Chapter 9

PRINCIPLES OF SOLIDIFICATION

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Chapter Learning Objectives

•Develop the expression for total free energy change during
solidification; calculate the critical radius for homogeneous
liquid-to-solid nucleation.
•Explain why liquids typically solidify via heterogeneous
nucleation.
•Describe factors that influence planar & dendritic modes of solid
growth from a liquid.
•Calculate solidification time for a casting from Chvorinov’s rule.
•Draw cooling curves for metals that are and are not well
inoculated.

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Chapter Learning Objectives

•Describe the structures and defects that occur in castings.
•Describe the most common casting processes used in
solidification.

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Technological Significance
•Solidification is one of the most important manufacturing processes
• Millions of kilograms of steel, aluminum alloys, etc. are produced via casting each
month.
•Solidification can be used in
• Primary processing to make ingots, slabs, etc.
• Secondary processing to make specific shapes (wires, plates, etc.)
•Solidification is also used in processing glass-ceramics and thermo-plastics.

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Nucleation
•In solidification, nucleation is the formation of the first nanocrystallites from
molten material.
• Nucleation can occur in solid materials as well, and is a general phase change phenomenon.

•The driving force for solidification is the free energy per unit volume

4 3
G   r Gv  4 r 2 sl
3

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Nucleation

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Nucleation
•Homogenous nucleation occurs when undercooling (cooling below melting temp.) is large
enough to allow formation of stable nuclei.
• The critical radius for a stable nucleus is
* 2 slTm
r 
H f T
• Homogenous nucleation almost never occurs in liquids

•Heterogeneous nucleation, requiring less undercooling, is the typical route, and it occurs on pre-
existing surfaces such as impurities/container walls.

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Nucleation
•The rate of nucleation is a function of temperature.
• There is an optimum rate where the temperature is low enough to maximize nucleation
driving force, but high enough to not inhibit diffusion.
• In heterogeneous nucleation, the rate is also a function of concentration of nucleating
species.

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Example problem #1

• Calculate the size of the critical radius and the number of atoms in the critical
nucleus when solid cooper forms by homogeneous nucleation. Comment on
the size of the nucleus and assumptions we made while driving the equation
for the radius of the nucleus.

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Applications of Controlled Nucleation

•Grain Size Strengthening:
• Smaller grain size, which strengthens materials, can be achieved by introducing
impurities/inoculants in a material to promote heterogeneous nucleation.

•Second-Phase Strengthening: Materials can also be strengthened by

heterogeneously nucleating ultra-fine precipitates of a second phase in a
parent phase. More detail in Chapter 11.

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Applications of Controlled Nucleation

•Glasses:
• In rapidly cooled/high viscosity melts, insufficient time for nucleation locks the
liquid structure in place, forming solid glasses.
• Colored/photochromic glass is formed by nucleating small nanocrystallites of
different materials in otherwise amorphous material.

•Glass-ceramics:
• These materials begin as amorphous glasses and end up as crystalline materials
with a super-fine grain size. This is accomplished by introducing nucleating agents
and controlled heating.

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Growth Mechanisms
•The manner of the growth of solid nuclei depends on how heat is removed
• During solidification, 2 types of heat must be removed: latent heat of fusion and
specific heat of the liquid

•Planar Growth:
• In a well-inoculated liquid at equilibrium, heterogeneous nucleation can occur
• Solidification occur via planar growth in this case: the material solidifies layer by
layer in front of a solidification front, which removes heat from the liquid-solid
interface via conduction

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Growth Mechanisms
•Dendritic Growth:
• In poorly inoculated liquids, the liquid has to be undercooled for solidification
• A small solid protuberance/dendrite at the interface is encouraged to grow since
the liquid ahead of the solidification front is undercooled.
• Dendritic growth proceeds until the liquid is not undercooled any more, after
which planar growth takes over
• Dendritic growth normally represents only a small fraction of the total growth in
pure metals.

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Growth Mechanisms

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Growth mechanisms

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Solidification Time & Dendrite Size

•Growth rate of a solid depends on the cooling rate.
• Chvorinov’s rule can estimate the time for a simple casting to solidify completely

ts B V / A 
n

•Effect on Structure & Properties:

• Solidification time affects dendrite size, in particular secondary dendrite arm
spacing (SDAS), which can be reduced when the casting freezes more rapidly
• Reduced SDAS can result in improved properties such as tensile strength and
ductility

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Dendrite size
𝑆𝐷𝐴𝑆 =𝑘𝑡 𝑚
𝑠

Where m and k are constants

depending on the composition
of the metal

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Cooling Curves

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Example problem #2
• Design a thickness of an aluminum alloy casting with a length of 12 in., a width of 8 in. and a tensile
strength of 42,000 psi. The mold constant in Chvorinov’s rule for aluminum alloys cast in a sand mold is
45 min/in2.

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Cast Structure
•A casting is the finished shape of a molten metal which has been cooled in a
mold.
• Sometimes the mold produced a simpler shape called an ingot.
• Castings have a large-scale structure consisting of 3 parts

•Chill Zone:
• It 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 and provides many nucleation sites.

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Cast Structure
•Columnar Zone:
• This zone contains elongated grains oriented in a particular crystallographic
direction, because grains grow fastest in certain directions
• Columnar zone grains often grow perpendicularly from the casting wall, and
result in anisotropic properties in the columnar region
• Formation of this zone is influenced more by growth than nucleation
phenomena.

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Cast Structure
•Equiaxed Zone:
• The solid may continue to grow in a columnar fashion until solidification is complete.
• However, frequently an equiaxed zone forms in the center of the casting
• This zone contains rounded, randomly oriented grains, which result in isotropic
properties
• The formation of the equiaxed zone is a nucleation-controlled process

•By understanding the factors that result in the formation of each type of zone,
we can develop casting process in which preferred zones/grain types dominate.

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Cast Structure

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Cast structure

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Solidification Defect
•Shrinkage:
• Since metals are more dense than liquids, shrinkage occurs upon cooling.
• Cavities form if solidification begins at all surfaces of the casting, and pipes if one
surface solidifies slower than others.
• Risers can be used to control shrinkage. A riser is an extra reservoir of liquid
metal that flows in as pipes or cavities are forming, thus filling the void.

•Interdendritic Shrinkage:
• This consists of small shrinkage pores between dendrites. It is difficult to prevent
with risers, but fast cooling rates can reduce this problem.

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Solidification Defects
•Gas Porosity:
• Metals often dissolve a large quantity of gas in their molten states
• Upon solidification, this excess gas forms bubbles in the solid metal, producing
gas porosity
• We can reduce gas porosity by many methods, such as:
• reducing partial pressure of gas
• reducing casting temperature
• flushing with an inert gas
• using additives which react with the gas to produce solids

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Solidification defects

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Solidification Defects

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Example problem #3

• Design a cylindrical riser, with a height equal to twice the diameter, that will compensate the shrinkage
in 2 cm x 8 cm x 16 cm casting.

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Casting Processes for Manufacturing Components

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Casting Processes for Manufacturing Components

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Casting Processes for Manufacturing Components

Die casting machines – YouTube
Investment Casting Process - Lost Wax Casting – YouTube
Investment Casting Process - YouTube

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Continuous Casting & Ingot Casting

•In ingot casting, molten steels or alloys are cast into large molds.
• The resultant ingots are then processed for conversion into useful shapes via
thermomechanical processing

•In continuous casting, we go from molten metal to a semi-finished shape

such as a slab, plate, etc.
• It is cost effective for many steels, stainless steels and aluminum alloys
• Ingot casting is also cost effective, especially for smaller batches
• Not all alloys can be cast using continuous casting

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Extraction and production of steel

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Continuous Casting & Ingot Casting

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Secondary processing in steel

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How steel is produced - YouTube

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Directional Solidification, Single Crystal Growth

& Epitaxial Growth
•Directional Solidification [DS]:
• In the DS process, better creep and fracture resistance are obtained, e.g., for turbines,
etc.
• The mold is heated from one end and cooled from the other, resulting in a columnar
microstructure with all grain boundaries aligned along an axis.

•Single Crystal Growth:

• Polycrystalline materials are not effective for electronic/optical use due to presence of
grain boundaries
• Single crystal growth (e.g., silicon for semiconductors) is obtained by using a small seed
crystal with preferred crystallographic direction and carefully controlling heat transfer in
the furnace

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Directional Solidification, Single Crystal Growth

& Epitaxial Growth
•Epitaxial Growth:
• Epitaxy is the process by which one material is made to grow in an oriented
fashion using a substrate with matching crystallographic direction
• Epitaxial growth is the growth of highly oriented or single crystal thin films on a
substrate
• There are numerous processes for thin film deposition

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Directional Solidification, Single Crystal Growth

& Epitaxial Growth

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Solidification of Polymers & Inorganic

Glasses
•Polymers:
• Many polymers do not crystallize during solidification due to slow nucleation and
the complexity of aligning long chains
• When polymers do crystallize, they do so as lamellar or plate-like crystals
• Bundles of lamellae grow from a common nucleus, producing a spheroidal shape
called a spherulite
• Amorphous regions are present between lamalle, bundles and spherulites
• In general, polymers such as PET, nylon and polyethylene crystallize easier than
other thermoplastics
• Crystallization may result from cooling or stress

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Solidification of Polymers & Inorganic

Glasses
•Inorganic Glasses:
• Also do not crystallize easily for kinetic reasons
• The melt is often too viscous and diffusion too slow for crystallization to occur
during solidification
• Most glasses are strengthened instead by tempering.

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Joining of metallic Materials

•In brazing, an alloy (‘filler’) is used to join two pieces of metal together
• Soldering is a brazing process
• In brazing, only the filler melts, not the metallic materials being joined

•Fusion welding for joining metals is also an important application of solidification

• A portion of the metals to be joined is melted, and a filler may be added
• During solidification of the fusion region, nucleation is not required and columnar
grains grow
• Structure & properties of the fusion zone depend on many of the same variables as
in a metal casting

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Joining of Metallic Materials

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Summary
•Transformation of a liquid to a solid is probably the most important phase change in
MSE applications.

•Solidification has a critical role in the processing of metals, alloys, thermoplastics &
inorganic glasses. It is also important in techniques for joining metallic materials.

•Nucleation produces a critical-size solid particle from the liquid melt.

•Nuclei formation is determined by the thermodynamic driving force for solidification.

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Summary
•Nuclei formation is opposed by the need to create a solid-liquid interface. As a
result, solidification may not occur at the freezing temperature.

•Homogenous nucleation requires large undercoolings of the liquid and isn’t

observed in normal solidification processing.

•Foreign particles introduced in the liquid (via inoculation or grain refining)

provide nuclei for heterogeneous nucleation. The process permits the grain size
of casting to be controlled.

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Summary
•Rapid cooling of the liquid can prevent nucleation & growth, producing
amorphous solids (glasses) with unusual mechanical & physical properties.

•Polymeric, metallic & inorganic materials can be made in the form of glasses.

•In solidification from melts, nuclei grow into the liquid melt. Either planar or
dendritic growth may take place.

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Summary
•In planar growth, a smooth solid-liquid interface grows with minimal
undercooling of the liquid. Special directional solidification processes take
advantage of planar growth.

•Dendritic growth occurs when the liquid is undercooled. Rapid cooling produces
a finer dendritic structure and leads to improved mechanical properties of a
metallic casting.

•To estimate the solidification time of a casting,

n we use Chvorinov’s Rule
ts B V / A 

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Summary
•Cooling curves indicate pouring temperature, any undercooling and recalescence &
solidification time.

•By controlling nucleation & growth, a casting may be given columnar grain structure,
equiaxed grain structure, or a mixture of both.

•Isotropic behavior is typical of equiaxed grains, while columnar grains show anisotropic
behavior.

•Porosity & cavity shrinkage are major defects which may be present in cast products, causing
catastrophic failure.

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Summary
•In commercial solidification processing methods, casting defects can be
controlled by proper design of casting & riser system, or by appropriate prior
treatment of liquid metal.

•Sand casting, investment casting & pressure die casting are some processes for
casting components.

•Ingot casting and continuous casting are employed in the production and
recycling of metals and alloys.

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Summary
•The solidification process can be carefully controlled to produce directionally
solidified materials as well as single crystals.

•Epitaxial processes make use of crystal structure matching between the

substrate and the material being grown, and are useful for making electronic &
other devices.

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