Principles of Solidification

Solidification

plays a critical role in the process of metals, alloys,

thermoplastics, and inorganic glasses. Solidification is also important in techniques
used for joining metallic materials.

Uses of Solidification Process in Industry:

as a primary processing step:

To produce metallic slabs or ingots (processed into useful shapes)

as a secondary processing step:

The ingots or slabs are then hot and cold worked (ex. Sheets, wires, rods, plates, etc.)


Nucleation

Produces

a critical-size solid particle from the liquid melt. Formation of nuclei is determined by the thermodynamics
driving force for solidification and is opposed by the need to create the solid-liquid interface. As a result, solidification
may not occur at the freezing temperature.

When the solid forms, however, a solid-liquid interface is created (Figure 9-1(a)). A surface free energy sl is associated
with this interface. Thus, the total change in energy G, shown in Figure 9-1(b), is

where
is the volume of a spherical solid of radius r, 4r2 is the surface area of a spherical solid, sl is the surface free
energy of the solid-liquid interface (in this case), and Gv is the free energy change per unit volume, which is negative
since the phase transformation is assumed to be thermodynamically feasible.

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.

Homogeneous Nucleation

occurs when the undercooling becomes large enough to cause the formation of a stable nucleus.

The size of the critical radius r* for homogeneous nucleation is given by:

where Hf is the latent heat of fusion per unit volume, Tm is the equilibrium solidification temperature in kelvin,
and T = (Tm - T) is the undercooling when the liquid temperature is T. Table 9-1 presents values for sl, Hf, and typical
undercoolings observed experimentally for homogeneous nucleation.

Heterogeneous Nucleation
This

process is dependent on the contact angle () for the nucleating phase and
the surface on which nucleation occurs. The same type of phenomenon occurs in
solid-state transformations.

Rate of Nucleation
The

number of nuclei formed per unit time.

Function

of temperature.

Applications of Controlled Nucleation

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. Such practices are called grain refinement or inoculation. Chemicals added to molten
metals to promote nucleation and, hence, a finer grain size, are known as

grain refiners

or inoculants.

Second-Phase Strengthening
In metallic materials, dislocation motion can be resisted by grain boundaries or the formation of ultra-fine precipitates of a
second phase. 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.
Glass
Alloys with special compositions have sufficiently complex crystal structures and form amorphous materials if cooled rapidly
from the melt. These materials are known as metallic glasses. Metallic glasses were initially produced via rapid solidification
processing in which cooling rates of 106C-1 were attained by forming continuous, thin metallic ribbons about 0.0015 in. thick.

Glass-ceramics
The term glass-ceramics refers to engineered materials that begin as amorphous glasses and end up as crystalline ceramics
with an ultra-fine grain size.

Growth Mechanisms

Two types of heat to be removed in the solidification process:

Specific heat of the liquid - the heat required to change the temperature of a unit weight of the material by one degree.

removed by either radiation into the surrounding atmosphere or by conduction into the surrounding mold,
until the liquid cools to its freezing temperature.

Latent heat of fusion - when solid crystals form from a liquid.

removed from the solid-liquid interface before solidification is completed.

Planar Growth
The growth of the smooth solid-liquid interface during solidification when no undercooling of the liquid is present.

Dendritic Growth (Greek word, dendron, means tree)

When the liquid is not inoculated and the nucleation is poor, the liquid has to be undercooled before the solid forms (Figure 9-4).
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 numerator represents the heat that the undercooled liquid can absorb, and the
latent heat in the denominator represents the total heat that must be given up during solidification. As the undercooling T
increases, more dendritic growth occurs. If the liquid is well-inoculated, undercooling is almost zero and growth would be mainly via
the planar front solidification mechanism.

Solidification Time and Dendrite Size

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 Chvorinovs rule:

where V is 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 and B is the mold constant.

Example:

Solidification begins at the surface, where heat is dissipated into the surrounding mold material. The rate of
solidification of a casting can be described by how rapidly the thickness d of the solidified skin grows:
d = ksolidification t - c1
where t is the time after pouring, ksolidification is a constant for a given casting material and mold, and c1 is a
constant related to the pouring temperature.

Effect on Structure and Properties

The secondary dendrite arm spacing (SDAS) is reduced when the casting freezes more rapidly. The finer, more extensive
dendritic network serves as a more efficient conductor of the latent heat to the undercooled liquid. The SDAS is related to the
solidification time by

SDAS = ktsm
where m and k are constants depending on the composition of the metal. This relationship is shown in Figure 9-6 for several
alloys. Small secondary dendrite arm spacings are associated with higher strengths and improved ductility (Figure 9-7).

Example:

Example:

Example:

Cooling Curves
Indicate the pouring temperature, any undercooling and recalescence and time for solidification.

Recalescence

Local Solidification Time

The increase in temperature of an undercooled liquid metal as a result of the liberation of heat during nucleation.

The time required for a particular location in a casting to solidify one nucleation has begun.

Thermal Rest

A thermal rest or plateau is produced because the evolution of the latent heat of fusion balances the heat being lost
because of cooling.

Total Solidification Time

is the time required to remove both the specific heat of the liquid and the latent heat of fusion

Cast Structure

In manufacturing components by casting, molten metals are often poured into molds and permitted to solidify. The mold
produces a finished shape, known as a casting. In other cases, the mold produces a simple shape called an ingot (a simple
casting that is usually remelted or reprocessed by another user to produce a more useful shape).

Macrostructure (or Ingot Structure)

Three regions:

Chill Zone a region of small, randomly oriented grains that forms at the surface of a casting as a result of
heterogeneous
nucleation.

Columnar Zone a region of elongated grains having a preferred orientation that forms as a result of competitive growth
during the solidification of a casting.

Equiaxed Zone a region of randomly oriented grains in the center of a casting produced as a result of widespread nucleation.

Solidification Defects

Shrinkage - contraction of a casting during solidification.

The bulk of the shrinkage occurs as cavities(small holes present in a casting), if solidification begins at all surfaces of the
casting, or pipes, if one surface solidifies more slowly than the others (Figure 9-11).

Pipe Shrinkage a large conical-shaped void at the surface of a casting caused by the volume contraction that occurs during
solidification.
Riser a technique used to control cavity and pipe shrinkage, an extra reservoir of liquid metal connected to a casting. If the riser
freezes after the casting, the riser can provide liquid metal to compensate for shrinkage.

Interdendritic Shrinkage small pores between the dendrite arms formed by the shrinkage that accompanies
solidification. Also known as microshrinkage or shrinkage porosity.

Gas Porosity bubbles of gas trapped within a casting during a solidification caused by the lower solubility of the gas in the
solid compared with that in the liquid.
The amount of gas that can be dissolved in molten metal is given by Sieverts 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.
Gas flushing a process in which a stream of gas is injected into a molten metal in order to eliminate a dissolved gas that
might produced porosity.
AOD(Argon Oxygen Decarburization) a process to refine stainless steel. The carbon dissolved in molten stainless steel is
reduced by blowing argon gas mixed with oxygen.

Casting Processes for Manufacturing Components

Sand Casting a casting process using sand molds.

Investment Casting a casting process that is used for making complex shapes such as turbine blades, also known as a lost
wax process(a process in which a wax pattern is used to cast a metal).

Lost Foam Process a process in which a polymer foam is used as a pattern to produce a casting.

Continuous Casting and Ingot Casting

Ingot Casting
Solidification of molten metal in a mold of simple shape. The metal then requires extensive plastic deformation to
create a finished product.

Continuous Casting
A process to convert a molten metal or an alloy into a semi-finished product such as a slab.

Directional Solidification(DS), Single Crystal Growth

and Epitaxial Growth

Directional Solidification(DS) a solidification technique in which cooling in a given direction leads to preferential growth
the
grain

of grains in the opposite direction, leading to an anisotropic and an oriented microstructure. In the DS process,
mold is heated from one end and cooled from the other, producing a columnar microstructure with all of the
boundaries running in the longitudinal direction of the part.

Single Crystal Growth one of the most important applications of solidification. Polycrystalline materials cannot be used
effectively in many electronic and optical applications. Grain boundaries and other defects interfere
with the mechanisms that provide useful electrical or optical functions.
- The Bridgman and Czochralski processes are some of the popular methods used for growing single
crystals of silicon, GaAs, lithium niobate (LiNbO3), and many other materials.

Epitaxial Growth growth of a single-crystal thin film on a crystallographically matched single-crystal substance. 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.

Solidification of Polymers and Inorganic Glasses

Crystallization in polymers is almost never complete and is significantly different from that of metallic materials, requiring
long polymer chains to become closely aligned over relatively large distances. By doing so, the polymer grows as lamellar, or
plate-like, crystals (Figure 9-22). The region between each lamella contains polymer chains arranged in an amorphous
manner. In addition, bundles of lamellae grow from a common nucleus, but the crystallographic orientation of the lamellae
within any one bundle is different from that in another. As the bundles grow, they may produce a spheroidal shape called a
spherulite. The spherulite is composed of many individual bundles of differently oriented lamellae. Amorphous regions are
present between the individual lamellae, bundles of lamellae, and individual spherulites.

Joining of Metallic Materials

Brazing an alloy, known as a filter, is used to join two materials to one another. The composition of the filter, which
has a melting temperature above 450C.

Soldering a joining process in which the filler has a melting temperature below 450C; no melting of the base
materials occurs.

Fusion Welding joining process in which a portion of the materials must melt in order to achieve god bonding.
Fusion Zone the portion of a weld heated to produce all liquid during welding process. Solidification of the fusion zone
provides joining.