Foundry Technology

Unit 2: Mold making

 Unit 2: Mold making
Syllabus
Mold making - Green sand moulding, dry sand
moulding, molding sands, Properties of foundry sands
and their testing, additives, Sand Control, core sands,
mould compaction machines, Jolt, Jolt-squeeze, high
pressure molding, sand slinger, refractory coatings,
Venting, molding boxes, chills,roll of additives &
technical terms in sand like total clay, active clay, latent
clay, dead clay
Stages in Mould Production
 Molding Sand
• The major production of castings is in sand molds.
• Typically molds for making a ton of castings may require 4
to 5 tons of molding sand.
• Sand is the principal molding material in the foundry shop
where it is used for all types of castings, irrespective of
whether the cast material is ferrous or non-ferrous, iron or
steel. This is because it possesses the properties vital for
foundry purposes.
• Sand is defined as granular particles resulting from
disintegration or crushing of rocks principally by the action
s of frost and rain.
• The sand
Molding Sand
may reside at its place of origin (angular shaped, wide size
distribution) or distributed by the action of wind and water (round
shaped , less wide size distribution)
• The grain size, shape and distribution is function of the history of the
sand.
• The most commonly used sand in the foundry is silica sand, produced
by the decomposition of granite.
• However, there are other sands, such as zircon, olivine which are used
as substitute for silica.
• The term sand is used in its generic sense although unless otherwise
stated, it can be assumed that the use of the word sand implies silica
sand.
• Several different types of sand are used for molding. Sand-casting
processes involving molds made of green sand, dry sand, core sand,
cement-bonded sand, shell-molding sand etc.
 Molding Sand
Why sand for molding?
• Sand possesses the properties vital for foundry purposes.
• The most important characteristic of sand is its refractory
nature due to which it can be easily withstand the high
temperature of molten metal and does not get fused.
• Molding sand has chemical resistivity. It does not chemically
react or combine with molten metal and can therefore be
used time and again
• Sand has a high degree of permeability; it allows gases and
air to escapes from mold when molten metal is poured
without interfering with the rigidity and strength of the mold.
• The degree of strength, hardness, the permeability can also be
adjusted, as desired, by varying the composition or the
ingredients of the sand. Such a flexibility is extremely difficult
to achieve with any other molding material.
 The properties and Characteristics of
Molding Sand
1. Refractoriness:
Refractoriness means ability of the sand to withstand the
pouring temperature of the metal without melting. The higher
the melting point, the better will be the refractoriness of the
sand. Pure silica melts at 1710oC. However, presence of
impurities impairs refractoriness. This is particular problem in
natural molding sands which contain materials which melts at
temperatures as low as 1350oC.
 The properties and Characteristics of
Molding Sand
2. Permeability:
It refers to the ease with which gases can permeate
through a bonded sand mould. This property is extremely
important when a mold is cast in air. When the metal enters
the mould cavity it must displace the air in order to replace it
and replicate the mold shape. Some of the air may be
displaced through open feeders but the bulk will be displaced
through the sand. Large sand grains have large pores between
them through which air and any other gases, such as those
generated by binder decomposition or water conversion to
steam, can readily permeate. On the other hand, small grains
have small pores which create a more difficult and tortuous
route through which the gas must pass. To provide high
permeability, therefore, a large grain size would be chosen,
but this would be at the expense of poor surface finish.
 The properties and Characteristics of
Molding Sand
2. Permeability:
 The properties and Characteristics of
Molding Sand
3. Expansion:
Most materials expand when heated and contract when
cooled. Silica sands are no exception to this rule. However,
silica undergoes a series of polymorphic changes as it is
heated and cooled. At room temperature silica exists as
quartz with alpha crystal structure. As α quartz is heated
it expands in a regular but comparatively high manner
until it reaches a temperature of 573oC. At this
temperature there is a change from α to β quartz which is
accompanied by a volumetric expansion. This can be the
cause of expansion-related defects such as scabs etc but
more importantly, is a major source of dimensional
variation in silica sand molded casting
 The properties and Characteristics of
Molding Sand
3. Expansion:
 The properties and Characteristics of
Molding Sand
3. Expansion:
Other mold materials expand at a lower and more
predictable rate and are therefore less susceptible to
expansion defects and more likely to produce castings with
improved dimensional consistency.

4. Strength
Sand by itself has no bonding characteristics, although
when vibrated to consolidate it, a sand mass can be quite
rigid. In general, however, a binder is used to provide
strength in the sand mould. Grain size, shape and
distribution and to a much smaller extent grain surface
influence the strength of the mold in several ways.
 The properties and Characteristics of
Molding Sand
4. Strength
For given amount of binder a sand consisting of large
grain would provide higher strength than a sand consisting
of small grains, because the larger grains would present a
smaller surface area and would therefore have a thicker
coating binder. To achieve the same strength the finer sand,
with the larger surface area, would require a higher binder
addition, that is, it would have a higher binder demand.
For a sand grain in which there is a distribution of sand
grain sizes such that smaller grains infill the voids between
larger grains, and still smaller grains infill the remaining
voids, a still higher strength would be obtained with the
given amount of binder.
 The properties and Characteristics of
Molding Sand
4. Strength
This occurs despite the fact that there is clearly an
increase in surface area to be coated by the binder. The
increase in strength is explained by the increase in the
number of points of contact between grains coated by the
binder.
The properties and Characteristics of
Molding Sand
 The properties and Characteristics of
Molding Sand
4. Strength
Grain shape influences strength in two ways. Firstly, in
relation to the way that the binder coats the grains and
how the individual grains contact one another. For
example, rounded grains have an even coating of binder
and present good contact area to their neighbours, but
angular grains have uneven coatings and poor areas of
contact.

Secondly, to achieve optimum strength, molding sands

must be compacted in some way to maximize their density
and improve the strength at the point of contact.
Consequently, the sand should flow readily and this is a
function of shape in that rounded grains flow more readily
than angular grains which tend to interlock .
 The properties and Characteristics of
Molding Sand

4. Strength
The influence of the grain surface is small by
comparison with the preceding factors, but it is likely that
grains with a very smooth surface do not provide as good a
surface for the binder to key to as a grain with roughened
surface.
 The properties and Characteristics of
Molding Sand
5. Surface Finish
• Sand grain size
• Grain size distribution
• Refractoriness
• Pouring Temperature
• Velocity of molten metal
 The properties and Characteristics of
Molding Sand
Sand Testing
1. Clay Content Test:
1. Total Clay Content
2. Active Clay Content :
Methylene Bue Dye Absorption Test
 The properties and Characteristics of
Molding Sand
Sand Testing
1. Clay Content Test: Total Clay Content
 The properties and Characteristics of
Molding Sand
Sand Testing
1. Clay Content Test: Total Clay Content
 The properties and Characteristics of
Molding Sand
Sand Testing
2. Grain Shape
3. Grain Size
4. Grain size distribution
 The properties and Characteristics of
Molding Sand
Sand Testing
 The properties and Characteristics of
Molding Sand
Sand Testing
5. Moisture Content
Conventional testing
Moisture Teller
 The properties and Characteristics of
Molding Sand
Sand Testing
5. Moisture Content
Conventional testing
Moisture Teller
 The properties and Characteristics of
Molding Sand
Sand Testing
6. Acid Demand Value (ADV)
7. Sintering Temperature or Fusion Point
 The properties and Characteristics of
Molding Sand
Sample preparation for mold testing
 The properties and Characteristics of
Molding Sand
8. Mold Hardness
 The properties and Characteristics of
Molding Sand
9. Permeability
 The properties and Characteristics of
Molding Sand
9. Permeability
 The properties and Characteristics of
Molding Sand
10. Strength

Universal sand strength testing machine

 The properties and Characteristics of
Molding Sand
9. Strength
 The properties and Characteristics of
Molding Sand
9. Strength
 The properties and Characteristics of
Molding Sand
9. Deformation (Plasticity) and
Toughness
 The properties and Characteristics of
Molding Sand
9. Shatter Index Tester
 The properties and Characteristics of
Molding Sand
10. Compactibility Test
 Ingredient of Molding Sand

Sand Binder Water Additives

• Natural • Western Bentonite /Moisture•

Molding • Southern Bentonite • Cereals

• High silica • Special clays • Ground Pitch
• Special sand
• Asphalt
•
• Sea Coal
• Zircon • Graphite
• Olivine • Fuel Oil
• Chamotte • Wood Flour
• • Silica Flour
• Perlite
• Molasses
• Dextrin
 Ingredient of Molding Sand

Sand
• Natural Molding
sand
• High silica sand
• Special sand
•

• Zircon
• Olivine
• Chamotte
•
 Ingredient of Molding Sand
• Natural Molding sand
•

• These sand contains appreciable amount of clay which

acts as a bond between the sand grains
• Natural molding sands are obtained by crushing and
milling soft yellow sandstone, carboniferous rocks etc.
• By virtue of their ease of availability and low cost,
natural molding sands are used for most casting of both
ferrous and non-ferrous metals.
• The requirement of these sands are satisfied by IS:3343-
1965 which has classified them into three grades as
follows:
•
Clay percentage 5-10 10-15 15-20
Sintering 1350-1450 1200-1350 1100-1200
Temperature
 Ingredient of Molding Sand
Sand
• High silica sand
• These sands contain less than 2% clay
• IS:1987-1974 covers requirement of these sand
and classify into three grades as follows:
•

Silica 98 95-98 90-95

percentage
Sintering 1685-1710 0C
Temperature
 Ingredient of Molding Sand
Sand
• Special sand
•

• Zircon
• Chemically zircon is zirconium silicate (ZrSiO4). This
sand has certain outstanding characteristics which
distinguish it from other sands.
• Low thermal expansion: 1/6th of silica sand
• Chemical inertness: useful for high alloy steel containing
Cr , Mn
• High thermal conductivity: double that of silica sand
• Greater density which prevents metal penetration
• High sintering temperature
•

•
 Ingredient of Molding Sand
Sand
• Special sand
•

• Zircon
• However on other side
• Zircon sand is required in greater volume than silica due
to its high density
• Mixing times are longer
• Good venting is requied
• Cost is high
•

•
 Ingredient of Molding Sand
Sand
• Special sand
•

• Olivine
• This is orthosilicate of iron and magnesium
(MgFe)O.SiO2
• Its density , conductivity and refractoriness are higher
than silica
•

• Chamotte
• is an aggregate produced from ground firebricks and
burnt fireclay and use because of its low expansion
characteristics.
•

•
 Ingredient of Molding Sand
Water/ Moisture
Ingredient of Molding Sand

Binder
• Western Bentonite
• Southern Bentonite
• Special clays
 Ingredient of Molding Sand
Additives
• Cereals
• Ground Pitch
• Asphalt
• Sea Coal
• Graphite
• Fuel Oil
• Wood Flour
• Silica Flour
• Perlite
• Molasses
• Dextrin
 Sand Molding

Flow chart of a metal casting system using sand molding

Sand Molding
Sand Molding
Sand Molding
Sand Molding
 Types of Sand Molding

1. Green sand molding

2. Dry sand molding
3. Skin-Dried Molding
4. Loam Moulding
5.
 Types of Sand Molding

Green Sand Molding

• Clay binders involve low material costs and avoid the additional costs
of mould hardening, whether by chemical or thermal means.
• The rapid turnround of moulding boxes and the smooth moulding and
casting cycle are advantageous in mechanized systems.
• The sand is readily reconditioned, since there is little dehydration of the
clay bond.
• Greensands, having lower compression strength, offer less resistance
to contraction than hardened moulds, so that the risk of hot tearing is
• reduced.
• Moulds joint closely, leaving little flash for removal by fettling.
• The process is environmentally friendly.
 Types of
2.Dry sand moldingSand Molding

• Hardened moulds offer maximum resistance to distortion under

metallostatic pressure, and to mould erosion during prolonged pouring.
They are therefore suitable for castings of the largest dimensions and
provide high standards of accuracy. In the production of cast irons in
particular, mould rigidity contributes to internal soundness as well as
to dimensional accuracy.
• The venting problem is reduced in the absence of steam generated from
moisture. Impervious mould surfaces are readily attainable, since sands
of lower permeability can be used, with coatings where required.
• Surface chilling is greatly reduced, facilitating metal flow in thin
sections. Problems of drying-out during delays in casting, leading to
surface friability, are avoided.
 Types of Sand Molding
3. Skin-Dried Molding
• Almost all dry sand molding has been replaced by the no-bake molding Sometimes
the pattern may be faced with a no-bake sand mixture and then backed up with a
green/dry sand mixture. An intermediate (between green sand and dry sand) type
of molding referred to as skin drying is sometimes used. The process is similar to
dry sand molding in that the same type of sand mixtures and equipment are used.
After coating the surface with a refractory wash, the molds are dried to a depth of 6
to 12 mm (0.25 to 0.5 in.). Skin-dried molds have some characteristics of green sand
molds and some of dry sand molds such as ease of shakeout and firm mold face,
respectively
 Types of Sand Molding
4. Loam Molding
• Loam molding is one of the oldest methods known. It requires the skill of an experienced
craftsman, and is seldom used today because of the lack of these craftsmen and the advent of
the no-bake systems that have a number of advantages over loam molding, especially greatly
reduced production time. Loam molding is particularly adapted to medium or large castings,
usually those of circular shape.
• The equipment required is relatively simple. No pattern is used; however, a flask or pit may be
necessary to support the finished mold. Replacing the pattern is one or more sweeps
conforming to the shape of the mold/core.
• The sweep is attached to an upright, rotating spindle. A bed plate, a cover plate, and arbors for
cores are also necessary items.
• Materials for making the molds consist of:
· Soft bricks capable of absorbing water
Molding sand that is quite coarse (sometimes referred to as gravel) and containing a
high percentage of clay
· Sawdust, straw, hay, hair, or cloth clippings may be used. These materials contribute to
mold strength and burn during casting, thus enhancing collapsibility (disintegration of
mold/core)
 Types of Sand Molding
4. Loam Molding
The molding sand is mixed with water to which molasses may be added until a thick loam
slurry resembling concrete is obtained. This mixture is used along with the bricks to build
up the general shape, using the same technique that a mason would use. Once the general
shape is attained, the bricks are covered with a layer of loam, and the sweep is used to
form the outside surface. A layer of loam from 6 to 25 mm (0.25 to 1 in.) thick remains.
The mold/core is then baked until thoroughly dry, after which a refractory coating is
applied. During the drying process, numerous small cracks form on the surface of the low
moisture content clay. These small cracks produce a surface that is very receptive to the
refractory coating, which may be brushed, swabbed, sprayed, or actually troweled on.
After application, the coating is brushed with molasses and water. A camel hair brush may
be used to impart an exceptionally smooth surface. The coating must be dried prior to
assembly. Loam molds impart a superior peel to castings.

Before the advent of spun cast pipe in metal molds, large-diameter pipe was made
in pits (pit cast pipe). The cores for these molds were made from loam. Hay rope
was wrapped around a metal mandrel and the loam slurry was applied, smoothed,
and dried, after which a refractory coating was applied
 Molding Process
1. Hand molding
2.

1. Floor molding
2.

1.

1. Open sand molding

2. One-box molding
3. Pit molding
4. Bench Molding
3. Machine molding
Molding processes are classified as hand molding or machine molding according to
whether the mold is prepared by hand tools or with the aid of some molding machin
Hand molding is generally found to be economical when the casting are required in
small
number.
On the other hand, when the casting are required in large quantities, hand molding
More time consuming and laborious and become expensive.
Considerable skill is also needed to make good molds by handIn such a cases,
machine molding is required.
Molding Process
 Molding Process
Bench Moulding
•

• Two Box Moulding

• Three Box Moulding
• Molding with a False Cheek
• Plate Molding
• Stack Molding
•
 Molding Process
A.Two Box Moulding
 Molding Process
A.Two Box Moulding
 Molding Process
A.Two Box Moulding
 Molding Process
B. Three Box Molding
 Molding Process
B. Three Box Molding
 Molding Process
B. Three Box Molding
 Molding Process
C. Molding with a False Cheek
 Molding Process
A molding methodE. Stack Molding
that makes use of both
faces of a mold section, with one face acting
as the drag and the other as the cope.
Sections, when assembled to other similar
sections, form several tiers of mold cavities,
and all castings are poured together through a
common sprue.
Molding Process
E. Stack Molding
 Molding Process
E. Stack Molding

Stack moulded cast iron piston rings

 Machine Molding
Hand molding is generally found to be economical when the casting are required
in small
number.
On the other hand, when the casting are required in large quantities, hand
molding is
More time consuming and laborious and become expensive.
Considerable skill is also needed to make good molds by handIn such a cases,
machine molding is required.
Advantages of machine molding
(1) It affords great saving in time, especially when a large number of similar casting in
small sizes are required.
(2) When the number of castings is substantial, the additional cost of metallic patterns
and other equipment is compensated by high rate of production, and overall cost
per piece works out lower than in case of hand molding
(3) The castings obtained are more uniform in size and shape and more accurate than
those obtained by hand molding
(4) A semi-skilled worker can do the machine job whereas hand molding requires
skilled craftsmanship
 Machine Molding

Flask Molds
•

• Snap flasks
• Tight flasks
Flaskless Molds
 Machine Molding
Jolt-type molding machines
These machines operate with the pattern mounted on a pattern plate (or plates), which
in turn is fastened to the machine table. The table is fastened to the top of an operating
air piston. A flask is placed on the pattern and is positively located by pins relative to the
pattern. The flask is filled with sand, and the machine starts the jolt operation. This is
usually accomplished by alternately applying and releasing air pressure to the jolt piston,
which causes the flask, sand, and pattern to lift a few inches and then fall to a stop,
producing a sharp jolt. This process is repeated a predetermined number of times,
depending on sand conditions and pattern configuration. Because the sand is compacted
by its own weight, mold density will be substantially less at the top of a tall pattern. The
packing that results from the jolting action will normally be augmented by some type of
supplemental compaction, usually hand or pneumatic ramming. When ramming is
complete, push-off pins, bearing against the bottom edges of the flask, lift the flask and
completed mold half off the pattern. Various mechanisms are used to lift the mold from
the pattern and turn it over (in the case of the drag mold) or turn it for finishing
operations (in the case of the cope mold).
 Machine Molding
Jolt-type molding machines

Primary components of a jolt-type molding

machine
 Machine Molding
Jolt squeeze molding machine with
solid squeeze heads
 Machine Molding
Jolt squeeze molding machine
with compensating heads
 Machine Molding

Sand slinger molding machines

 Machine Molding
Match Plate Pattern Machine

Primary components of a match plate

(squeezer) pattern
 Machine Molding
Match Plate Pattern Machine

Gravity-fill pressure squeeze molding machine using match plate patterns

 Machine Molding
Match Plate Pattern Machine

Blow-fill pressure squeeze molding machine using

match plate patterns
 Machine Molding
Pressure Wave Method

Pressure wave molding machine that compacts sand by the

rapid release of air pressure or an explosive combustible gas
mixture. Part (a) shows the mold filled by gravity prior to
being compacted by the pressure wave at (b).
 Machine Molding
Horizontal flaskless molding machines

Vacuum-fill pressure squeeze machine that

uses cope and drag patterns
 Machine Molding
Vertically parted molding machines

Blow-fill pressure squeeze molding machine making

vertically parted molds.
(a) Molding chamber filled with sand.

(b) Sand compacted by squeeze pressure.

(c) Finished sand mold pushed out of molding chamber

 Machine Molding
Molding Media Preparation

Essential components of a conventional vertical wheel

batch-type muller
 Machine Molding
Molding Media Preparation

Primary components of a continuous muller

 Machine Molding

High-speed batch-type muller with

horizontal wheels
 Machine Molding
Intensive mixer

Top views of an intensive mixer.

 Machine Molding

Side views of an intensive mixer

 Contents

• Solidification of Metals
• Nucleation and Grain Growth
• Cooling Curves
• Homogenous Nucleation
• Heterogeneous Nucleation
• Dendrites
• Shrinkage
Solidification of a pure metal.
 Solidification of Metals
1. During solidification, the liquid changes in to solid during cooling.
2. The energy of liquid is less than that of the solid above the melting point. Hence
liquid is stable above the melting point.
3. Below the melting point, the energy of liquid becomes more than that of the solid.
4. Hence below the melting point, the solid becomes more stable than the liquid.
5. Therefore at the melting point, liquid gets converted in to solid during cooling.
6. This transformation of liquid into solid below melting point is known as
solidification.
 Solidification of Metals
1. Thermodynamically, both liquid and solid have equal energy at melting point and
therefore both are equally stable at melting point.
2. Therefore, no solidification or melting will take place at the melting point. Liquid will
remain liquid and solid will remain solid.
3. Some under-cooling will be essential for solidification.
4. This transformation occurs by nucleation and growth.
 Cooling curve for a pure metal showing
possible undercooling.
• The transformation
temperature, as shown on the
equilibrium diagram, represents
the point at which the free
energy of the solid phase is
equal to that of the liquid phase.
• Thus, we may consider the
transition, as given in a phase
diagram, to occur when the free
energy change, ΔGV , is
infinitesimally small and
negative, i.e. when a small but
positive driving force exists due
to undercooling.
 Nucleation and Growth of Crystals
• At the solidification temperature, atoms
from the liquid, such as molten metal,
begin to bond together and start to form
crystals.
• The moment a crystal begins to grow is
know as nucleus and the point where it
occurs is the nucleation point.
• When a metal begins to solidify, multiple
crystals begin to grow in the liquid.
• The final sizes of the individual crystals
depend on the number of nucleation
points.
• The crystals increase in size by the
progressive addition of atoms and grow
until they impinge upon adjacent
growing crystal.

a)Nucleation of crystals, b) crystal growth, c)

irregular grains form as crystals grow together,
d) grain boundaries as seen in a microscope.
 Cooling Curve
• A cooling curve is a graphical plot of the
changes in temperature with time for a
material over the entire temperature range
through which it cools.
 Cooling Curve for Pure Metals
• Under equilibrium conditions, all metals
exhibit a definite melting or freezing point.
• If a cooling curve is plotted for a pure metal, It
will show a horizontal line at the melting or
freezing temperature.
 Cooling Curve of Alloys
• In this method, alloys with different compositions are melted and then the
temperature of the mixture is measured at certain time intervals while
cooling back to room temperature.
• A cooling curve for each mixture is constructed and the initial and final
phase change temperatures are determined.
 Cooling Curve
• Then these temperatures are used for the construction of the
phase diagrams
Cooling curve for the solidification of
a pure metal.
Cooling curve for a solid solution.
• In case of alloys, the solidification does not
take place at a constant temperature.
• In such cases, the solidification occure in a
range of temperature.
Series of cooling curves for different alloys in a completely
soluble system. The dotted lines indicate the form of the
phase diagram
Phase Diagram of Solid Solution
Cooling Curves for Solid Solution
 Mechanism of Solidification of Metals

• The solidification of metals occur by

nucleation and growth transformation.
• In nucleation and growth transformation, the
nuclei of the solid phase are formed and then
they grow.
 Nucleation and Growth Transformation

• Nucleation – The physical process by which a new phase is produced in a

material. In the case of solidification, this refers to the formation of tiny
stable solid particles in the liquid.
• Growth - The physical process by which a new phase increases in size. In
the case of solidification, this refers to the formation of a stable solid
particle as the liquid freezes.
 Nucleation and Growth Transformation

• The Nucleation and Growth Transformation

may be of two types
• 1. Homogeneous Nucleation
• 2. Heterogeneous Nucleation
 Homogeneous Nucleation

• Homogeneous Nucleation – Formation of a

critically sized solid from the liquid by
clustering together of a large number of
atoms at a high undercooling (without an
external interface).
 Solidification of Metals

• The transformation temperature, as shown on

the equilibrium diagram, represents the point
at which the free energy of the solid phase is
equal to that of the liquid phase.
• Thus, we may consider the transition, as given
in a phase diagram, to occur when the free
energy change, ΔGV , is infinitesimally small
and negative, i.e. when a small but positive
driving force exists.
Cooling curve for a pure metal showing possible
undercooling.
Energy barrier separating structural
states.
 Free Energy Changes

• The second phase has lower free energy than

the first phase
• Activation energy may be required for the
transformation to occur as shown above.
Nucleation and Growth Transformation

(1) The volume free energy ΔGV – free energy difference between the liquid and
solid
Δ GV = 4/3πr3ΔGv
(2) The surface energy ΔGs – the energy needed to create a surface for the spherical
particles
ΔGs = 4πr2γ
γ → specific surface energy of the particle

Total free energy Change

ΔGT = ΔGV + ΔGs
 Nucleation and Growth Transformation

• Embryo - 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 in to
a stable nucleus or re-dissolve.
• Nucleus – It is a tiny particle of solid that forms
from the liquid as atoms cluster together. Because
these particles are large enough to be stable,
nucleation has occurred and growth of the solid
can begin.
 Critical Size of Nucleus

• The minimum size that must be formed by

atoms clustering together in the liquid before
the solid particle is stable and begins to grow.
 r* : critical radius(where ΔGT reaches
the maximum)
• liquid metal is cooled below
freezing point, slow moving
atoms bond together to create
homogeneous nuclei
• Nucleus – larger than critical
size, can grow into a crystal
• Embryo – smaller than critical
size, continuously being formed
and redissolved in the molten
metal
•
For Critical size of nucleus
d(ΔGT)/dr = 0 when r = r*
Or r* = - 2γ/ΔGv
 critical nucleus size

• Critical nucleus size mainly determined by ΔGV

• Amount of undercooling increases, the critical
nucleus size decreases the relationship is
R* = 2γTm / ΔHf ΔT

Where γ: surface free energy

Tm: freezing temperature
ΔHf : latent heat of fusion
ΔT: amount of undercooling
critical radius versus undercooling
 critical nucleus size - Example

• calculate the critical radius of homogeneous

nucleus forms from pure liquid Cu.
• Assume
ΔT = 0.2ΔTm , γ = 1.77 × 10-7 J/cm2
Tm = 1083oC, Δ Hf = 1826 J/cm3
• calculate the number of atoms in criticalsized
nucleus at this undercooling
 critical nucleus size - Solution
•
ΔT = 0.2ΔTm = 1356 K × 0.2 = 271 K
2γTm 2(1.77 × 10-7 J/cm2)(1356 K )
•
r* = ─── = ───────────── = 9.70 × 10-8 cm
ΔHf ΔT (1826 J/cm3)(271 K)

•
volume of nucleus = 4/3 π (9.70 × 10-8 cm) 3
= 3.82 × 10-21 cm3
•
Cu: FCC structure, unit length a = 3.61 × 10-8 cm
• 4 atoms per unit cell
•
volume of unit cell = (3.61 × 10-8 cm) 3
= 4.70 × 10-23 cm 3
3.82 × 10-21 cm 3
• number of atoms = ─────── × 4 = 325 atoms
4.70 × 10-23 cm 3
 critical nucleus size

• d(ΔGT)/dr = 0 when r = r*
• r* = - 2γ/ΔGv
(a) Effect of nucleus size on the free energy of nucleus
formation. (b) Effect of undercooling on the rate of
precipitation.
 Homogeneous Nucleation

• Quantitatively, since ∆ Gv depends on the

volume of the nucleus and ∆ GS is
proportional to its surface area, we can write
for a spherical nucleus of radius r
∆ G = (4 π r3 /3) ∆ Gv + 4 π r2γ
• where ∆ Gv is the bulk free energy change
involved in the formation of the nucleus of
unit volume and γ is the surface energy of
unit area.
 Critical Size of Nucleus
• When the nuclei are small the positive surface energy term predominates,
while when they are large the negative volume term predominates, so that
the change in free energy as a function of nucleus size. This indicates that a
critical nucleus size exists below which the free energy increases as the
nucleus grows, and above which further growth can proceed with a
lowering of free energy; ∆ Gmax may be considered as the energy or work
of nucleation W. Both rc and W may be calculated since
•

d ∆G/dr = 4 π r2∆Gv + 8 π rγ = 0 when r = rc and thus

rc = -2γ / ∆G v

• Substituting for rc gives

•

W =16 π γ 3/3 ∆Gv2

• The probability of an atom having sufficient energy
to jump the barrier is given, from the Maxwell–
Boltzmann distribution law, as proportional to exp
[Q/kT] where k is Boltzmann’s constant, T is the
temperature and Q is usually expressed as the
energy per atom in electron volts.1
• The rate of reaction is given by
Rate = A exp [- Q/kT]
where A is a constant
• The surface energy factor is not strongly dependent on
temperature, but the greater the degree of undercooling or
supersaturation, the greater is the release of chemical free
energy and the smaller the critical nucleus size and energy of
nucleation.
• This can be shown analytically since
∆Gv = ∆H - T∆S,
• and at T = Te, ∆Gv = 0, so that ∆H = Te ∆S.
It therefore follows that
∆Gv =(Te -T) ∆S = ∆T∆S
• and because ∆Gv is proportional to ∆T, then
W is proportional to ∆S3 / ∆T2
• Heterogeneous Nucleation – Formation of a
critically sized solid from the liquid on an
impurity surface.
• heterogeneous nucleation occurs in a liquid
on the surface of its container, insoluble
impurities and other structural materials that
lower the critical free energy required to form
a stable nucleus
 Heterogeneous Transformation

• In practice, homogeneous nucleation rarely

takes place and heterogeneous nucleation
occurs either on the mould walls or on
insoluble impurity particles.
• A reduction in the interfacial energy would
facilitate nucleation at small values of ∆T.
• This occurs at a mould wall or pre-existing
solid particle
Chill-cast ingot structure
 crystal growth and grain formation
• nuclei → crystals → grains
• polycrystalline – solidified metal containing many crystals
• grains – crystals in solidified metal
• grain boundaries – the surfaces between the grains
• two major types of grain structures:
(1) equiaxed grains – crystals grow about equally in all
directions, commonly found adjacent to a cold mold
wall
(2) columnar grains – long, thin, coarse grains, created
when metal solidifies rather slow in the presence of a
steep temperature gradient. columnar grains grow
perpendicular to the mold surface
Ingot Structure

Al ingot
Nucleation and Growth Transformation
in solid solution
Nucleation and Growth Transformation
in solid solution

T(°C) L (liquid) L: 35wt%Ni

130 0
A + α
L
35 46

120 0 α
L+
32 43
α
(solid)
110 0
20 30 35 40 50
C0 wt% Ni
 Nucleation and Growth Transformation

• The factors which determine the rate of phase

change are:
• (1) the rate of nucleation, N (i.e. the number
of nuclei formed in unit volume in unit time)
and
• (2) the rate of growth, G (i.e. the rate of
increase in radius with time)
 Dendrites
• In metals, the crystals that form in the liquid during freezing
generally follow a pattern consisting of a main branch with many
appendages. A crystal with this morphology slightly resembles a
pine tree and is called a dendrite, which means branching.
• The formation of dendrites occurs because crystals grow in defined
planes due to the crystal lattice they create.
• The figure to the right shows how a cubic crystal can grow in a melt
in three dimensions, which correspond to the six faces of the cube.
• For clarity of illustration, the adding of unit cells with continued
solidification from the six faces is shown simply as lines.
• Secondary dendrite arms branch off the primary arm, and tertiary
arms off the secondary arms and etcetera.
Dendrites
 Dendrites
• During freezing of a polycrystalline material, many
dendritic crystals form and grow until they eventually
become large enough to impinge upon each other.
• Eventually, the interdendriticspaces between the
dendrite arms crystallize to yield a more regular
crystal.
• The original dendritic pattern may not be apparent
when examining the microstructure of a material.
• However, dendrites can often be seen in solidification
voids that sometimes occur in castings or welds, as
shown in the next slide..
Dendrites
Computer simulated image of dendritic growth using a cellular automata technique.
Notice the branching on the dendrites. Photograph courtesy of the Institute of
Materials, based on the work of U. Dilthey, V. Pavlik and T. Reichel, Mathematical
Modelling of Weld Phenomena III, eds H. Cerjak and H. Bhadeshia, Institute of
Materials, 1997.
 Steady-state patterns formed at the crystal–melt interface of a binary alloy of succinonitrile and
coumarin 152 during directional solidification.

Losert W et al. PNAS 1998;95:431-438

©1998 by National Academy of Sciences

 (A) Time evolution of the interface morphology for SCN/rhodamine 6G at constant pulling speed V (V
= 3.11 μm/s, G = 2.8 K/cm, C∞ = 0.325 wt%).

Losert W et al. PNAS 1998;95:431-438

©1998 by National Academy of Sciences

 Shrinkage
• Most materials contract or shrink during solidification and cooling.
Shrinkage is the result of:
•

• Contraction of the liquid as it cools prior to its solidification

• Contraction during phase change from a liquid to solid
• Contraction of the solid as it continues to cool to ambient temperature.
• Shrinkage can sometimes cause cracking to occur in component as it
solidifies.
• Since the coolest area of a volume of liquid is where it contacts a mold or
die, solidification usually begins first at this surface.
• As the crystals grow inward, the material continues to shrink.
• If the solid surface is too rigid and will not deform to accommodate the
internal shrinkage, the stresses can become high enough to exceed the
tensile strength of the material and cause a crack to form.
• Shrinkage cavitation sometimes occurs because as a material solidifies
inward, shrinkage occurred to such an extent that there is not enough
atoms present to fill the available space and a void is left.