Chapter-6

Cooling and Solidification of Casting

Outlines
Introduction
Freezing of a pure metal
Freezing of alloys
Dendritic growth and segregation.
Directional solidification
Other properties related to the freezing
mechanism fluidity, hot tearing, evolution of
dissolved gases, effect of inoculation)

Introduction
The majority of metals and alloys are melted and then allowed to
solidify as a casting;
Solidification conditions determine the structure, homogeneity and
soundness of cast products ;
The transition from a highly disordered liquid to an ordered solid is
accompanied by a lowering in the energy state of the metal and the
release of thermal energy (latent heat of solidification), forming the
arrest on the cooling curve.
The properties of the casting significantly depends on the
solidification time cooing rate.
Shrinkage of casting, during cooling of solidified metal should not be
restrained by the mould material, otherwise internal stresses may
develop and form cracks in casting.
Proper care should be taken at the design stage of casting so that
shrinkage can occur without casting defects.
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Solidification

Solidification is a phase transformation process in

which liquid is transformed to solid when superheat
and latent heat are removed.
It is involving crystallization of the liquid phase,
segregation of impurities and alloying elements,
liberation of the gases dissolved in fine and
homogeneous grain structure is the most desirable for
the common castings and ingots;
In this connection it is important to distinguish between
solidification of pure metals and alloys.
Pure metals solidify at constant temperature, whereas
alloys solidify over a range of temperature.
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Solidification Process
There are two general stages of phase transformation
(crystallization) process:
Nucleation; and
growth of Nuclei (crystal growth).

Solidification = nucleation + growth of nuclei

Nucleation:
Nucleation is the appearance at points in the liquid of centers
upon which further atoms can be deposited for the growth of
solid crystals;
Nucleation may occur by either homogeneous or heterogeneous
mechanism, depending on the value of undercooling of the
liquid phase (cooling below the equilibrium freezing point);
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Contd
Under cooling value determines quantity of nuclei, forming
in the crystallizing alloy. When a liquid comes into a contact
with cold and massive mold wall (chill zone), it cools fast
below the freezing point, resulting in formation of a large
quantity of stable nuclei crystals;
In order to promote the nucleation process, surface-active
additives are used. They decrease interfacial energy of the
nuclei crystals, causing formation of many more new stable
nuclei.

Time

Schematic Representation of Solidification

(a)

Formation of stable
(b) Growth of (c) Grain structure
nuclei
crystals
Solidification = nucleation + growth of nuclei

Mechanisms of Nucleation
The two main mechanisms by which nucleation
of a solid particles in liquid metal occurs are:
1. Homogeneous nucleation, and
2. Heterogeneous nucleation.

Homogeneous Nucleation
Homogeneous nucleation occurs when there are no
special objects inside a phase which can cause
nucleation;
For instance when a pure liquid metal is slowly
cooled below its equilibrium freezing temperature to
a sufficient degree, numerous homogeneous nuclei
are created by slowmoving atoms bonding together
in a crystalline form;
If there is no solid substance present, undercooling of
a hundred degrees is required in order to form stable
nuclei or seeds crystals, providing following crystal
growth (homogeneous nucleation)
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Homogeneous Nucleation

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Contd

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Heterogeneous Nucleation

Heterogeneous nucleation is the nucleation that

occurs in a liquid on the surfaces of its container,
insoluble impurities or other structural material
(catalyst) which lower the critical free energy
required to form a stable nucleus.
Presence of foreign particles or other foreign
substance in the liquid alloy (walls of the casting
mold) enables to initiate crystallization at minor
value of under cooling (few degrees below the
freezing point);This is heterogeneous nucleation.
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Heterogeneous Nucleation
Heterogeneous nucleation facilitated by:
Similar crystal structure (low misfit strain);
Chemical affinity;
Rough surface (reduced melt/nucleus surface).

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Growth of Nuclei (crystal growth):

Growth process during nucleation determine final crystallographic structure of
the solid;
The mode of growth, both of individual grains and of the general mass of solid,
depends upon thermal conditions in the solidification zone and the constitution
of the alloy;

When a large number of stable nuclei are present in chill zone of mold, fine
equiaxed grains form.
Latent crystallization heat, liberating from the crystallizing metal,
decreases the under cooling of the melt and depresses the fast grains
growth.
At this stage some of small grains, having favorable growth axis, start to
grow in the direction opposite to the direction of heat flow. As a result
columnar crystals (columnar grains) form.
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Contd

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Solidification of Metals and Alloys

Most metals are melted and then cast into semi-finished or finished shape.
Metals temperature remains constant while grains grow.
Some metals undergo allotropic transformation in solid state.
Solidification of a metal can be divided into the following steps:
Formation of a stable nucleus
Growth of a stable nucleus.

(a)Formation of stable nuclei (b) Growth of crystals

(c) Grain structure

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Solidification of Pure Metals

Figure: (a) Cooling curve for a pure metal
that has not been well inoculated. Liquid
cools as specific heat is removed
(betweens points A and B). Undercooling
is thus necessary (between points B and
C). As the nucleation begins (point C),
latent heat of fusion is released causing an
increase in the temperature of the liquid.
This process is known as recalescence
(point C to point D). Metal continues to
solidify at a constant temperature (T
melting). At point E, solidification is
complete. Solid casting continues to cool
from the point. (b) Cooling curve for a
well inoculated, but otherwise pure metal.
No undercooling is needed. Recalescence
is not observed. Solidification begins at
the melting temperature.
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Contd
UndercoolingThe temperature to which the liquid metal
must cool below the equilibrium freezing temperature
before nucleation occurs.
RecalescenceThe increase in temperature of an undercooled liquid metal as a result of the liberation of heat
during nucleation.
Thermal arrestA plateau on the cooling curve during the
solidification of a material caused by the evolution of the
latent heat of fusion during solidification.
Total solidification timeThe time required for the casting
to solidify completely after the casting has been poured.
Local solidification timeThe time required for a particular
location in a casting to solidify once nucleation has begun.
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Contd
Characteristic grain structure in a casting of a pure metal,
showing randomly oriented grains of small size near the
mold wall and large, columnar grains oriented toward the
center of the casting as shown in the figure below.

Figure: Grain structure of pure metal

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Solidification of Alloys
The alloys normally solidify in a temperature range.
For alloys, the solidification occurs over a temperature
range depending upon the composition. A typical
cooling curve for Ni-Cu system is given in Figure below

Fig1. A typical cooling curve for Ni-Cu system.

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Solidification of Alloys

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Polycrystalline Metals
Metals in most cases, solidification begins from multiple sites, each
of which can produce a different orientation.
The result is a poly-crystalline material consisting of many small
crystals of grains;
Each grain has the same crystal lattice, but the lattices are
misorientedfrom grain to grain.

Fig: Orientation of grain structures for polycrystalline metals

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Mechanism of Solidification
Pure metals solidifies at a constant temperature equal to
its freezing point, which same as its melting point.
The change form liquid to solid does not occur all at
once.
The process of solidification starts with nucleation, the
formation of stable solid particles within the liquid metal.
Nuclei of solid phase, generally a few hundred atom in
size, start appearing at a temperature below the freezing
temperature. The temperature around this goes down and
is called super-cooling or undercooling. In pure metals
super-cooling is around 20% of the freezing temp.
A nuclease, more than a certain critical size grows, and
causes solidification.
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Contd
By adding, certain foreign materials (nucleating agents)
the undercooling temperature is reduced which causes
enhanced nucleation.
In case of pure metals fine equi-axed grains are formed
near the wall of the mold and columnar grain growth
takes place up to the centre of the ingot.
In typical solid-solution alloy, the columnar grains do
not extend up to the center of casting but are interrupted
by an inner zone of equiaxed grains.
By adding typical nucleating agents like sodium,
magnesium or bismuth the inner zone of equiaxed
grained can be extended in whole casting.
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Crystal structure in Castings

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Solidification variables

Solidification behavior depends on parameters such as growth

rate, temperature gradient, under cooling and alloy constitution.
The temperature gradient (G) and growth rate (R) influence the
solidification morphology and solidification substructure
respectively.
Growth rate or solidification rate is the rate of advance of the
solid/liquid interface into the liquid.
The rate of movement of solidification front determines solute
redistribution during solidification, scale of solidification
substructure and the growth undercooling.
Rapid solidification (faster movement of solid/liquid interface)
minimizes the tendency of segregation of elements.
Undercooling is the difference between the liquid temperature of
the alloy of nominal composition and the actual temperature.
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Solidification Time
Once the material cools down to freezing temperature,
the solidification process for the pure metals does not
require a decrease in temperature and a plateau is
obtained in the cooling curves, called thermal arrest.
The solidification time is total time required for the
liquid metal to solidify.
Solidification time has been found to be directly
proportional to volume and inversely proportional to
surface area.

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Dendrite formation
If a protruding finger forms on the solidifying surface, its tip may reach the region of
constitutional under cooling. In this case the protuberance starts accelerated growth,
forming the main dendrite arms.
Under certain conditions the same process may occur on the surface of the main
dendrite arms, causing branching off the secondary arms and then arms of higher
orders.
In alloys, such as Fe-C, freezing and solidification occurs over a wide range of
temperature. There is no fine line of demarcation exists between the solid and liquid
metal.
Here, start of freezing implies that grain formation while progressing towards the
center does not solidify the metal completely but leaves behind the islands of liquid
metals in between grains which freeze later and there is multidirectional tree like
growth.

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Types of Cast Structures

Fig: Schematic illustration of the three basic types of cast structures : a)

columnar dendritic; b) equiaxed dendritic; and c) equiaxed nondendritic
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Directional solidification
"Directional solidification" is a metal casting term. It refers to the
process of controlled feeding of the molten metal into a temperaturecontrolled mold to produce a part that is free of hollow spots, called
shrink defects.
Directional solidification is also used to refine the metal during the
casting process because the impurities found in the molten metal will
continue to rise to the surface of the pool, following the path of least
resistance as they are pushed up by the solid materials below.
In the directional solidification process, the molten metal at the far end
of the mold begins to cool and solidify before the rest of the mold
does. As the metal on the bottom of the mold cools, this line of
solidification moves steadily upward toward the molten metal feed.
By controlling the rate of flow for the molten metal feed and
introducing thermal variations in the mold, shrink defects can be
eliminated, because the liquid metal will naturally run into these dips
and vacant areas.
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Directional solidification
Directional solidification is accomplished by removing all of the heat from one end of the
casting. This is done by establishing a strong thermal gradient and passing it from one end of
the casting to the other. In this way, large, columnar grains are produced that are oriented
such that they provide maximum strength in service;
Alloys developed for single-crystal casting are characterized by the absence of grainboundary strengthening elements such as carbon, boron, zirconium, and hafnium;
The removal of these alloying elements results in materials with very high incipient melting
temperatures.
Directional solidification is important for the quality of the casting (solidification proceeds
from the most remote section to the points of feeding). Directional solidification occurs:
1. Feeder heads (risers):
They serve as wells of liquid metal to compensate for shrinkage during solidification.
2. Chills:
They are heat-absorbing devices for fast freezing;
They are used to change progressive solidification to directional solidification;
Naturally, solidification is progressive from the wall of the mold towards the inner sections .
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Progressive solidification
The process of directional solidification is not to be confused with
progressive solidification, also called parallel solidification. Although
these processes share some similar traits, in progressive solidification, the
cooling and solidifying process begins at the walls of the casting and
works its way inward. With directional solidification, the process of
solidification begins at the bottom of the casting and works its way to the
top.
To control parallel solidification and encourage directional solidification
in the casting process, several techniques are employed.
Thermal variations are introduced into the mold by using risers or chills
to control hot or cold spots that might create problems with the cast part.
Insulated sleeves also are used to ensure a steady, controlled temperature
for the mold.
Finally, the rate of flow and temperature of the molten metal feed are
carefully controlled to ensure directional solidification.
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Contd
Most metals and alloys shrink as the material changes from a liquid state
to a solid state. Therefore, if liquid material is not available to
compensate for this shrinkage a shrinkage defect forms.
When progressive solidification dominates over directional solidification
a shrinkage defect will form.
In order to induce directional solidification chills, risers, insulating
sleeves, control of pouring rate, and pouring temperature can be utilized.

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