The solidification of metallic, polymeric, and ceramic materials is an important

process to study because of its effect on the properties of the materials involved.

The solidification of crystalline materials requires two steps.

In the first step, ultra-fine crystallites, known as the nuclei of a
solid phase, form from the liquid. In the second step, which can overlap with the first,
the ultra-fine solid crystallites begin to grow as atoms from the liquid are attached to
the nuclei until no liquid remains.
Thousands of years later meltIng of a metal founded, solidification is still considered
one of the most important manufacturing processes.

Industry also uses the solidification process as a primary processing step to produce metallic
slabs or ingots (a simple, and often large casting that later is processed into useful shapes).

The ingots or slabs are then hot and cold worked through secondary processing steps into more
useful shapes (i.e., sheets, wires, rods, plates, etc.).

Solidification also is observed when joining metallic materials using techniques such
as welding, brazing, and soldering.
In the context of solidification, the term nucleation refers to the formation of the first
Small (nano) crystallites from molten material. For example, as water begins to freeze,
nanocrystals, known as nuclei, form first. (But first embryo forms with aggregation of two atoms)

We expect a material to solidify when the liquid cools to just below its freezing
(or melting) temperature, because the energy associated with the crystalline structure of
the solid is then less than the energy of the liquid. This energy difference between the
liquid and the solid is the free energy per unit volume ∆Gv and is the driving force for
solidification.
When the solid forms, however, a solid-liquid interface is created.

A surface free energy 𝜎𝜎sl is associated with this interface.

Thus, the total change in energy ∆G is:

An embryo is a tiny particle of solid that forms from the liquid as

atoms cluster together. The embryo is unstable and may either grow
into a stable nucleus or redissolve.
When the solId Is very small wIth a radius less
than the critical radius
for nucleation (r*) (Figure), further
growth causes the total free energy to increase.

The critical radius (r*) is the minimum

size of a crystal that must be formed by atoms
clustering together in the liquid before the
solid particle is stable and begins to grow.
 NucleatIon CrIstal Growth GraIn boundarIes

b
The undercooling (∆T) is the difference between the equilibrium freezing
Te
temperature and the actual temperature of the liquid. As the extent of ∆T
undercooling increases, the thermodynamic driving force for the formation a
of a solid phase from the liquid overtakes the resistance to create a
solid-liquid interface.
Homogeneous nucleatIon occurs when the
undercoolIng becomes large enough to
cause the formation of a stable nucleus; and
can be achieved only in lab conditions.

The size of the critical radius r* for

homogeneous nucleation is given by:
Except in controlled laboratory experiments, homogeneous nucleation never occurs in liquids.
Instead, impurities in contact with the liquid, either suspended in the liquid or on the walls of the
container that holds the liquid, provide a surface on which the solid can form.

Nucleation on preexisting surfaces is known as heterogeneous nucleation. This process is

dependent on the contact angle (θ) for the nucleating phase and the surface on which nucleation
occurs.
Surfaces affecting as nucleus in heterogeneous nucleation:
• Die or mold walls
• Carbites, nitrides, oxides and other alloying elements
(intermetalic compounds etc.)
• Same or different nucleus additions (inoculation etc.)
(ex: %0.1 Na addition to Al-Si alloy)
The rate of nucleation (the number of nuclei formed per unit time) is a function of temperature.

As the temperature drops, the driving force for nucleation increases; however, as the
temperature decreases, atomic diffusion becomes slower, hence slowing the nucleation process.

Cooling Rate Grain size Number of Grains Strength

Fine grains
Coarse grains

What If thIs materIal works on hIgh-temperature envIronment?

Grain Size Strengthening: When a metal casting freezes, impurities in
the melt and the walls of the mold in which solidification occurs serve as heterogeneous
nucleation sites. Sometimes we intentionally introduce nucleating particles into the liquid.
Such practices are called grain refinement or inoculation.
The greater grain boundary area provides grain size strengthening
in metallic materials. The Hall-Petch equation

Second-Phase Strengthening: Strengthening materials using ultra-fine

precipitates is known as dispersion strengthening or second-phase strengthening; it is used
extensively in enhancing the mechanical properties of many alloys. This process involves
solid-state phase transformations.
Once the solid nuclei of a phase form (in a liquid or another solid phase), growth begins
to occur as more atoms become attached to the solid surface.

In the solidification process, two types of heat must be removed:

• the specific heat of the liquid and
• the latent heat of fusion.

The specific heat is the heat required to change the temperature of a unit weight of the
material by one degree.
When solid crystals form from a liquid, heat is generated. This type of heat is called the latent heat of
fusion (∆Hf).
The latent heat of fusion must be removed from the solid-liquid interface before solidification is
completed.
During solidification, the latent heat of fusion is removed by conduction from the solid liquid
interface. Any small protuberance that begins to grow on the interface is surrounded by liquid
above the freezing temperature.

The growth of the protuberance then stops until

the remainder of the interface catches up.

This growth mechanism, known as planar growth,

occurs by the movement of a smooth
solid-liquid interface into the liquid.
When the liquid is not inoculated and the nucleation is
poor, the liquid has to be undercooled before the solid
forms.

Under these conditions, a small solid protuberance called a

dendrite, which forms at the interface, is encouraged to
grow since the liquid ahead of the solidification front is
undercooled.

In pure metals, dendritic growth normally represents only a

small fraction of the total growth and is given by:

where c is the specific heat of the liquid.

The rate at which growth of the solid occurs depends on the cooling rate, or the rate of
heat extraction. A higher cooling rate produces rapid solidification, or short solidification
times. The time ts required for a simple casting to solidify completely can be calculated
using Chvorinov’s rule:

SolidIfication Modulus (M)

where Vis the volume of the casting and represents the amount of heat that must be removed
before freezing occurs, A is the surface area of the casting in contact with the mold and represents
the surface from which heat can be transferred away from the casting, n is a constant
(usually about 2), and B is the mold constant.

ts ↓ vs ↑ Grain Size ↓
The slope of the cooling curve before solidification begins is the cooling rate
As nucleation begins (point C), latent heat of fusion is given off, and the temperature rises; known
as recalescence (point C to D).
Solidification proceeds isothermally at the melting temperature (point D to E): thermal arrest.
The mold produces a finished shape, known as a casting.
In other cases, the mold produces a simple shape called an ingot.

Chill Zone: The chill zone is a narrow band of randomly oriented

grains at the surface of the casting. The metal at the mold wall is the
first to cool to the freezing temperature.
Columnar Zone The columnar zone contains elongated grains
oriented in a particular crystallographic direction.
Equiaxed Zone The equiaxed zone contains new, randomly
oriented grains, often caused by a low pouring temperature,
alloying elements, or grain refining or inoculating agents.
These grains grow as relatively round, or equiaxed, grains with a random orientation, and they stop
the growth of the display. This zone displays isotropic behavior.
Shrinkage: Almost all materials are more dense in the solid state than in the liquid
state. During solidification, the material contracts, or shrinks. Often, the bulk of the shrinkage
occurs as cavities, if solidification begins at all surfaces of the casting, or pipes, if one surface
solidifies more slowly than the others.

A common technique for controlling cavity and pipe shrinkage is to place a riser,
or an extra reservoir of metal, adjacent and connected to the casting.

SolIdIfIcatIon modulus
should be calculated for
each part of the castIng.
PourIng basIn and rIsers
should be added to
the parts that own
hIgh modulus.
Interdendritic Shrinkage: This consists of small shrinkage pores between dendrites.
This defect, also called microshrinkage or shrinkage porosity, is difficult to prevent by the use
of risers. Fast cooling rates may reduce problems with interdendritic shrinkage; the dendrites
may be shorter, permitting liquid to flow through the dendritic network to the solidifying solid
interface.
Gas PorosIty: Many metals dIssolve a large quantity of gas when they are molten. The excess gas that
Cannot be incorporated in the solid metal or alloy crystal structure forms bubbles that may be trapped
in the solid metal, producing gas porosity. The amount of gas that can be dissolved in molten metal is
given by Sievert’s law:

where pgas is the partial pressure of the gas in contact with the metal and K is
a constant which, for a particular metal-gas system, increases with increasing
temperature.
We can minimize gas porosity in castings by keeping the liquid temperature
low, by adding materials to the liquid to combine with the gas and form a solid,
or by ensuring that the partial pressure of the gas remains low.
Gas flushing is also a process in which bubbles of a gas, inert or reactive, are
injected into a molten metal to remove undesirable elements from molten metals andalloys.
Crystal growth furnaces containing molten materials must be maintained at a precise
and stable temperature. Often, a small crystal of a predetermined crystallographic orientation
is used as a “seed.” Heat transfer is controlled so that the entire melt crystallizes
into a single crystal. Typically, single crystals offer considerably improved, controllable, and
predictable properties at a higher cost than polycrystalline materials.
Epitaxy is the process by which one material is made to grow in an oriented fashion using a substrate
that is crystallographically matched with the material being grown. If the lattice matching between the
Substrate and the film is good (within a few %), it is possible to grow highly oriented or single crystal
thin films. This is known as epitaxial growth.

The Molecular Beam Epitaxy System