4/11/2018

Physical Metallurgy 2 ( 2017/2018)

Solidification

Dr. Deni Ferdia n, M. S c

Disclaimer: This lecture note is edited from different sources for the solely of teaching and
learning purposes. It may contain copyrighted materials from their respective owners; therefore,
apart form teaching and learning purposes, this lecture note may not be reproduced, stored, or
transmitted in any form or by any means.

Length-Scale in Solidification Analysis

10-3 m
meso 10-9 m
macro nano
10-4 m 10-6 m
micro

mushy liquid
solid zone

Stefanescu, 2011

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Growth conditions
Heat Transfer at the solidification front Microstructure/
macrostructure

Casting Melt control:

process Trace elements
Inoculation, refining
modification

Alloy composition

Solidification as a means
for assembling or manufacturing

Welding

Brazing

Spray deposition Prototyping

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Outline

 Introduction
 Nucleation
 Growth of Solid
 Lever and Scheil Equation
 Solidification Cooling Curves
 Heat Flow and Dendrite Growth
 Alloys Solidification
 Cast Structure
 Rapid Solidification
 Solidification Defects

Introduction

 Solidification and melting of metals and their alloys are

important in industrial process.
 In general, solidification and melting are transformations
between crystallographic and non-crystallographic states of a
metal or alloy.
 These transformations are basic to such technological
application as ingot casting, foundry casting, continuous casting,
directionally solidified, single-crystal growth, and many more.
 An understanding of the mechanism of solidification and how it
is affected by parameters such as temperature distribution,
cooling rate and alloying is important in the control of
mechanical properties of the materials.

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 In large bulk castings, the solidification temperature corresponding to

the onset of freezing is often close to but slightly less than the melting
point or equilibrium liquidus temperature.
 The offset of the solidification temperature with respect to the
equilibrium temperature is called the undercooling or supercooling,
ΔT, and it plays a vital role in the overall description of the initial
stage of the solidification that is controlled by nucleation.
 The level of melt undercooling at the onset of solidification is
important to consider in developing an understanding of the variety of
structural modifications and grain-refining practices in common
casting alloys
 Moreover, it is the basis of more recent solidification processing
technologies by using a method called rapid solidification.

Nucleation

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Nucleation terminology

 Nucleation - The physical process by which a new phase is produced

in a material.
 Critical radius (r*) - The minimum size that must be formed by
atoms clustering together in the liquid before the solid particle is
stable and begins to grow.
 Undercooling or Supercooling - The temperature to which the
liquid metal must cool below the equilibrium freezing temperature
before nucleation occurs.
 Homogeneous nucleation - Formation of a critically sized solid from
the liquid by the clustering together of a large number of atoms at a
high undercooling (without an external interface).
 Heterogeneous nucleation - Formation of a critically sized solid
from the liquid on an impurity surface.

Nucleation Phenomena

 Nucleation during solidification is a thermally activated process

involving a fluctuational growth in the sizes of clusters of solids.
 Changes in cluster size are considered to occur by a single atom
addition or by removal exchange between the cluster and the
surrounding undercooled liquid.
 At small cluster sizes, the energetics of cluster formation reveal that the
interfacial energy is dominant.
 For the smallest sizes, clusters are called embryos; these are more likely
to dissolve than grow to macroscopic crystals.

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 In fact, the excess interfacial energy due to the curvature of

small clusters is the main contribution to the activation
barrier for solid nucleation.

 This accounts for the kinetic resistance of liquids to

crystallization and is manifested in the frequent
observation of undercooling effects during solidification.

Homogeneous Nucleation

 Homogeneous nucleation occurs at

which formation of a critically sized
solid from the liquid by the clustering
together of a large number of atoms at a
high undercooling (without an external
interface).
 There are no special objects inside a
phase which can cause or induce
nucleation.
 For instance, when a pure liquid metal
is slowly cooled below its equilibrium
freezing temperature to a sufficient An interface is created when a solid
degree numerous homogeneous nuclei forms from the liquid
are created by slow-moving atoms
bonding together in a crystalline form.

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Nucleation Energy

Liquid Liquid

Solid
a b
G2
G1 G2 = VsGvs + VLGvL + ASLSL
G1 = (Vs + VL)GvL G2 = G1 + G
G = G2 – G1
If Gv = GvL - Gvs
Then:
G = - VsGv + ASLSL

Nucleation Energy

Volume free energy Gv Surface energy Gs

 Released by liquid to solid  Required to form new solid
transformation. surface
 ΔGv is the change in free energy per  ΔGs is energy needed to
unit volume between liquid and solid create a surface
 ΔGv is negative  γ is the surface free energy
 This is the energy that drives the per unit area, then
transformation
G s  4r 2
 The free energy change for a
spherical cluster of radius r is given  ΔGs is a retarding energy
by
4 3
r Gv
3

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Nucleation activation energy

If the total change for Gibbs

free energy is:
G = - VsGv + ASLSL
4
; sphere volume
3
4 ; surface area
Energy
Lowered by
and at critical size,
redissolving r = r* and dG/dr = 0

Energy
lowered by
It can be shown that:
growing into
∗
2
crystals
Δ
16
Δ ∗
3 Δ

G and Temperature

From Gibbs-Thomson
GvL equation, sphere of radius r
will have a free energy
greater than that of bulk
solid by 2Vm/r per mole or
Gv r  r* 2/r per unit volume.
Gvs 2 It can be seen from the
r* figure that
r 
Gv = 2sL/r*
T

Tm T

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 The magnitude of DGV increases as temperature decreases below

the melting point, while γ does not change significantly
 It can be shown that the radius, r*, of the cluster of critical size at
a transformation temperature as T decreases, i.e., with
increasing undercooling
 2  2 T m  1   2 T m  1 
r *= =    
 GV  L  Tm  T    L   T 
where Tm is the melting temperature in Kelvin, L is the latent
heat of fusion and DT is the under-cooling
 As a result, it becomes easier to form nuclei, and the number of
nuclei per unit volume increases as the temperature T drops
further and further below the melting point (known as
undercooling)

Critical Radius Versus Undercooling

 For an undercooling (T), Gv is given by = where

Lv is latent heat of fusion per unit volume and Tm is melting
temperature.

 Thus:
∗
2 1 ∗
16 1
= ; Δ =
Δ 3 Δ
r* = critical radius of nucleus
γ = Surface free energy

 As the amount of undercooling increases, critical nucleus

size decreases.

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r*, rmax, and T

 At small undercooling, r* is so large that there will be no chance of
forming a stable nucleus.

 As T increases, r* and G* decrease, and for undercoolings of TN or

greater there is a very good chance of some clusters reaching r* and
growing into stable solid particles.

 As the size of the cluster of atoms increases, total free energy change
increases up to a size r*

 Any further increase in size results in a decrease in free energy change

 A cluster of critical size (r*) is called a nucleus

 Smaller clusters will redissolve into the liquid
 Once a cluster reaches critical size it can grow

Nucleation in Pure Metals

 If a liquid is cooled below its equilibrium

melting temperature there is a driving liquid
force for solidification (GL-GS) and it
might be expected that the liquid phase G
would spontaneously solidify.
 However, this is not always the case,
solid
especially in homogeneous nucleation.

 Let consider a pure metal in which at the

fusion temperature (melting) Tf, G = 0,
so that:
Tf
G = Hf - Tf Sf = 0 Temperature
or Hf = Tf Sf
where Hf (Lv) is the latent heat of fusion
and Sf entropy is positive for melting.
The driving force is therefore proportional to the undercooling provided that the
latent heat and the entropy of fusion do not vary much with temperature.

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Maximum observed undercooling during Droplet

Solidification

Undercooling for Alloys -during Droplet

Solidification

D.M. Stefanescu, Science and Engineering of Casting Solidification, 2015

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Heterogeneous Nucleation

 Heterogeneous nucleation occurs when there are

special objects inside a phase which can cause
nucleation.
 A solid forming on an impurity can assumed the
critical radius with a smaller increase in the surface
energy; and thus, heterogeneous nucleation can
occur with relatively low undercooling.

Heterogeneous Nucleation

 Occurs at a preexisting imperfection, such as the mold wall

(during solidification of an ingot) or impurities (such as
grain refiner)
 During nucleation, two types of interfaces that require
energy are formed

 Solid-liquid (SL) and Solid-Imperfection (SI)

 One type of interface, the Liquid-Imperfection (IL) interface

is removed. This provides additional energy to drive the
transformation

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Heterogeneous Nucleation
SL
Liquid (L)
Solid (S)  ML
2 cos 1 cos
SM 4
Mould (M)
 Thus:
∗
2
r Δ
∗
16
Δ .
cos 3 Δ
 Hhet depends on wetting angle and
Ghet = - VsGv + ASLSL+ ASMSM- cap radius
ASMML  The tendency of a crystal to spread
4
 Δ 4 over the surface is called wetting,
3 that is
cos

Wetting and contact angle

 If m > 1, then there is no stable
 A spherical cap can form on a substrate
contact angle, and the surface free for which 0 < m < 1.
energy is decreased continuously
 Thus, the condition for nucleation can
as the embryo spreads over the
substrate. occur with less supercooling when a
suitable substrate is present than
 If m < -1, then again no stable
without a substrate.
contact angle, and any contact
between embryo and substrate
causes an increase in surface free
energy. h q

 Stable contact angle will be given Substrate

by m value between +1 and -1. q

r

 If m value approaching unity, then 0

a nucleus of critical radius can
form with a volume that is much
less then would be necessary in the
absence of the substrate.

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Relation between volume of an embryo and contact

angle

h/r Vc/V m
 If the volume of spherical cap of height
1 0.5 0
h is given by 1/3 h2 (3r – h) where r is 0.8 0.35 0.21
the radius of the sphere; it then can be 0.5 0.16 0.50

shown that the ratio of the cap volume 0.3 0.06 0.72
0.1 0.007 0.9
to the volume of complete sphere is,
0.01 0.00007 0.99
0.001 0.0000 0.999
3 07
4
 If the ratio h/r is represented by q,
then

3
4
 Vc/V can be calculated for various
values of h/r,

Diffusion controlled growth

 Once stable nuclei have formed, they grow by diffusion of

atoms to the interface, and their migration across the
interface from the liquid to the solid phase
 It can be shown that the radius of a spherical particle will
increase according to the equation below, where D is the
diffusion coefficient
r =  Dt
where
  Qd 
D  D0 exp 
 RT 

 As the temperature T decreases, the diffusion coefficient

decreases exponentially. This results in a rapid decrease
in growth rate

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Overall Transformation Kinetics

 The overall rate of

transformation depends
on both nucleation and
growth
 At low under-cooling,
nucleation rate is low
resulting in a low
transformation rate
 At high under-cooling,
the growth rate is low,
also resulting in a low
transformation rate
 The fastest
transformation occurs
at an intermediate
temperature

Nucleation Rate – Temperature Diagram

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Comparison Homogeneous and Heterogeneous

Schematic comparison of
(a) homogeneous and (b)
heterogeneous nucleation
of a crystal in a
supercooled liquid.

The interface energies are

assumed to be isotropic
and in (b) the catalytic
surface is assumed to be
flat.

Excess free energy

 Activation energy barrier G

against heterogeneous G*hom
nucleation is smaller than
that of homogeneous
nucleation by the shape G*het
factor, S().
r
G*het = S() G*hom
r* Ghet

Ghom

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Effect of undercooling on nucleation

Decrease in critical nucleus size

Decrease in activation energy to form nuclei
Increase in nucleation rate

Homo- and Heterogeneous Nucleation Rates

 At low undercooling, the additional

energy provided by the removal of the
IL interfaces aids heterogeneous
nucleation
 At high undercooling, the
homogeneous nucleation rate
becomes higher than heterogeneous
nucleation rate because there are
many more potential sites for
homogeneous nucleation to occur
 At very high undercooling, the
nucleation rate drops off because
atoms are not able to diffuse fast
enough for nucleation to occur (Solid
state solidification)

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Applications of
Controlled Nucleation

Applications of Controlled Nucleation

 Grain refinement - The addition of heterogeneous nuclei in

a controlled manner to increase the number of grains in a
casting.
 Dispersion strengthening - Increase in strength of a
metallic material by generating resistance to dislocation
motion by the introduction of small clusters of a second
material.
 Solid-state phase transformation - A change in phase that
occurs in the solid state.
 Rapid solidification processing - Producing unique material
structures by promoting unusually high cooling rates
during solidification.

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Grain Structure in Industrial castings

 To produce cast ingots with fine grain size, grain refiners are added.
 Example: For aluminum alloy, small amount of Titanium or Boron.

Grain structure of
Aluminum cast
with (a) and
without (b)
grain refiners.

(a) (b)

Nucleation on AlB2 substrate particles, inoculation

AlB2(grain refiner)

Grain refiner addition

No addition

Cooling curve of Al 9.6Si with grain

refiner and without.
*Cooling curve will be discuss later

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Grain Refinement Nucleation Theory:

Free growth model

 heterogeneous nucleation
on a catalytic surface of
limited lateral extent
cannot produce growth
until the triple junction
between liquid, solid and
heterogeneity reaches the
edge of the catalytic
surface and the size.

 When the solid reaches

the critical hemispherical
condition it is free to
effectively produce
solidification. A.L. Greer, 2003

Other Grain Refinement Theory

 Boride/Carbide Theory
 Peritectic Hulk Theory
 Duplex Nucleation
Theory
 Solute Theory (Growth
Restriction Factor)

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Conditions for efficient nucleation

 Small wetting angle, 

 Low surface energy between substrate and crystal
 Good crystallographic match

Lattice match between

Al and AlB2

Grain refinement of Aluminium

X-ray video of Al-20%Cu

Al-5%Ti-1%B type grain refiner

Addition 1g / kg melt

Growth from top

Dendrite coherency – network

formation

Video : courtesy of R. Mathiesen

and L. Arnberg

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In-situ X-ray radiographic - Al-10Cu

(Cooling rate effect)

Grain structure development of Al-10Cu alloy inoculated by 500 ppm of Al-5Ti-1B grain
refiners, with two different cooling rates, 0.5K/s for images at the above and 0.025 K/s for
the images at the below
Li et al, MCWASP, 2015

Substrate particle size, d

1
T for Grain Initiation (K)

4 0.8
d
s f T 0.6

Too small particles will 0.4

need high undercooling
0.2

 0
0 2 4 6 8
Particle Diameter (m)

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Fading effect of grain-refiner

Growth of Solid

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Growth of pure solids

There are two different types of solid/liquid interfaces:

 an atomically rough or diffuse interface associated with
metallic system, and
 an atomically flat or sharply defined interface often
associated with non-metals.
 Because of the differences in atomic structure – they
migrate in quite different ways.
 Rough interfaces migrate by a continuous growth.
 Flat interfaces migrates by a lateral growth process
involving ledges.

Interface morphology

• Facetted
• Atomically smooth
• =sf /R>2
• Non-metals
•Intermetallic phases
•Growth by nucleation
of new atomic layers

• Non-facetted
• Atomically rough
• =sf/R<2
• metals

Reproduced from:W. Kurz & D. J. Fisher: Fundamentals of Solidification

Trans Tech Publications, 1998

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Growth mechanisms

Twinning or dislocation:
Nucleation of new planes not necessary

Screw
dislocation
Twinning

Reproduced from:W. Kurz & D. J. Fisher:

Fundamentals of Solidification
Trans Tech Publications, 1998

Growth Anisotropy

Cubic crystal bounded by (111) planes

Growth of (100)

Bounded by (110) planes

Growth of (100)

•Fastest growing planes disappear V  K(hkl )Tk

•Crystals bounded by slow growing planes
Anisotropy increases with α



Reproduced from:W. Kurz & D. J. Fisher:

Fundamentals of Solidification
Trans Tech Publications, 1998

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Growth rate versus interface supercooling

V  K 2 (Tk ) 2
Screw dislocation


V  K1Tk

K4
V  K 3 exp( )
 Tk
Two dimensional
nucleation



Continuous growth

 The driving force for solidification (ΔG) will be given

by:
Δ = Δ
where L = latent heat of melting
ΔTi = undercooling of the interface below the
equilibrium melting temperature
 By analogy with this equation, the rate of
solidification will be given by:

= Δ

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Lateral growth

 If a single atom leaves the

liquid and attaches itself to
the flat solid surface, number
of broken bonds associated
with the interface, i.e.
interfacial energy will be
increased.
 Therefore, only little probability
that the atom will remain attached
to the solid and is likely to jump
back into the liquid (a).
 If the interface contains ledge,
liquid atoms will be able to join the
ledges with a much lower resulting
increase in interfacial energy (b).

Growth Ledges

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Different ways for lateral growth

1. Surface Nucleation
 There will be a critical radius (r*) which
will decrease with increasing the interface
undercooling.
 Once nucleated the disc will spread rapidly
over the surface and the rate of growth
normal to the interface will be governed by
the surface nucleation rate, given by:
v  exp (-k2/ΔTi)
 This mechanism is very ineffective at small
undercooling where r* is very large.

2. Spiral Growth
 If the solid contains dislocations
that intersect the S/L interface
the problem of creating new
interfacial steps can be
circumvented.
 The rate will be given by:
v = k3 ( ΔTi)2, where k3 is a
material constant.
 This variation is shown in the
figure along with the variations
for continuous growth and two
dimensional system.

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3. Growth from Twin Intersections

 In solidification, it is quite common for materials showing

faceting to solidify as two crystals in twin orientations.

 Interfacial facets will therefore intersect at the twin boundary

which can act as a permanent source of new steps thereby
providing an easy growth mechanism similar to the growth
spiral mechanism.

Lever Rule And

Scheil-Gulliver Equation

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Alloy solidification

 Solidification in pure materials is rarely encountered

in practice!
 Let see single-phase alloy for 3 limiting cases:
 Infinitely slow (equilibrium) solidification.
 Solidification with no diffusion in the solid, but perfect mixing
in the liquid.
 Solidification with no diffusion in the solid, and only
diffusional mixing in the liquid.

Infinitely slow solidification

 k = Partition Coefficient
– Constant for any T
 Cooling slow enough to
allow extensive solid-
state diffusion
 Solid & liquid always
homogeneous with
compositions following
solidus and liquidus.
A hypothetical phase diagram. k = Xs/XL is constant

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Partition coefficient (k)

Eutectic phase diagram

T
• Lower solubility
C0 l of alloying elements
Tl in solid than in liquid

Ts T0 • k= <1 and m= <0

Cl
Cs C0
s • k and m constants if solidus
& liquidus lines are straight

C0 (1  k)
C T0  mC0  m
k



Partition coefficient in Al alloys

Al-Fe Al-Mg
k=0.03 k=0.44 Example of Al-X
phase
diagrams with
different
Al-Mn Partition
Al-Si
k=0.90 k=0.14 coefficients
k=

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Lever Rule

 The composition of various phases in a phase

diagram can be determined by a procedure called the
lever rule.
S C  CL L C  C0
 0 or  s
S  L Cs  CL S  L Cs  CL

 Example: Calculate the relative proportions of the

phases in a Cu-Ag alloy of eutectic composition just
below the eutectic temperature.
 C E  C  71.9  91.2
   23.2%
   C  C  7.9  91.2

Lever Rule

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Lever Rule

 (a) A planar S/L

interface and axial heat
flow.
 (b) Corresponding
composition profile at
T2 assuming complete
equilibrium.
 Conservative of solute
Unidirectional solidification of alloy X0
requires the two shaded from the previous figure.
areas to be equal.

Lever Rule

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Non-equilibrium lever rule (Scheil-Gulliver

equation)

 In metallurgy, the Scheil-Gulliver equation (or Scheil

equation) describes solute redistribution during
solidification of an alloy.

 This approach by assuming a local equilibrium of the

advancing solidification front at the solid-liquid interface.

 Unlike equilibrium solidification, solute does not diffuse

back into the solid and is rejected completely into the
liquid.

 Equilibrium is assumed at the interface which allows the

use of an equilibrium phase diagram.

Scheil – Gulliver Equation

 The hatched areas in the figure represent the

amount of solute in the solid and liquid.
 Considering that the total amount of solute in the
system must be conserved, the areas are set equal
as follows:

 Since the distribution coefficient is

(determined from the phase diagram)
 and mass must be conserved the mass balance may
be rewritten as

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Scheil – Gulliver Equation

at

Scheil model and Lever rule

Read work related to Brody – Fleming model for back diffusion and
further work by Himemiya dan Umeda (1998)

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Liquidus Projection – Ternary Alloy

3D isometric 2D Liquidus Projection

Solidification path – Ternary Alloy

3D
isometric

2D Liquidus
projection

Schematic description of solidification path and pattern for a ternary eutectic alloy with an initial
composition at O point. (a) Threes solidification stages along the liquidus projections of ternary phase
diagram; (b) The relationship between the interfacial temperature and the fraction of solid; (c) The
solidification pattern related to the microstructure formation corresponding to each stage.

(Erhu Yan et al. 2014)

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Ternary & higher eutectics (example in Al-Si alloy)

Al-Fe-Mg-Si phase diagram

Liquidus Projection of Al-Mg-Si – Fe

quarternary system

Chinese script

Liquidus Projection of Al-Mg-Si

ternary system

π-Al-(FeMg)-Si

Example of Ternary Eutectic Phase

β
Si

Mg2Si

Cooperative growth of 3 or more phases

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Coring microstructure

May be eliminated by heat

treatment/ homogenization

Liquid Entrapment

Sequence of 2D (left) and 3D (right) images extracted from the volume of the specimen held for various times at
570°C showing the different coarsening mechanisms occurring on the scale of the dendrite arms (dark grey on the 2D
images): a) progressive small dendrite arm melting; b) progressive interdendritic groove advancement; c) progressive
interdendritic groove advancement and joining of the tips of the dendrite arms, leading to the formation of entrapped
liquid.
L. Salvo, 2009

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Rosettes of Al-Si-Fe alloy (Liquid entrapment) - Optical

metallography
77
D. Ferdian, These, INPT 2014

Various multi phases appearance within the rosettes

Solidification Cooling
Curve

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Cooling Curves

 Recalescence - The increase in temperature of an

undercooled liquid metal as a result of the liberation of
heat during nucleation.
 Thermal arrest - A plateau on the cooling curve during the
solidification of a material caused by the evolution of the
latent heat of fusion during solidification.
 Total solidification time - The time required for the casting
to solidify completely after the casting has been poured.
 Local solidification time - The time required for a particular
location in a casting to solidify once nucleation has begun.

Cooling curve and Nucleation

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©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under
Solidification Cooling Curve of Pure Metal

(a) Cooling curve for a pure metal

that has not been well inoculated.
Liquid cools as specific heat is
removed (betweens points A and B).
Undercooling is thus necessary
(between points B and C). As the
nucleation begins (point C), latent
license.

heat of fusion is released causing an

increase in the temperature of the
liquid. This process is known as
recalescence (point C to point D).
Metal continues to solidify at a
constant temperature (T melting). At
point E, solidification is complete.
Solid casting continues to cool from
the point.

(b) Cooling curve for a well

inoculated, but otherwise pure metal.
No undercooling is needed.
Recalescence is not observed.
Solidification begins at the melting
temperature

Example video of Recalescence

Pyroxene liquid (Ca,Fe.Mg)Si2O6 allowed to cool Recalescence causing the temperature to

and crystallize in air on a copper plate. Note rise to the equilibrium freezing
recalescence visible starting at about 0:35 and temperature.(Taken by FLIR camera)
lasting for 10 seconds.

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 4/11/2018

Cooling Curve of Alloy Solidification

Typical terminology used in

Thermal Analysis for casting
process control:
TL—equilibrium liquidus
temperature,
TE—equilibrium eutectic
temperature,
TLA—temperature of liquidus
arrest (nucleation),
TEmin—temperature of eutectic
undercooling,
TEmax—temperature of eutectic
recalescence,
T—undercooling/recalescence,
 Tmax—maximum undercooling,
 Tmin—minimum undercooling

Phase Diagram and Cooling Curve

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 4/11/2018

Phase Diagram and Gibbs Energy

Heat Flow and

Dendrite Growth

43
 4/11/2018

Growth Mechanisms

 Specific heat - The heat required to change the temperature of a

unit weight of the material one degree.
 Solidification front - Interface between a solid and liquid.
 Planar growth - The growth of a smooth solid-liquid interface
during solidification, when no undercooling of the liquid is
present.
 Dendrite - The treelike structure of the solid that grows when an
undercooled liquid solidifies.

Heat flow and interface stability

 In pure metals, solidification is controlled by the rate at

which the latent heat of solidification can be conducted away
from the solid/liquid interface.

 Conduction can take place either through the solid /liquid

depending on the temperature gradients at the interface.

 The temperature gradient in the liquid ahead of the nodule

will increase while that in the solid decreases.

 More heat will be conducted into the protruding solid and less
away so that the growth rate will decrease below that of the
planar regions and the protrusion will disappear.

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 4/11/2018

 For example solid growing at a velocity v with a

planar interface into superheated liquid, figure (a).

 The heat flow away from the interface through solid

must balance that from the liquid plus the latent heat
generated at the interface:

KsG’s = KLG’L + VLv

where K = Thermal conductivity,
G’ = temp. Gradient (dT/dx),
S/L = solid or liquid,
V = the rate growth of the solid,
Lv = the latent heat of fusion/unit
volume.

 The situation is quite different for a solid growing

into supercooled liquid.
 If a protrusion forms on the solid in this case the
negative temperature gradient in the liquid
becomes even more negative (a).
 Heat is removed more effectively from the tip of the
protrusion than from the surrounding regions
allowing it to grow preferentially (b).
 A solid/liquid interface advancing into supercooled
liquids is thus inherently unstable (c).
 Heat conduction through the solid arises when
solidification takes place from mould walls which are
cooler than the melt.
 Heat conduction into the liquid, can only arises if the
liquid is supercooled below Tm.

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 4/11/2018

Planar Growth
When the temperature of the
liquid is above the freezing
temperature a protuberance
on the solid-liquid interface
will not grow, leading to
maintenance of a planer
interface. Latent heat is
removed from the interface
through the solid
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson
Learning™ is a trademark used herein under license.

 For the formation of stable protrusions on a planar interface,

constitutional supercooling (or known as well as constitutional
undercooling) must exist in the liquid.
 Constitutional supercooling is supercooling arising from compositional
effects, in which varying solute concentration results in varying
solidification temperatures!

Cellular and dendritic

 Diffusion of solute into the liquid during
solidification of an alloy is similar to the conduction
of latent heat into the liquid during the
solidification of a pure metal.
 Temperature gradients in the liquid complicate the
problem.
 Dendrites (from Greek dendron, a tree) are
ramified (branched) crystals, exhibiting
morphological features that display
crystallographic directionally, such as straight
primary stems, secondary side arms, and even
tertiary arms.

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 4/11/2018

Growth Interfaces
 Growth of Interfaces depends on
 Concentration Gradient

 Temperature Gradient

 undercooling

 Growth Rate

 Types of Interfaces
 Planar

 Cellular
V = 0.2 1 µm/s 3 µm/s 7 µm/s
 Dendritic
µm/s
 Equiaxed

Transition growth

Transition of
growth
morphology from
planar to cellular, to
dendritic, as
compositionally
induced
undercooling
increases
(equivalent to G/V
being reduced).

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 4/11/2018

Plane Front to Cell and Dendrite Transition

Kurz, EPFL Lausanne

effect of alloying
Structure refinement

Increasing concentration

Increasing constitutional
undercooling (Tc)

Increasing morphological
instability

Increasing cooling rate

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 4/11/2018

Dendrite Growth

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under
license.

If the liquid is undercooled, a protuberance on the solid-liquid interface can grow

rapidly as a dendrite. The latent heat of fusion is removed by raising the temperature of
the liquid back to the freezing temperature. (b) Scanning electron micrograph of
dendrites in steel (x 15)

Development of thermal dendrites

 Heat flow through the solid only arises when

solidification takes place from mold walls (cooler than
melt)
 Heat flow into the liquid only happens if the liquid is
supercooled below Tm (melting T)
 This happens if nucleation occurs at impurity particles in
the bulk of the liquid.
 Since supercooling is required before nucleation, the first
solid particles will grow into the supercooled liquid and
the latent heat is conducted away into the liquid.
 So, spherical particles will then form “arms” in many
directions (dendrites); these are thermal dendrites,
different from dendrites in alloys.

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 4/11/2018

Dendritic growth

 (a) Spherical nucleus

 (b) The interface becomes
unstable
 (c) Primary arms developed
in crystallographic direction
 (d) Secondary and tertiary
arms developed
How do such complicated structures arise?
Secondary arms arise because there is a
falling temperature gradient between arms
such that Ta > Tb

Free growth of pure solid or alloy is intrinsically

unstable

Glicksman ∆T = 4 K
∆T = 1 K

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 4/11/2018

3D model – Dendrite Growth

The surface coloring represents the

relative concentration of each of the
two metals at the surface of the
dendrite. This simulation uses the
phase-field method for modeling

Microstructure transitions: summing up for G>0

T
cells dendrites
TL(x0)
G1>0
Absolute stability
Plane front

G2>G1

TS(x0)

10-4 10-2 1 102

V (mm/s)

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 4/11/2018

Dendrite fragmentation

 Fragmentation mechanism
 Mechanical fracture
 Melting

 Transport of fragments out of mushy zone

 Gravity/buoyancy
 Convection - stirring

 Survival and growth of dendrite

fragments
 Low temperature gradients

 Constitutional undercooling

Segregation at Dendrite tip - Cellular Automaton

(CA) Model

The addition of a strongly partitioning

solute

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 4/11/2018

Solute enrichment / tip undercooling and grain

competition

Films by Esaka/Kurz, EPFL, Switzerland, 4-3

+ Fleurentin, grain selection

Microstructure transitions: what does affect CET

transition

CET transition by increased

withdrawal rate
Hunt, 1985 And decreased gradient
Growth front
undercooling (V)
Number of nuclei Billia, X-ray video of Al-20wt%Cu

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 4/11/2018

CET (columnar to equiaxed transition)

A schematic illustration of the growth of columnar grains,

showing the competition near a converging and a diverging
grain boundary. We also show the extension of the left
columnar grain into the open space after a re-entrant corner,
and the competition with equiaxed grains that nucleate in the
undercooled region ahead of the columnar dendrite front.
(Rappaz and Gandin, 1993). two-dimensional simulation shows CET

Dendrite fragmentation and columnar front

blockage

Mathiesen, 2006

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 4/11/2018

Dendrite Arm Spacing

• Dendrite morphology in usual
casting and ingot-making processes
remains largely unchanged over
wide ranges of cooling rates. It
simply becomes finer as heat is
extracted at greater rate.
• At very high cooling rates, when
primary arm spacing becomes very
small, secondary and tertiary arms
may be absent;
• The dendrite is able to branch
sufficiently to reduce this
supercooling to a very low value.
• Secondary dendrite arm spacings
also depend directly on cooling
rate. ∆
. -n

n : 1/3 for SDAS, ½ for Primary

DAS vs Cooling rate

(Characteristic sizes)

Dendrite
spacing (µm)

Cooling rate G.V (°C/s)

 p  G  V 0 .5  s  G  V 0.3
coarsening controlled by
Space filling condition
solute diffusion in the liquid

Allows evaluating
local cooling rate in castings

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 4/11/2018

Growth modes
morphology & temperature distribution

Directional Growth of Free growth of equiaxed

Columnar crystals crystals

Pure
metal

Alloy

Positive G Negative G

Reproduced from:W. Kurz & D. J. Fisher:

Fundamentals of Solidification
Trans Tech Publications, 1998

G/V Map

skin

center

Kurz

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 4/11/2018

Eutectic growth, the

coupled zone

Three phase solidification

Eutectic Peritectic Monotectic

l α+β l+α β l1 α+l2

Ce

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 4/11/2018

The types of invariant reactions in a binary equilibrium phase

diagram at constant pressure

Eutectic solidification
 When a binary eutectic solidifies, two solid
phases form cooperatively from the liquid:
Lα+β
 Normal or Anomalous
Alternate lamellae
 Normal = alternate lamellae, or rods of the
minor phase embedded in the major phase
 Anomalous = faceting; has high entropy of
melting
Anomalous Solidification:
 Occur in systems when one of the solid phases is Rod-like eutectic
capable of faceting, i.e. has a high entropy of
melting.
 There are many variants of these structures the
most important commercially being the flake
structure of Al—Si alloys.

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 4/11/2018

Eutectic growth

Growth
direction

•Simultaneous, cooperative
growth of 2 or more phases
•Diffusion parallel to growth front
•Isothermal growth front
•Characteristic lamellar spacing, 
determined by diffusion and curvature

2V  K1 T  K 2 T  K 3 V

  

divorced eutectic (Fe-spheroidal graphite)

Stefanescu, 2011

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 4/11/2018

Different types of eutectic microstructures

More complex arrangements of the two phases occurs if interface attachment kinetics are sluggish
(usually encountered for crystals that grow from liquid with crystallographic facets). Then two solid
phases grow independently from the melt with very little communication of the solute fields in the
liquid. This leads to much coarser mixture of the two solid phases (divorced eutectic).

a - globular eutectic
b – acicular (needle-like) eutectic
c - lamellar eutectic
d – Chinese script

Growth of lamellae
 2 phases grow cooperatively
behind a planar solidification
front.
 As the alpha rich phase solidifies, 
B A
excess B atoms diffuse laterally
and is incorporated into the beta 

rich parts. 

B A

 A atoms rejected ahead of the beta

phase diffuse into the alpha parts.  V

 Growth Rate dependent on

interlamellar spacing, lambda
(small spacing = fast growth).

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 4/11/2018

2D model directional solidification - Eutectic

colonies

Phase field calculation results showing the time evolution of colony formation for an alloy with a small amount of
third element (impurity) added to a binary eutectic. The smooth contours ahead of the front represent isoconcentration
lines of the ternary impurity; the small “halos” just in front of the growing lamellae are a visualization of the interlamellar
eutectic diffusion field, (Plapp and Karma, 2002).

M. Plapp, Laboratoire de Physique de la Matière Condensée, Ecole Polytechnique , France

T = Tc + Tr
Undercooling

V C Tbr
 2C  0 Irregular eutectics
D x Regular eutectics

Assumptions:
isothermal interface
densities of all phases are the same ex Spacing br
10 -1
r
T    c V Nieswaag/Zuithoff 1975
Lamellar spacing, cm

ex Tiso  2 r Assumption:

10-2
Lakeland
ex2 V   r / c extremum criterion 1964

Tiso2 V 1  4  r c Jackson-Hunt
10 -3
10 -5 10 -4 10 -3
Growth velocity, cm/s

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 4/11/2018

J-H Theory

Diffusion front assumed to be planar

• α and β have equal undercooling
• Does not not give upper or lower
bounds on λ
• Experimentally one observes that the
stable λ is the one at which the average
undercooling of the front is minimum
(this idea goes back to Zener)
• The average undercooling as function
of λ can be numerically calculated to a
high precision.
• How λ is selected is still somewhat
controversial

The J-H theory works well for Sn-Pb but not for other systems.

Proposed growth behavior of irregular eutectics

Proposed growth behavior of irregular eutectics, showing branching at λbr and termination
at λex. (a) Fe-graphite eutectic growth at V: 1.7x10-2 µm/s and (b) schematic representation
of solid–liquid interface during growth (Magnin and Kurz, 1987).

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 4/11/2018

Interface instabilities of eutectics

Off-eutectic
Composition

3:rd element

a Instability of one phase resulting in dendrites +

interdendritic eutectic.
b Instability of both phases resulting in twophase Reproduced from:W. Kurz & D. J. Fisher:
eutectic cells or dendrites Fundamentals of Solidification
Trans Tech Publications, 1998

Off-eutectic

 Solidification of an off-
eutectic alloy in a
temperature gradient:
a. Alloy composition in
relation to the phase
diagram
b. Schematic solidification
front
c. Temperature variation
across solidification front
d. Inset is a transverse
section through a dendrite

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 4/11/2018

Off eutectic growth

Example in Al-30%Cu

Low temperature
gradient, high growth
rate

Dendrites + eutectic

Reproduced from:W. Kurz & D. J. Fisher:

Fundamentals of Solidification
Trans Tech Publications, 1998

Coupled Zone

• The coupled zone represent the range

of the chemical composition, growth
rate that depend of interface
temperature (solidification rate) in
which a completely eutectic structure
obtained .
• Way of marking coupled zone on the
basis of the theory of the competitive
growth

(a) The coupled zone encompasses the α

liquidus extension: coupled eutectic growth
occurs directly from the primary α dendrites.
(b) The coupled zone does not encompass the α
liquidus extension: haloes of β form around
the primary α dendrites for any significant β
nucleation undercooling Tn

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 4/11/2018

Sensor 

Parvati, Chennai government museum,

Copper-base statue (Cu>96%)
Sharada Srinivasan, JOM, 2016

Decoupled, divorced eutectic

Al-5Cu

•Major phase grows on existing dendrites.

•Small amount of eutectic
•No cooperative growth
Evolution during solidification of an Al-8%Cu
specimen. the primary Al-rich phase forms and
grows. At the same time, the remaining liquid
becomes more and more absorbent (lighter and
lighter) indicating Cu enrichment.

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 4/11/2018

Eutectic Modification

Modification of growth mechanism

Eutectic silicon crystals in Al-Si

Transition from coarse lamellar

to fine fibrous eutectic

Improves ductility

Addition of small amounts

(100 ppm) of Na, Sr, (Ca, Sb)

Increases porosity

100 ppm Sr

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 4/11/2018

Mechanism of Eutectic modification (Al-Si)

Atoms of modifier causes growth "twin plane re-entrant

branching (Impurities Induced edge" (TPRE) mechanism
Twinning)

IIT Mechanism

(a) BF STEM image. An

internal boundary of the
eutectic Si phase along a
{111} plane is visible.
Both Si fibre segments
are oriented close to
the [011] zone axis. An
enlarged view of the
area marked by the
rectangle in (a) is imaged
using: (b) BF STEM, (c)
HAADF STEM, (d) and
(e) EDX mapping of Sr
and Al, respectively. The
internal boundary of the
eutectic Si phase is
Microstructure showing a eutectic Al/Si interface of Al– marked by arrows
10 wt.% Si–0.1wt. % Fe alloy modified by 200 ppm Sr in (b) and (c).

Timpel et al., 2012

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 4/11/2018

TPRE Mechanism
a) shows Eu atoms between
every two Si atomic
columns are located at
the twin plane re-entrant
edge, indicating that
poisoning of the TPRE
mechanism is active.
b) shows Eu-rich atomic
columns are located at
the intersection of Si
facets and respectively
twins, indicating that the
IIT mechanism is active.
c) shows Eu atoms are
located ahead of the
growing Si twins, forming
a continuous Eu-rich
layer, indicating that a
solute entrainment
occurs within eutectic Si.

The roles of Eu during the growth of eutectic Si in Al-Si alloys. Li et al., Sci Report, 2015

Modification of graphite in cast iron

Small additions of Mg and FeSi to cast iron changes

morphology of facetted graphite from flakey to nodular

Effect of both nucleation and growth mechanism

Grey cast iron Ductile iron

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 4/11/2018

Growth mechanism of graphite

For recent study regarding

the graphite growth, look at
the work by K. Theuwissen
and J. Lacaze, INPT
(http://ethesis.inp-
toulouse.fr/archive/0000239
3/) – In Francais)

Spheroidal Graphite Growth Model

a Growth by helical bending—conical helices radiating from a

common center (Double and Hellawell 1975).
b Circumferential growth of graphite (Sadocha/Gruzleski 1975).
c Circumferential growth with boundary tilt through twinning.
d Three stages growth (Amini and Abbaschian 2013).

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 4/11/2018

Peritectic
Solidification

Peritectic solidification

 L + α  β, but
hardly ever happens

 In reality, it’s more

like L + α  β + γ
called a divorced
eutectic.

Primary: L→α
Peritectic: L + α →β
Eutectic: L → β+γ

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 4/11/2018

Peritectic reaction and peritectic transformation

The peritectic solidification starts with a peritectic reaction in which all three phases, α, β, and liquid are
in contact with each other. The peritectic β phase will grow along the S/L interface α/L, driven by liquid
supersaturation. Solute rejected by the β phase will diffuse through the liquid to the α phase contributing
to its dissolution. The β phase will also thicken in the direction perpendicular to its growth, by direct
growth in the liquid and at the expense of the α phase by solid state diffusion. Once the reaction is
completed and all the α/L interface is covered by β, the peritectic transformation starts.
The liquid and the primary α phase are isolated by the β phase. The transformation α ⇒ β takes place by
long-range solid-state diffusion through the peritectic β phase.

Peritectic reaction

Peritectic reaction: Ferrite + Liquid reacting to Austenite

Clearly visible in experimental cross-section and is the austenite rim surrounding the
primary ferrite

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 4/11/2018

Cast Structure

Ingots and castings solidification

Ingot structure consists of 3 zones:

 Chill Zone: of equiaxed crystals, high
pour temp, crystals close to mold wall
form chill zone

 Columnar Zone: elongated, column-

like grains, grown perpendicular to
mold wall, and close to the direction
of heat flow

 Equiaxed Zone: grains randomly

oriented in the center of the ingot.
Perhaps formed by melted-off
dendrite arms.

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 4/11/2018

Chill zone

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Competitive growth of the grains in the chill zone results in only

those grains with favorable orientations developing into
columnar grains

Different cast structure of turbine blade

146

Left to right: polycrystalline turbine blade, directionally solidified multi-grain blade, single
crystal jet engine blade
Dendrite micrograph of nickel-base superalloy aligned during DS processing of turbine
blade.

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 4/11/2018

Solidification of Single Crystal

 For some applications (Ex: Gas

turbine blades-high temperature
environment), single crystals are
needed.
 Single crystals have high
temperature creep resistance.
 Latent heat of solidification is
conducted through solidifying
crystal to grow single crystal.
 Growth rate is kept slow so that
temperature at solid-liquid
interface is slightly below melting
point.

(After Pratt and Whitney Co.) Growth of single crystal for turbine airfoil.

Czochralski Process – Si single crystal

 This method is used to produce single crystals of silicon for

electronic wafers.
 A seed crystal is dipped in molten silicon and rotated.
 The seed crystal is withdrawn slowly while silicon adheres
to the seed crystal and grows as a single crystal.

Silicon Boule

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 4/11/2018

Continuous casting

 Molten metal is cast into either semi finished or finished parts.

Continuous casting of steel ingots

4-10

Direct Chill (DC) casting

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 4/11/2018

Solidification in Welding

Schematic diagram showing interaction between the heat source and the base metal. Three distinct regions in the
weldment are the fusion zone, the heat-affected zone, and the base metal. (S.A. David and T. DebRoy, 1992)

 Depending upon the type of mated being welded as well as plate

thickness, the base metal behaves as a very efficient heat sink,
and already at T  Te solidification nuclei form at the oxide-free
surface of the melted-back base material.
 Since the melt has approximately the same composition as the
base metal, 'wetting' of the base metal is very efficient and  = 0.
 This implies in turn that there is almost no nucleation barrier to
solidification and hence very little undercooling occurs.
 Solidification is thus predicted to occur epitaxially, i.e. nuclei will
have the same lattice structure and orientation as the grains at
the solid-liquid surface of the base metal, and this is what is
observed in practice.

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 4/11/2018

Growth in Weldpool

Illustration of the growth of Illustration of the effect of

columnar crystals in the weld, increasing welding speed on
and how growth continues to the shape of the melt pool and
occur approximately normal to crystal growth in fusion welds.
the isotherms.

Weld metal grain structure – Welding Speed

Schempp et al., Welding Journal, 2014

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 4/11/2018

Weldment Cross section

Rapid Solidification

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 4/11/2018

History

Long produced - without being aware of it - in electrolytic plating

• Rapid solidification at ~ 106C/sec cooling rate (Cooling Rate >104 -107
oK/s)

• Splat cooling 1963 (P. Duwez and R. H. Willens)

• “Melt Spinning” 1969 (R. Pond, Jr. and R. Maddin) molten metal
stream impinges on the inner surface of a rapidly rotating hollow
cylinder. Ribbons of 10’s of micron in thickness
• ~ 1985 ..1990 “Bulk” Metallic Glass. First Au80Si20 (Harvard,
Turnbull), later Zr and Pd based (Tohoku, Cal Tec). Up to 5 mm. Rates
as low as 1oK/s

Metallic Glass Structure

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 4/11/2018

Amorphous Alloys Properties

Amorphous metallic alloys combine higher strength than

crystalline metal alloys with the elasticity of polymers.

Rapid Solidification - Liquid Phase Deposition

Chill Block Melt Spinning

-Like free flight melt spinning, chill block melt
spinning employs a jet of liquid metal extruded
through an orifice.

-In chill block melt spinning, however,

solidification is achieved when the molten jet
impinges on the surface of a rotating solid
substrate (rotating water cooled metal disks

- Filaments several mm wide and 25

micrometers thick are produced

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 4/11/2018

The critical casting thickness versus the year in which alloys were discovered.
Over 40 years, the critical casting thickness has increased by more than three
orders of magnitude.

Metallic Glasses Application

Sport equipment

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 4/11/2018

Solidification Defect

Shrinkage effects

 Most metal shrink on solidification and this has

important consequences for the final ingot structure.
 Narrow freezing range = mushy zone is narrow, and
as the outer shell of solid thickens, the level of
remaining liquid decreases until final solidification
when the ingot contains a cavity (pipe).
 Wide freezing range = mushy zone occupies whole of
the ingot….no pipe formed, but the liquid level falls
across the width of the ingot…..leaves voids or pores.

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 4/11/2018

Shrinkage Defect

©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used
herein under license.

Figure (a) Shrinkage can occur between the dendrite arms. (b) Small secondary dendrite
arm spacings result in smaller, more evenly distributed shrinkage porosity. (c) Short
primary arms can help avoid shrinkage. (d) Interdendritic shrinkage in an aluminum
alloy is shown (x 80)

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 4/11/2018

Defect in Single Crystal Casting

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 4/11/2018

Segregation in ingots and casting

 Macrosegregation
: composition
changes over
distances
comparable to the
size of the
specimen

 Microsegregation:
occurs on the
scale of dendrite
arm spacing

Grain Movement simulation in an Al-Si Ingot Casting

In large castings, when equiaxed solidification occurs, the equiaxed grains may move, due
to fluid convection ahead of the mushy zone. The evolution of the temperature and velocity
fields during the solidification, one can well see the vortex due to natural convection
Rappaz, 1996, Gandin,1998 in Thevoz, JOM, 2002

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 4/11/2018

Microsegregation
Intercellular solute control
volume within a cellulated solid-
melt region.
 The expanded inset shows
the solute mass flows
occurring in the steady-state
cellular microsegregation
model.

Factors that lead to segregation

 Shrinkage due to solidification and thermal

contraction
 Density differences in the interdendritic liquid
 Density differences between the solid and liquid
 Convection currents in the liquid….
 all cause mass flow over large distances during
solidification

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Freckle Formation - Channeling

The formation of the defect has been defined as bouyancy-driven flow in the
liquid/solid region of the casting

Fig. (a) 2-D FVM simulation of a freckle formation in an Ni-Al alloy. The left
and right panels show positive and negative segregation index maps

Freckles Formation – Indium Gallium Alloy

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References

 M. Fleming, Solidification Processing, 1974

 D. A Porter and K.E Easterling, Phase Transformation in Metals
and Alloys, 2nd ed. Chapman and Hall, London, 1992.
 R.W. Chan, P. Haasen, Physical Metallurgy, North-Holland,
1996.
 W. Kurz and D.J. Fisher, Fundamental of Solidification, Trans
Tech Publication, 1998
 ASM Handbook Vol. 15, Casting, ASM International, 2008.
 J.A. Dantzig and M. Rappaz, Solidification, CRC Press, 2017
 D.M. Stefanescu, Science and Engineering of Casting
Solidification, Springer US, 2015
 D. Ferdian, INPT, 2014
 J. Lacaze, Solidification course, 2018

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