Lecture – 11

Solidification Basics

K. Devendranath Ramkumar
Assistant Professor (Sr.)
School of Mechanical & Building Sciences
Contents
 Homogeneous Nucleation
 Heterogeneous Nucleation
◦ Nucleation
◦ Grain Growth
Basics of Solidification
 Solidification of metal consists of two different
steps; nucleation and growth.
 Nucleation is the formation of stable solid
particles of certain size, called nuclei, within the
molten metal.
 These nuclei are the places where growth of the
metal crystals occurs.
 Growth is when nuclei grow into grains. Growth
includes the formation of a solid within the
molten metal.
 Critical radius is the minimum size of the solid
particle formed that is stable and grows further in
size.
Some terms
 Embryo – A tiny particle of solid that forms from the
liquid as the atoms cluster together. The embryo may
grow into a stable solid or may remelt .
 Nuclei – Matured Embryos for nucleation. Because
these atoms are large enough to be stable , nucleation
has occurred and growth of the stable solid can begin
Nucleation
 Refers to the nano-sized crystallites from the molten
metal
 Nucleation is the transformation phase
 We expect that a solidification occurs when the liquid
cools to just below its freezing temperature, because
the energy associated with the crystalline structure of
solid is then less than the energy of liquid
 This energy difference between the liquid and solid is
termed as “free energy per unit volume” and is the
driving force for solidification
 For the crystals to grow, these nuclei have to achieve a
size known as “critical radius”
Contd...
 The formation of embryo is a statistical process
 Many embryos form and re-dissolve. If by chance, any
embryo forms which has a radius greater than the
critical radius, further growth causes the free energy to
decrease
 The new solid is then stable and sustainable since nuclei
has occurred and the growth of solid particle – which is
now called as nucleus and begins to grow
 At the thermodynamic melting / freezing temperatures,
the probability of forming stable nuclei is extremely
small
Cont...
 Therefore the solidification does not begin at
thermodynamic melting / freezing temperature
 If the temperature continues to decrease below the
equilibrium freezing temperature, the liquid phase that
should have transformed into solid becomes
thermodynamically increasingly unstable
 Because the liquid is below the equilibrium freezing
temperature, the liquid is considered to be “under-
cooled”
 Under-cooling = Equilibrium freezing temperature –
actual temperature
 Homogeneous Nucleation
 Homogeneous solidification is when the solidification
starts within the liquid.
 As a result of homogeneous solidification, the structure is
very uniform throughout the solid
 If there is no solid substance/foreign substance present,
under-cooling of a hundred degrees is required in order
to form stable nuclei or “seeds” crystals, providing
following crystal growth (homogeneous nucleation)
 When a pure liquid metal is cooled below its freezing
temperature to a sufficient degree, many homogeneous
nuclei are created by slow moving atoms bonding
together
Homogeneous Nucleation
 formation of critically sized solid from the liquid
by the clustering together of a large number of
atoms at a high undercooling (without an
external surface) ;
 rarely occurs except under extreme laboratory
conditions
Heterogeneous Nucleation
 Heterogeneous solidification occurs at mold walls
and impurities.
 With heterogeneous solidification, the solid is not
uniform, instead having three distinct regions within
the solid.
 These regions are the chill zone, columnar zone, and
equiaxed zone.
 The chill zone is nearest to the mold wall and
contains a band of randomly oriented grains.
 The columnar zone consists of long columnar grains
that grow opposite to the direction of heat flow.
 The equiaxed zone is in the center of the mold and
has uniform equiaxed grains and controlled
nucleation.
Grain Structure
Summary of Nucleation
 It is the beginning of phase transformation;
 Nucleation may involve.
◦ Assembly of proper kinds of atoms by diffusion.
◦ Structural change into one or more unstable intermediate
structures.
◦ Formation of critical size particle (nuclei) of the new phase
(solid phase).
 Nucleation of super cooled grains is governed by two
factors.
◦ Free energy available from solidification process. This depends on the
volume of the particle formed.
◦ Energy required to form a liquid to solid inter phase. This depends on
the surface area of particle.
Grain Growth
 Grain growth may be defined as the increase
of nuclei in size.
 Grain growth follows nucleation; during this
phase - the nuclei grow by addition of atoms.
 The nuclei reduce the total free energy by
continuous growth.
 Number of stable nuclei per unit volume of
crystallizing alloy determines the grain size.
 When a large number of stable nuclei are
present in chill zone of mold, fine equiaxed
grains form.
Cont…
 There are two types of growth,
 Planar /equiaxed
 Dendritic
 Planar growth is growth under equilibrium
conditions.
 Dendritic growth is when the liquid is under-
cooled and does not properly nucleate
 Solidification can be broken down into
homogenous and heterogeneous.
Planar Growth

 Well innoculated (many

sites for heterogeneous
nucleation)
 Cooled under
equilibrium conditions
(very, very slowly)
 Thermal arrest on
cooling curve
Planar growth
• During solidification, the latent
heat of fusion is removed by
conduction from the solid –liquid
interface
• Well inoculated liquid cools
under equilibrium conditions
• No undercooling is required
• Temp of the liquid ahead of the
solidification front is greater than
the freezing temperature
• The temp. of the solid is at or
below the freezing temperature
 Dendritic growth

Niobium Carbide
melt

Cu – Sn Melt
Growth Mechanisms
Dendritic Growth
Dendritic Growth
 Poor nucleation
 Requires undercooling (recalescence part
of cooling curve)
 Dendritic growth continues until the
undercooled liquid is warmed to the
freezing temp, any remaining liquid
solidifies by planar growth.
Remarks
 Latent crystallization heat, liberating from
the crystallizing metal, decreases the
undercooling 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.
 Contrary to the pure metals, in alloys
different type of under-cooling takes place. It
is called constitutional undercooling.
Cont…
 Dendritic growth and
solidification:
(a) nucleation of crystals
in the melt
(b) growth of crystals
into dendrites
(c) complete
solidification
(d) final grain structure
Segregation
 Composition of solidified alloy is not uniform.
 Concentrations of impurities and alloying elements
are different in different parts of the casting.
 This difference is a result of different solubility of
impurities in liquid and solid phases at the equilibrium
temperature.
 Segregation is a result of separation of impurities
and alloying elements in different casting regions.
 Micro-segregation is a segregation of impurities
between the dendrite arms.
 This kind of segregation may be considerably
diminished by diffusion of the impurities atom into
the dendrite arms during homogenizing annealing.