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Solidification Lecture 2

Solidification, Lecture 2 NTNU Homogeneous and heterogeneous nucleation occur during solidification. Heterogeneous nucleation lowers the activation energy barrier by occurring on a substrate. Grain refinement can be achieved through inoculation of potent substrate particles and controlling undercooling. Columnar to equiaxed transition occurs through dendrite fragmentation, which produces new grains when fragments survive transport and growth in the undercooled melt. Facetted crystals like non-metals grow through successive nucleation of atomic planes while non-facetted crystal growth in metals occurs via a rough interface. Growth mechanisms and rates depend on the type of solidification and can be modified through impurity additions.

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87 views

Solidification Lecture 2

Solidification, Lecture 2 NTNU Homogeneous and heterogeneous nucleation occur during solidification. Heterogeneous nucleation lowers the activation energy barrier by occurring on a substrate. Grain refinement can be achieved through inoculation of potent substrate particles and controlling undercooling. Columnar to equiaxed transition occurs through dendrite fragmentation, which produces new grains when fragments survive transport and growth in the undercooled melt. Facetted crystals like non-metals grow through successive nucleation of atomic planes while non-facetted crystal growth in metals occurs via a rough interface. Growth mechanisms and rates depend on the type of solidification and can be modified through impurity additions.

Uploaded by

Shabid Ashraf
Copyright
© © All Rights Reserved
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Solidification, Lecture 2

NTNU

Nucleation
Homogeneous/heterogeneous
Grain refinement
Inoculation
Fragmentation
Columnar to equiaxed transition
Crystal morphology
Facetted non-facetted growth
Growth anisotropy / growth mechanisms
Modification of Al-Si and cast iron
1

Nucleation

NTNU

Spontaneous formation of new


crystals
Cluster formation
Homogeneous nucleation
Number of clusters with radius r:

nr n0 exp

Gr
kT

Gr cluster free energy


n0 total number of atoms
k Boltzmans constant
T temperature
2

Nucleation activation energy

NTNU

Change in free energy


solidification

s/l interface

4 3
G = r g + 4r 2
3
Spontaneous growth 2
above radius r * =

s f T

Activtion
energy

3
16
G * =
3s2f (T) 2

Nucleation

NTNU

Rate
B
N = A exp(
2)
(T)

Undercoooling

nr n0 exp

Gr
kT

r* =

2
s f T

Heterogeneous nucleation
Nucleation on solid substrate
Reduction of nucleation barrier
Wetting angle

NTNU

Ghet Ghom f ()

Conditions for efficient nucleation


NTNU

Small wetting angle,


Low surface energy between substrate and crystal
Good crystallographic match

Lattice match between


Al and AlB2

Nucleation on AlB2 substrate


particles, inoculation

NTNU

AlB2

AlB2 addition

No addition

Nucleation and growth in a pure metal

NTNU

T
Recallescence
Growth

Tg

Nucleation

Tn

Undercooling ahead of
solidification front is
needed for nucleation
of new grains.
Can be achieved by
alloying.

Conditions for grain refinement


Substrate particles

NTNU

Undercooling

Potent

Constitutional

Large number

Growth restriction

Well dispersed

Strongly segregating
alloying elements

A pure metal can not be efficiently grain refined!

Growth restriction in aluminium

NTNU

Q mC0 k 1
Element

m(k-1)

max C0 (wt%)

Ti
Si
Mg
Fe
Cu
Mn

246
6.1
3.0
2.9
2.8
0.1

0.15
12
35
1.8
33
1.9
10

Aluminium grain refiner master alloys


NTNU

Typical composition: Al-5%Ti-1%B


Formation of insoluble TiB2
Ti/B ratio in TiB2 : 2.2/1
Large TiAl3
Small TiB2
10-50 m
1-3 m

50 m
11

Grain refinement of aluminium

NTNU

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

12

Substrate particle size, d


NTNU

4
d=
s f T
Too small particles will
need high
underecooling

T
GrainInitiation
Initiation(K)
T for
for Grain

1
0.8
0.6
0.4
0.2
0

2
4
6
Particle Diameter (m)

13

Industrial grain refinement practice

NTNU

Alcoa
14

Dendrite fragmentation

NTNU

X-ray video of Al-20wt%Cu


Growth of collumnar front
Dendrite fragment by melting
Formation of new grain
New front established
New fragments melt

15

Columnar-to-equiaxed transition;
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

NTNU

Electromagnetic stirring of steel


NTNU

Stirring gives
larger fraction
of equiaxed
grains

17

Growth

NTNU

Controlling phenomenon

Importance

Driving force

Diffusion of heat

Pure metals

Tt

Diffusion of solute

Alloys

Tc

Curvature

Nucleation
Dendrites
Eutectics

Tr

Interface kintetics

Facetted crystals

Tk

18

Interface morphology

NTNU

Facetted
Atomically smooth
=sf /R>2
Non-metals
Intermetallic phases
Non-facetted
Atomically rough
=sf/R<2
metals
Reproduced from:W. Kurz & D. J. Fisher:
Fundamentals of Solidification
Trans Tech Publications, 1998

19

Facetted crystals

NTNU

Atomically smooth interface


Large entropy of fusion
Growth by nucleation of new atomic layers
Large kinetic growth undercooling, Tk
Large growth anisotropy

20

Growth anisotropy

NTNU

Cubic crystal bounded by (111) planes


Growth of (100)
Bounded by (110) planes
Growth of (100)
Reproduced from:W. Kurz & D. J. Fisher:
Fundamentals of Solidification
Trans Tech Publications, 1998

Fastest growing planes disappear


Crystals bounded by slow growing planes

21

Growth anisotropy
Anisotropy increases with

NTNU

V = K(hkl )Tk

22

Growth mechanisms

NTNU

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

23

Growth rate

NTNU

V = K 2 (Tk ) 2

V = K1Tk

K4
V = K 3 exp(
)
Tk

Reproduced from:M. C. Flemings


Solidification Processing
Mc Graw Hill, 1974

24

Modification of growth mechanism


Eutectic silicon crystals in Al-Si

NTNU

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

25

Mechanism of modification

NTNU

Atoms of modifier
causes growth branching

26

Modification and growth undercooling


NTNU

Eutectic growth
temperature
decreases about
10 K.
Fading due to
oxidation of
modifier.
Faster fading
with Na than Sr

27

Modification of graphite in cast iron


NTNU

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

28

Summary / conclusions

NTNU

Spontaneous formation of solid clusters. Homogeneous nucleation


Energy barrier due to s/l interface large at small crystal sizes. Needs
undercooling
Heterogeneous nucleation on solid substrate. Lower activation energy
lower undercooling
Low wetting angle potent substrate for nucleation good
crystallographic match between substrate / growing crystal
Undercooling ahead of growing front necessary for nucleation of new
equiaxed grains. Provided by strongly segregating alloying elements
Efficient grain refinement can be achieved in aluminium alloys by
inoculation of substrate particles, TiB2 and Ti for growth restriction
Substrate particles must not be too small. That will give large
undercooling.

29

Summary / conclusions

NTNU

Columnar to equiaxed transition grain refinement can be achieved


by fragmentation of columnar dendrites. Provided by convection.
Transport out of M.Z and survival in undercooled melt at low
temperature gradient.

30

Summary / conclusions

NTNU

Metals have low entropies of fusion and grow in a non-facetted way


with an atomically rough interface
Non-metals and intermetallic compounds have normally high fusion
entropies and grow in a facetted way with a smoth interface.
Growth of facetted crystals occurs by successive nucleation of new
atom planes at high kinetic undercooling
Facetted crystals show large growth anisotropy. Fast growing planes
disappear while slowest growing planes bounds the crystals
Facetted crystals often provide nucleation sites for new atom planes at
twin boundaries or screw dislocations
Growth rate of non-facetted crystals is proportional to kinetic
undercooling. Dislocation growth shows a parabolic law and growth by
two-dimensional nucleation an exponential growth law

31

Summary / conclusions

NTNU

Growth mechanisms in facetted crystals can be very sensitive to


impurities. Can be utilised for modification of morphology, Examples
are modification of Si in Al-Si by Na or Sr and modification of graphite
in cast iron eutectics by Mg.

32

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