L13-CRYSTALLIZATION

Volcanic Haystack-rock
in Canon beach,
OR,USA

ALSO KNOWN AS SOLIDIFICATION

COOLING/LOWERING OF
TEMPERATURE EVENTUALLY
BRINGS IN CRYSTALLIZATION
WHICH IS A SOLIDIFICATION
PROCESS
CRYSTALLIZATION
CRYSTALLIZATION, THE OLDEST KNOWN MATERIAL PROCESSING TECHNIQUE
PRACTISED BY PRIMEVAL COMMUNITIES, INVOLVED DRYING SEA WATER FOR SALT
COLLECTION.. SLOW HEAT REMOVAL UNDER SUN SHINE AND EVAPORATION OF WATER
CAUSES TINY CRYSTALLITES TO GET NUCLEATED AND GROW. THE ANALOGY CLEARLY
REFLECTS IN SOLIDIFICATION OF MELT..THE MELT COOLS.. TINY CRYSTALLITES
NUCLEATE..THEY GROW IN SIZE.

WHEN THERMODYNAMIC PARAMETERS, TEMPERATURE ,FREE ENERGY ARE UNIQUE IN A

PHASE TRANSFORMATION/SOLIDIFICATION-CRYSTALLIZATION PROCESS.. THE GROWTH
KINETICS AND GROWTH DIRECTION AS WELL AS PATTERN CAN BE INGENEOUSLY
CONTROLLED BY UTILIZING MATERIALS TECHNOLOGY PRINCIPLES.

HOW DOES
SOLIDIFICATION
—FORMATION
OF SOLID CRYSTALS FROM MELT
DIFFER?.. IT IS INDEED SAME
DESPITE BEING A HIGH
TEMPERATURE PROCESS-
TEMPERATURE IS RAISED TO
ACHIVE MELTING OF
CONSTITUENTS-THIS IS THEN
COOLED IN A CONTROLLED
MANNER TO ACHIVE
SOLIDIFICATION
CRYSTALLIZATION OF METALS
Basic thermodynamics principles state that both solid and liquid that results
upon melting have similar energy content. Both are equally stable at melting
point and no solidification will be initiated.

Some undercooling is essential to initiate solidification based on Nucleation and

Growth Process

Undercooling / sometimes referred as super-cooling points to further cooling

below melting point to remove latent heat, so that cluster nucleation and their
aggregation to form solid becomes favoured.
COOLING CURVE AND SOLIDIFICATION
TEMP, T LIQUID SOLID
PHASE PHASE

MELTING
POINT
FREEZING
POINT

T
EVOLUTION OF
UNDER LATENT HEAT
COOLING
CRYSTALLIZATION FROM MELT Time, t
 Phenomenon of Undercooling
At the thermodynamic melting or freezing temperatures, the probability of
forming stable, sustainable nuclei is extremely small. Therefore, solidification
does not begin at the thermodynamic melting or freezing temperature.

If the temperature continues to decrease below the equilibrium freezing

temperature, the liquid phase that should have transformed into a solid
becomes thermodynamically increasingly unstable.

Because the temperature of the liquid is below the equilibrium freezing

temperature, the liquid is considered undercooled.

The undercooling (∆T) is the difference between the equilibrium freezing

temperature and the actual temperature of the liquid.

As the extent of undercooling increases, the thermodynamic driving force for

the formation of a solid phase from the liquid overcomes the resistance to
create a solid-liquid interface.
Technological Significance of Solidification Process

Primary processing – Metal-working is

initiated with converting the raw
materials to molten form and then
casting them into desired shapes.
Secondary Processing -
Processes such as rolling,
extrusion, forging are used to
process ingots or slabs and
other semi-finished shapes.
 Nucleation and Growth
NUCLEATION: In cooling down phase of a melt, atomic aggregations in
fundamental nanoscale occurs giving rise to clusters. The clusters are
basically molecular, multi-atomic and lack long range order. Few such clusters
execute random hopping/migration and encounter each other giving rise a
rudimentary form of crystal that can transit to long range order, if survives.
Upon survival and further growth crystalline order do manifest with appropriate
cohesiveness coming into picture.

The rudimentary crystallite, once formed, need to withstand competitive forces

acing upon it. These are rapid thermal motion, instability at interface and
mobility. It is found that only beyond a critical size, a nucleated cluster entity,
here after termed as germ nucleus can not only survive but also proceed
towards further growth.

It can be quantitatively established that for a given material system in

molten liquid state, there exists a critical cluster radius for enabling
survival.
In addition, as stated, thermodynamic constraint impose certain
undercooling requirement.
In order to make the process kinetically viable, rate of formation of
clusters should exceed rate of their disassembly.
Only a surviving Nucleus allows working out of a kinetics formalism to
address its GROWTH
TYPES OF NUCLEATION EVENTS

HOMOGENEOUS HETEROGENEOUS
NUCLEATION NULEATION
Genesis and aggregation of clusters to Genesis of critically sized
surviving nuclei uniformly through out surviving nuclei at an impurity
the melt volume-a process driven by
surface/walls of container.
thermodynamic free energy difference.
Often strained
pockets/dislocations/impurities
provide nucleation pathways .
Heterogeneous nucleation
becomes a 3-body process—
The crystallites/
supersaturated solution or
melt/ impurity
STEPS IN HOMOGENEOUS
NUCLEATION
A MOLTEN LIQUID COOLS DOWN TO A TEMPERATURE
BELOW FREEZING POINT

LOSS OF THERMAL ENERGY OF ATOMS PROMOTES

PROBABILITY OF ENCOUNTER THAT EVENTUALLY LEADS
TO EMBRYO FORMATION AND EMBRYO CROSSES CRITICAL
SIZE TO BECOME A NUCLEUS

LARGER THE FREE ENERGY DIFFERENCE BETWEEN MELT

AND THE CONDENSED PHASE, LOWER IS THE VALUE OF r*:
THE CRITICAL RADIUS OF CLUSTERS THAT SURVIVES AND
GROWS INTO NUCLEI.

HOMOGENEOUS NUCLEATION IS BY AND LARGE DRIVEN BY

UNDERCOOLING THAT BRINGS ABOUT LARGE POPULATION
OF CLUSTERS EXCEEDING CRITICAL SIZE r*
WHY SHOULD CLUSTERING AND CRYSTALLIZATION
OCCUR IN A MOLTEN MATERIAL?
Thermodynamically the energy cost in maintaining a liquid is
higher. The crystal system has lower energy than the molten
liquid. An equilibrium system always moves to energy
minimum
−∆𝑮𝒗 = 𝑭𝒓𝒆𝒆 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝑺𝒐𝒍𝒊𝒅 𝒑𝒆𝒓 𝑼𝒏𝒊𝒕 𝑽𝒐𝒍𝒖𝒎𝒆
− 𝑭𝒓𝒆𝒆 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝑳𝒊𝒒𝒖𝒊𝒅 𝒑𝒆𝒓 𝑼𝒏𝒊𝒕 𝑽𝒐𝒍𝒖𝒎𝒆 = 𝑮𝒔𝒐𝒍𝒊𝒅 − 𝑮𝒍𝒊𝒒𝒖𝒊𝒅
A negative value of free energy change implies onset of spontaneous
nucleation
BEFORE PROCEEDING TO DISCUSS MECHANISM FURTHER, LET US CONSIDER A
RUDIMENTARY NUCLEUS r

For every cluster that aggregate

to form a crystallite there is
critical size r = r* beyond which
the aggregate survives and
becomes a nucleus for r r*, the
aggregate is an embryo which
disassembles and dissolves back
into molten liquid.
THE FREE ENERGY CHANGE HAS TWO DISTINCT TERMS- A
THERMODYNAMIC TERM THAT QUANTIFIES THE ENERGY DIFFERENCE
AND AN INTERFACE ENERGY TERM BASED ON SOLID-LIQUID
INTERFACE (σsl )
EVALUATION OF CRITICAL RADIUS

𝒅(∆𝑮) 𝟒
= 𝝅 ∆𝑮𝒗 𝟑𝒓𝟐 + 𝟒𝝅𝝈𝒔𝒍 𝟐𝒓 = 𝟎
𝒅𝒓 𝟑

2𝝈𝒔𝒍 ∗ 𝟏𝟔𝝅𝝈𝟑𝒔𝒍
r*=− ∆𝑮 =
∆𝐺𝑣 𝟑 ∆𝑮𝒗 𝟐

∆𝑯𝒇(𝑻𝒎 − 𝑻)
∆𝑮𝒗 =
𝑻𝒎
𝟐𝝈𝒔𝒍𝑻𝒎 𝟏
𝒓∗= −
∆𝑯𝒇 𝑻𝒎 − 𝑻

𝝈𝒔𝒍 =interfacial tension, Tm= Melting Temperature in K, ∆𝑯𝒇=Latent Heat of Fusion

Δ T = (Tm - T) is the undercooling when the liquid temperature is T.

Experimentally Observed Values for Homogeneous
Nucleation
 THE CRITICAL RADIUS OF GERM NUCLEUS/ NANO-
CLUSTURE IS INVERSELY DEPENDENT ON HEAT OF
FUSION AND DEGREE OF UNDER-COOLING

T /°C AS THE UNDERCOOLING INCREASES, CRITICAL

NUCLEUS SIZE DECREASES

500

400

300
REGION OF EMBRYONIC NUCLEI THERMAL
STABILTY INSTABILITY
200 REGION
EMBRYOS DO
NOT SURVIVE
100

5 nm 10 nm 15 nm
GERM NUCLEI FORMING DURING COOLING
OF HOT MOLTEN LIQUID. VARIOUS SIZES
OD NANO-CLUSTER NUCLEI ARE FORMED.
ONLY CERTAIN SIZES SURVIVE AND GROW.
OTHERS DISAPPEAR BY RE-DISSOLVING.
Only nano-cluster nuclei wit h 𝒓 ≥ 𝒓 ∗ survives

THE DARWINIAN SEA

Calculation of Critical Radius for the Solidification of Copper

Calculate the size of the critical radius and the number of

atoms in the critical nucleus when solid copper forms by
homogeneous nucleation. Comment on the size of the nucleus
and assumptions we made while deriving the equation for the
radius of the nucleus.

USING EXPERIMENTAL VALUES REPORTED FOR COPPER FROM

TABLE IN EARLIER SLIDE
Calculation of Critical Radius for the Solidification of Copper
THE SOLIDIFICATION PROCESS-EVOLUTION OF GRAIN
BOUNDARIES AND GRAIN STRUCTURE

FIGURE COURTESY: BASED ON MSE/CALLISTER

EVOLUTION OF POLYCRYSTALLINE MORPHOLOGY

MOLTEN METALLIC LIQUID

FURTHER DIFFUSION
CONTROLLED GROWTH
GROWTH OF NANO- LEADS TO EVOLUTION
ORIGIN OF NANO- CLUSTERS INTO OF EQUIAXED GRAIN
STRUCTURE AND GRAIN
CLUSTERS/ TINY CRYSTALLITES- BY
BOUNDARIES( ONSET OF
NUCLEI DURING COALESCENCE OF POLYCRYSTALLINE
SOLIDIFICATION CLUSTERS- ONSET MORPHOLOGY WITH
OF LONG RANGE RANDOMLY ORIENTED
PROCESS GRAINS)
ORDER
PRACTICE PROBLEM----HOME WORK

During solidification of Gold (Au), a critical nucleus that formed

contained 548 atoms. Predict the Degree of undercooling for a
homogeneous nucleation event. Following data on Gold can be made
use of in calculation.

Latent Heat of Fusion. 1.16 X 109 J/m3

Surface Free Energy: 0.123 J/m2

Lattice parameter: 0.413 nm

Melting point of Au: 1064 °C

THANK YOU ALL FOR YOUR ATTENTION