spherical nucleus of solid of radius r formed in a pool of liquid.
This has a volume r3 and surface area 4 r2 . The creation of a new surface needs energy. Note that GS < GL,
∆G L‐S < 0. This can help do so. Assuming that surface energy / unit area is σ and free energy change / unit
volume is ∆fv it is possible to derive an expression for the total change in energy for solidification.
Figure 7 shows the sketch of a nucleus of solid in a pool of liquid. From the details given in the caption the net
energy of transformation is given by the following expression.
∆fT = r3 ∆fV + 4 r2 σ = ar3 + br2 ------------------------(6)
Note that the volume free energy (or the driving force) term increases as the cube of the radius and the surface
energy term increases as the square of the radius. The former is negative whereas the latter is positive. At
extremely smaller values of r the surface energy term is more dominant and the net energy is positive.
However as r grows the energy is likely to increase and pass through a peak.
∆fr
The location of the peak can be estimated by equating =0
∆fr
= 4 r2 ∆fV + 8 r2 σ = 0; rc = - ---------------- (7)
∆fV
This gives the critical size of the nucleus. Note that ∆fV is negative. Therefore rC has a finite positive value.
On substitution of the size of the critical nucleus in the expression for the total energy one obtains the
maximum value it can have. This is given by:
∆fTmax = ∆
----------------------- (8)

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Fig 8: Sketch showing how surface energy which is positive, volume energy and the total energy change with
the size of nucleus. Initially SE contribution far exceeds VE so that the net energy is positive. However VE
increases faster with increasing size of the nucleus. The total energy passes through a peak. The corresponding
value of r is the critical nucleus size. Nuclei with r < rC are called unstable nuclei (embryo) and those with r >
rC are the stable nuclei (embryo) that can grow spontaneously.
From the above analysis of the energetic of solidification the following conclusions can be drawn. (i)
Super‐cooling is necessary for stable nuclei of solid to form in a pool of liquid. (ii) Only nuclei having size
greater than a critical value rC can grow spontaneously. (iii) Higher the super cooling lower is the size of
critical nucleus (iv) Higher the super‐cooling lower is the nucleation barrier (∆fTmax). This is also called the
activation hill.

NUCLEATION AND GROWTH OF CRYSTALS

 At the solidification temperature, atoms from the liquid, such as molten metal, begin to bond together
and start to form crystals.
 The moment a crystal begins to grow is known as nucleus and the point where it occurs is the
nucleation point.
 When a metal begins to solidify, multiple crystals begin to grow in the liquid.
 The final sizes of the individual crystals depend on the number of nucleation points.
 The crystals increase in size by the progressive addition of atoms and grow until they impinge upon
adjacent growing crystal.

Fig: (a) Nucleation of crystals, b) crystal growth, c) irregular grains form as crystals grow together, d) grain
boundaries as seen in a microscope

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ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

CONCEPT OF NUCLEATION AND GROWTH

Solidification takes place by nucleation and growth. Atoms in a solid or in a liquid are never stationary.
Assume that in a pool of molten metal there is a virtual boundary that separates a potential stable nucleus
(embryo) from the surrounding liquid. Such virtual nuclei infinitesimally small in size may be assumed to be
present in the liquid that is about to solidify. Atoms keep trying to cross the barrier. Let be the number of
attempts per unit time made by an atom to cross the boundary. The number of successful attempt is given by
the Boltzmann statistics. This is represented mathematically as follows:
V = v 0 exp (- ) ----------------------- (9)
Note that k is Boltzmann constant and E is the energy needed by atom to overcome the barrier to cross the
boundary. In this case this corresponds to∆fTmax. However this represents the total energy needed by all the
atoms in a unit volume (n). Therefore the energy needed by a single E = ∆fTmax / n. This shows that with
increasing E the probability of formation of stable nuclei should decrease. Once stable nuclei form they would
continue to grow. Initially the growth occurs at same rate in all direction until the growth is hindered due to
impingement. The formation of new nuclei within the remaining liquid also continues. When the process is
complete the solid is found to consist of several grains (crystals). The size of the grains may differ depending
on whether it developed from a nucleus formed right in the beginning or towards the end of the process. This
is shown pictorially in fig 9.

Fig 9: A sketch showing a schematic representation of nucleation and growth of solid nuclei during
solidification from the molten liquid state. Colours denote different orientations of grains. (a) Shows that
growth ceases along certain directions due to impingement. A few more nuclei have formed. All of these
continue to grow. (b) Shows a state when most of the space is filled up indicating that the process is nearly
complete. Grains appear to be randomly oriented.

GRAIN ORIENTATION
The process of nucleation described above is totally random. Grains may nucleate anywhere in the melt. It is
also known as homogeneous nucleation. If the orientations of the grains are represented in a standard
projection by their cube poles these will be located uniformly all over the entire standard projection. Such
plots are known as pole figures.
We have so far looked at homogeneous nucleation. This is most likely to happen if the molten pool of metal
has no free surface. This however is only a hypothetical case which may occur only at the centre of the mould
containing the molten metal. Mould surface provides an interface where solid may nucleate. When it takes
place on a pre‐existing solid surface the process is known as heterogeneous nucleation. This is illustrated in
fig 11. Since the mould surface provides a part of the surface energy it would need less driving force (super
cooling). Thus by providing such nucleation sites it is possible to promote solidification. More the number of
sites for nucleation finer are the grains. This is one of the ways of having fine grain structure on solidification.

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ISSN 2394 – 3386
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The process is known as inoculation where very small amount of easily dispersible fine solid particles are
added to the metal as it is poured into mould.

Fig 11 a) A sketch showing homogeneous nucleation of a solid spherical ball in a molten pool of metal in a
hypothetical mould without any boundary.

Fig 11 b) Sketch showing a case where apart from an embryo at the centre there are several nuclei each
formed on the interface between the mould wall and the liquid metal.

DIRECTIONAL SOLIDIFICATION
How the heat is extracted from the molten pool of metal is of considerable importance in determining the
structure of the solid. When liquid metal is poured into a mould (sometime preheated) the heat flows from the
liquid through the mould wall to the surrounding environment. Heat flows from higher to lower temperature.
The rate is proportional to thermal gradient. It also depends on the effective heat transfer coefficient of the
entire system consisting of the liquid, solidified layer, the mould and the region surrounding the mould. Figure
13 illustrates a case where heat is being extracted in one direction from the liquid metal through solid metal
and the mould. Note that the solid liquid interface is flat in this case. The liquid to solid transformation is
accompanied by evolution of heat at the interface. This can only be extracted down the temperature gradient.
Figure 14 shows a sketch why any unevenness is likely to disappear.

Fig 13: Sketch showing the direction of heat flow from the liquid metal through the solid and the mould. It
also gives the temperature as a function of distance. The S/L interface is likely to be flat. The rate at which it
moves would depend on how fast the heat can be extracted.

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ISSN 2394 – 3386
Volume 4, Issue 12
December 2017

Fig 14: Sketch showing a bulge in the S/L interface. The arrow denotes the direction of heat flow. This makes
it unstable as the heat flowing into the bulge would melt it again.

SUMMARY
This module describes the important features of the cooling curve of a pure metal. The reason for the
occurrence of a step has been explained by using Gibb’s phase rule. The equation describing the effect of
pressure on the melting point has been derived. The importance of super‐cooling in on the evolution of the
structure of metal has been explained. The concepts of nucleation & growth and directional solidification have
been introduced.

REFERENCES
[1] E. Majchrzak, M. Jasinski, G. Kaluza, Application of shape sensitivity analysis in numerical modelling of
solidification process, Archives of Foundry 5/15 (2005) 259-264.
[2] E. Majchrzak, J.S. Suchy, R. Szopa, Linear model of crystallization - identification of nuclei density,
Giessereiforschung, International Foundry Research 2 (2006) 29-32.
[3] E. Majchrzak, A. Piasecka, The numerical micro/macro model of solidification process, Journal of Materials
Processing Technology 64 (1997) 267-276.
[4] E. Majchrzak, M. Dziewonski, A. Metelski, Estimation of nuclei density in solidifying casting using the
Kolmogoroff model, Archives of Foundry 5/15 (2005) 253-258.
[5]. W. Kapturkiewicz, Modelling of Cast Iron Crystallization, AKAPIT, Cracow, 2003 (in Polish).

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