Annie Antoni -Zdziobek

Kader Zaidat
Philippe Jarry
 CONTENTS

I. Solidification
S f processing in relation with macro / micro-structure

II. Solute partitioning : equilibrium / non-equilibrium solidification

III. Solidification microstructures : cells - dendrites - eutectics - peritectics

IV Solidification paths in ternary systems

IV.

4
Is solidification a crucial topic?
Ex1: Turbine blades

Turbine disk

2 juin 2006, Turbine blade

Los Angeles airport!

Creep 5

Ex2: Packaging in microelectronics: flip-chip interconnection

Structural integrity of solder joint:

Æ electrical performance
Æ thermal performance

New soldering materials:

Ternary alloys SnAgCu, AuSnCu…

Solidification path? Brittle phases??

Needles
N dl off
intermetallic
phases
Cu6Sn3, Agg3Sn

6
 1. Introduction
1.1 Solidification p
parameters
ex : moulding
Co initial alloy concentration

Tl liquidus
q temperature
p

Tc casting temperature Æ superheat 'T = Tc - Tl

Te mould (external) temperature

Co țs thermal conductivity of solid alloy [W.K-1.m-1]
Tc țm thermal conductivity of mould [W.K-1.m-1]

h alloy mould heat transfer coefficient [W

alloy-mould m-22.K
[W.m K-11]

Dm mould thermal diffusivity [m2.s-1]

G thermal gradient [K.m-1]

T’ cooling rate dT/dt [K.s-1]

C
h
Tl V growth (solidification) rate (velocity) [m.s-1]
Te
G,T’,V ?
ks km

Dm

Solidification : a matter of heat and mass transfer

Heatt transfer:
H t f Solute
S l t and d mass transfer:
t f
- Diffusive - Diffusive
- Convective - Convective
- Radiative
R di ti
8
Heat diffusion in solidification
K = conductive heat transfer
N = Newtonian transfer across
mould/metal interface
C = convective heat transfer
R = radiative
di ti h heatt ttransfer
f

J = -K
K grad T thermal flux [W
[W. m-22]
K = thermal conductivity [W. m-1.K-1]
Lf = latent heat of solidification [J. m-3]
V = velocity of interface [m.s-1]

Liquid and solid regions Liquid/solid interface Solidification is exothermic

wTs
div >K s grad Ts @ C p ,s + Jth conservation K sGth ,s K LGth ,L  Lf V
wt
wT + T continuity TL Ts Ti
div >K L grad TL @ C p ,L L
wt

Solid/mould interface J th hi Ti ,s  Ti ,Mould h = heat transfer coefficient [W. m-2.K-1]

9

1.2 - Structure of ingots

1 2 1 Macrostructure = scale of the ingot (eye)
1.2.1
1
2 3
(1) outer chill zone : easy nucleation against
mould walls (equiaxed zone)
(2) columnar zone : selection of grains that
grow faster than the neighbours Æ anisotropic
(3) central equiaxed zone
Æ not always present

dendrites

heat flux
* columnar growth : rapid growth of
some crystallographic directions
when // heat flux
<100> for cubic structures
_
 10 1 0 ! for hexagonal structure

[POR2001]
(b)
10
* transition from columnar (2) to central equiaxed zone

mould solid Liq + solid Liq

TM TS mushy zone TL T
xm

* small dendrite arms are broken by the liquid flow (convection) and brought ahead of the
liquid-solid interface
Æ nuclei for equiaxed growth

* key parameters (promoting equiaxed transition)

¾ small superheating of the liquid
¾ high convection of the liquid
¾ large size of the mushy zone (xm) xm = ǻT0 / Gm .
i range ('T0) or llow th
--> smallll ffreezing thermall gradient
di t (Gm)
11

* Transverse cross sections of cylindrical ingots

(a) pure metal ?
(b) alloy M-X poured in a sand mould ?
(c) same alloy M-X poured in a metal mould ?

mushy mode skin mode

* examples for sand casting :

Al and Mg alloys Æ mushy mode 20
mm
low alloy steel Æ skin mode

* ffor isotropic mechanical properties : need to promote mushy mode + small grains
Æ introduction of a nucleating agent which promotes heterogeneous nucleation (sl 16)

12
* Macro-defects in castings material ǻV/V
(%)
* shrinkage :
Al -7
7.0
0
- in the last region to solidify
Cu -5.1
- origin : liquid-solid contraction Mg -4.0
Zn -3.7
Fe -3.4
Pb -2.7 pure Al Al-4.5Cu
Ga +3.2
* macro-porosities H2O +8 3
+8.3
[FLE 74] Æ use of a riser
- gas dissolved in the liquid

* macro-
segregations
- heterogeneous
distribution of the
phases in the ingot

• effect of the gravitation

(a) ( densities)
* cross-section of an electrical • effect of liquid flow
connector in a Zn
Zn- 4% Al alloy • changes in heat
(zamak), processed using pressure die transfer velocity
casting [FLE 76]
13

1.2.2 Microstructure : scale of the phases (optical microscopy or SEM)

Al - 5% Si - 3% Cu alloy (wt%)

Solidification path :
(1) Liq Æ D<<Al>>
primary phase
Liq Æ D<<Al>>
(2) Li  Al + Si
binary eutectic
(3) Liq Æ D
D<<Al>>
Al + Si

+ TAl2Cu
1
ternaryy eutectic
D<<Al>>
2
solidification
path (S-G model) * Micro-defects :
3
<<Si>> • micro-porosities
• micro-shrinkage
• micro-segregation (part 2)
14
1.2.3 - Nucleation (some reminders) --> for details, see Thermodynamics lecture book
(Phelma-1A) --> Chapter 2 - small systems
Ch i l d
Chemical i i fforce : 'Gv
driving G
'Gv < 0 at T = Teq - 'T But : problem = creation of interfaces

'Gsurf > 0
'T : undercooling T < Teq

'Gv < 0

'T small ¾ with increasing g 'T :

g undercooling
'T high
• the chemical driving force 'Gv n
• r* and 'G* p
--> easier nucleation
15

Heterogeneous nucleation / homogeneous

'G*het = 'G*hom * f(T)

T
wetting
angle f(T)

0 0
10°
10 1.7
1 7EE-4
4
30° 1.3 E-2
90° 0.5
180° 1

¾ wetting
etting on solid particles alread
already
present (impurities, mould walls)
promotes easier nucleation
p
--> heterogeneous

16
 • example : undercooling during solidification of pure Ni in an Al2O3 crucible
Differential Thermal Analysis (DTA) experiment)

sample T (°C)
ref

Tm =1455

furnace

Ts Tref
time

'Theat
= 'T = heat
- Tref
Tsampleflow Nis Æ Nil
Tm
Tsample - T
flow
ref Nil Æ Nis
1455°C

endoth exoth

heating cooling
1355°C
T(°C) T(°C)

undercooling | 100°C !
Æ measure melting (liquidus)T upon heating 17

Industrial process: --> use of nucleating agents to promote nucleation / reduce grain size

example : Al -5%
5% Si - 3% Cu alloy (wt%)
1 2 3
1 : no addition
2 : medium addition
3 : correct addition addition of Al- 5% Ti- B before
pouring
Æ precipitation of TiB2 from
620 the liquid
q ((Tm=3225°C)) = nuclei
for D<<Al>> primary dendrites

564 onset of
Al-Si
eutectics

ternary eutectics
CET Al-Ni + refiner

18
 1.3 - Some solidification processes

1 3 1 Continuous-casting
1.3.1 Continuous casting

(Ladle)
Fos sur Mer : (x2 installations)
‰ 2.4 Mt / year
‰ Extraction speed : V § 1.5 m/min
(Tundish)
‰ total length : 5.7 to 14.3 m
‰ width : 1.5 to 2.2 m
‰ thickness : 0.22 m
(Mould)

Appendix 2 :
electromagnetic stirring
((2nd cooling)
g)
(Blowtorch)
(plate levelling) (cutting)
[BIR 94] 19

1.3.2 Directional solidification

- Thermal gradient G (# 10 -100

100 K/cm) and solidification rate V (# some μm/s to cm/h)
are controlled separately (= controlled solidification)

z Bridgman solidification z Czochralski pulling z Floating zone process

of Si monocrystals for monocrystalline Si
Æ § 3.2
Æ § 3.2 Æ § 3.2

melt Si-poly
Si -
mono RF coil
solid

Si-mono

http://soliditice.minatec.grenoble-inp.fr/ 20
 1.3.3 Welding and superficial remelting

z several heating processes : arc

arc, plasma
plasma, laser
laser, electron beam
- high convection V | 10-3 - 1 m.s-1
- high
g values of solidification p
parameters: G | 106 K.m-1
T’ | 104 K. s-1

Electron Beam welding of Fe-15Cr-15Ni [RAP 1989]

1.3.4 Rapid
p solidification

* high values of solidification rate V (| 1 m.s-1) and cooling rate T’ (| 106 K.s-1)
* several effects may be obtained with increasing V
21

(1) the size of the microstructure decreases (dendritic and eutectic spacings)
Cs
(2) solute trapping : k Æ1 at high growth rate and T < T0 temperature
CL

(3) production of amorphous alloys CCT diagram

(or nanocrystallized)

Conditions to produce metallic glasses :

high cooling rate # 105 – 106 K.s-1
Æ "melt
melt spinning
spinning" or "splat
splat cooling
cooling".
22
 1.4 - G(V) map for the solidification processes
melt spinning
laser remelting

welding

continuous casting
105

10-3 K/s 10-1 10 103

Thermal g
gradient G(K.m
( -1) versus g
growth rate V ((m.s-1) for the different solidification
processes. from [GAU 1997].
23

2- Solute partitioning and non-equilibrium solidification

z Solute partitioning
Solid crystals solidifying from a liquid of solute composition Xl have a different
solute composition: Xs z Xl (see phase diagram)
Ö Solute atoms redistribute between solid and liquid phases
Ö In the following cases, the equilibrium partition coefficient k, k = Xs / Xl < 1
Tm Æ composition of first solid nuclei @TL : X1 = k X0
TL
T2 XL Liq
* for k < 1 Æ solute atoms B are
XS
TS "rejected" from the growing solid
phase into the liquid

D
TE solid liquid ((A,B))
D B
B

X1= X0 Xmax XE (t,T2 ,XL ) (t+dt,T2+dT, XS)

A %B
k X0
24
 Ö Three limiting cases for solute redistribution, depending on the rate of solute
diffusion in the solid and in the liquid
Solute B is rejected
at the S/L interface

B atoms diffuse: B atoms diffuse: B atoms diffuse:

x at infinite rate in the x at infinite rate in the • at a finite rate in the

liquid liquid liquid
x at infinite rate in the x at infinitely slow rate x at infinitely slow rate
solid in the solid in the solid

" Equilibrium Scheil – Gulliver Diffusion layer in the

solidification " or model liquid
q
"Reversible solidification" Æ creation of cells or
(See phase diagram) dendrites
Æ Scheil – Gulliver
model can be used at
microscopic scale
Segregations at a
No segregations macroscopic scale
Microsegregations
25

z Equilibrium solidification ("equilibrium freezing")

Solidification path : evolution of liquid and solid amounts and compositions versus T°
ƒ Qualitative description : nature of phases grown from the liquid

Example : cast Mg-Al alloy A1: composition X0 < XM (with dendritic structure)

ƒ only 1 stage : TL Ì TS : Liq Æ D(Mg) "primary phase"

Tm A1
TL solid solution
T2 Liq @ TL (liquidus) : onset of solidification (first solid nuclei)
TS

D M E1 *

ƒ equilibrium @ T2 :

@ TS (solidus) : end of solidification (last liquid disappears)

X0 Xl XE X*
X1 X X(Al)
s
26
ƒ Quantitative description : lever rule (liquid and solid amounts and compositions versus T)

‰ equilibrium @ T2 : Liq l D(Mg)

Tm A1
XL XS
TL
T2 Liq Liq (XL)
global composition X0
TS
D(XS)
D D ( fD , XS) Liq ( fL , XL)
M E1 *

Phase diagram + mass balance Æ lever rule

ƒ solid fraction

ƒ fraction of
remaining liquid
X0 Xl XE X*
X1 Xs X(Al)

Æ "equilibrium" description assumes instantaneous homogeneization of liquid and

solid phases by infinitely rapid solute diffusion during cooling
Æ in most cases non realistic for the solid phase but more accurate for the liquid
27

Fractions of phases : units

D
‰ from phase diagram + lever rule :
mole fractions or mass fractions
‰ more important for the properties : volume fractions E

Æ starting from mass (wt) fractions: fDwt , fEwt

wt
fD

vol UD wt
fD
UD  UE : densities
fD
wt  U D 1 
wt
fD f wt
E
 fD wt
fD
UD UE UE

Æ starting from mole (mol) fractions : fDmol , fEmol VDmol VEmol : molar volumes

vol
mol
fD . VDmol mol
fD
fD
mol
fD . VDmol  f mol
E . VEmol VEmol
f mol
D  1 mol
fD
VDmol
28
ƒ "Equilibrium freezing" (lever rule)
Underlying hypotheses
(H1) Infinite diffusivity of solute (Al) in the liquid Æ homogeneous liquid (XL)
(H2) Infinite diffusivity of solute (Al) in the solid Æ homogeneous solid D (XS)
(H3) Local
L l equilibrium
ilib i att the
th interface
i t f : liquid
li id and
d solid
lid compositions
iti are given
i b
by
the phase diagram @ any interface temperature T

Result
 Using the Mg-Al phase diagram (sl. 26), draw the composition profile XAl through an ingot
(including solid and liquid phases) unidirectionally solidified along x direction (  casting)

@ T = T2

Heat flux solid liquid

x
XAl

X0

f f+df solid fraction f

29

ƒ Lever rule : simplification with linearization of liquidus and solidus

¾ 3 simplifications for solving analytically the problem :

(S1) liquidus equation with slope ml ȉ ȉ m  ml X l

(S2) Linearisation of solidus Æ slope ms ȉ ȉ m  ms X s

Xs X max ml
Æ the equilibrium partition ratio k is then constant: k
Xl XE ms

One can express Xl and Xs as a function of the solid fraction f

Xs

One can express f as a function of T, using:

Ö the
th liquidus
li id equation
ti : T = Tm + m. Xl
1 TL  T
Ö the definition of partition coefficient k Æ f
1  k Tm  T hyperbolic function

30
 Using Al-Si binary phase diagram, draw the evolution of T versus f
for 2 alloy compositions : Al-1%Si
Al 1%Si and Al-5%Si
Al 5%Si

31

z BUT : this model is not relevant for most practical cases of solidification because of
non realistic (H2) hypothesis for substitutional solute atoms Æ in fact substitutional
solute atoms do not diffuse at infinite rate in the growing solid

32
ƒ What is actually observed during most solidification cases ? @ T2

‰ Example : cast Mg-Al alloy A1: composition X0 < Xmax

ƒ unsufficient solid diffusion

to homogeneize the solid
phase DÆ "coring"

Æ departure from "global" equilibrium

Æ but the 2 phases are in "local" equilibrium at
interface : @ T2 @ interface : Liq (XL) l D (XS)

‰ 2 main observations :
(1) composition of primary solid solution D
is not homogeneous Æ microsegregation

(2) there is less primary phase than predicted by

XE = 33.25 "equilibrium" conditions
X1 = Æ accurate predictions with Scheil-Gulliver model
k X0

33

z Non-equilibrium solidification : Scheil-Gulliver model (no diffusion in the solid phase)

z relevant for most cases : "normal
normal freezing
freezing" solidification
Hypothesis of the model :
Ö (H1) Infinite diffusivity of solute in the liquid (// strong convection) Æ homogeneous liquid
Ö (H2*) "null diffusivity" of solute atoms in the solid Æ non homogeneous solid
Æ segregation of solute
Ö ((H3)) Local equilibrium
q at the interface : liquid
q and solid compositions
p are g
given by
y the p
phase
diagram at any interface temperature T

Simplifications for solving analytically the problem : similar to the equilibrium case : (S1) (S2)

* Solidification path
Heat flux solid liquid

(1) Mass balance for solute atoms B XB

when the solid fraction (f) increases
Xl+dXl
by (df).
Xl
Xs
(X l -X s ).df ( 1  f ) . dX l
kXo
f
f f+df
34
 f XL
df dXl dXl df dXl df dXl
1 f Xl  Xs Xl (1k )
(1k )
1 f Xl ³
(1k )
1 f ³ Xl
0 X0

 (1k ) > ln (1 f )@ 0f > ln XL @ XX0L >

l (1 f )  (1 k )
ln @ l
ln
XL
X0

XL X0 k X0
(1 f )  (1 k ) XL XS k XL
X0 (1 f )(1 k ) ( 1  f )1 k

¾ Mathematical limits for Xl and Xs when f Æ1 XS o f

XL o f

¾ Physical
Ph i l lilimits
i ffor Xl and
d Xs when
h f Æ1 XS o
XL o

Ö look at the phase diagram to stop the calculation at relevant values of (Xs , Xl )
35

Main results of Scheil-Gulliver model Tm

in a simple case of phase diagram TL
with eutectic Liq
T2
TS

D
TE

X1= X0 Xmax XE
A %B
k X0

ƒ non homogeneous
g composition
p of p
primary
ypphase Æ coring,
g, micro-segregation
g g
ƒ solidification ends at T =
ƒ last liquid : composition =
ƒ last solid (D) : composition =
ƒ for X0 < Xmax : eutectic structure may be observed in the ingots even for X0 < Xmax
ƒ solidus Ts is no more a specific
p T

36
 * Solid fraction (f) as a function of (T) Xl
Ö liquidus equation T Tm  m l X l
X0

Ö the Scheil-Gulliver relation (1f ) (1 k ) Xl Tm  T (1  k ) Tm  TL

œ (1f )
X0 Tm  TL Tm  T

1 1
§ Tm  TL · ( 1  k ) § Tm  TL · ( 1 k )
(1 f ) ¨¨ ¸¸ Ö simple case: phase ( 1  f )eut ¨¨ ¸¸
© m
T  T ¹ diagram with eutectic © m
T  TE ¹

37

ƒ Computed solidification paths for Mg – 10 mass% Al

Pandat + PanMg8 database

"Equilibrium" model

ƒ T < TS 476
476°C)
C)
Mg - 10 wt% Al
650

600

550
T (°C)

"Scheil-Gulliver" model
500
equilibrium

450

400
0 0,2 0,4 0,6 0,8 1
solid fraction f

Æ predictions of "Scheil-Gulliver" model

( cored dendrites) D  84 mass% (wt%)
ƒ fraction of primary phase ("cored"
ƒ eutectic (DJ : 16%
38
 ƒ Computed Al microsegregation profile for Mg – 10 mass% Al

Pandat + PanMg8 database

Al segregation
g g in D ((Mg)
g) p
phase
(Scheil-Gulliver model)
14

12
Mg)
D(M

10

8
Al in

6
mass % A

4 Locate points A, B and

2  C on the above
microstructure.
0
0 0,2 0,4 0,6 0,8 1

A solid fraction f B C

39

ƒ Computed solidification paths for Mg – 16 wt% Al

Pandat + PanMg8 database

EQUIL --> J : 10% vol

Mg - 16 wt% Al
560

540

520

500
EQUIL
C)
T (°C

480 Scheil-Gulliver -->

460 Scheil –
Gulliver
J 20 vol% predicted
440 - 18 vol%
l% experimentally
i t ll
420

400
0 0,2 0,4 0,6 0,8 1
fD fD
Solid fraction
 

40
 ƒ Experimental / computed solidification path for Mg – 16 wt% Al

Microsegregation profile in D(Mg) dendrites

"coring" from center to edge (EDS maps)

equil
XM
wt% Al

ScheilͲGulliverprediction

solid fraction

- good prediction from Thermo-kinetic modelling with Scheil-Gulliver model

in the range 20 – 60 vol% J
41


Solidification path
for Al- 4.5 mass% Cu alloy.

(1) Describe the "equilibrium"

equilibrium solidification path : Liq
Calculate 660.5

(a) temperature at which solidification begins

D 5.7 548°C 33 52
(b) temperature at which solidification ends
(at which liquid disappears)
(c) Solid and liquid composition for f equal to :
0 – 0.25
0 25 – 0.50
0 50 – 0.75
0 75 – 0.90
0 90 – 0.95
0 95 - 1 T
(d) Draw the composition profile through the entire
ingot (including solid and liquid phases) for 2
values of f : 0.25 and 0.90
(2) Describe the solidification path if solidification Al mass % Cu
conditions lead to "normal freezing" (Scheil –
Gulliver conditions) : same questions as (1).
Precise the relative amounts of the various phases
and constituents : mass and volume fractions at T
just below Tend
Data : densityy of Al : 2.7 g.cm
g -3 and T : 4.4 g
g.cm-3

(3) Comment the "as-cast" microstructure shown

on the micrograph (SEM-BSE image) and draw the
composition profile along the black line in the
picture.
42
z Scheil-Gulliver model : solute diffusivities in the liquid and solid phases
wrought Al cast Al plain C cast
alloys y
alloys steels iron Fe-Ni


Which
Whi h model
d l
(Equilibrium / Scheil-
Gulliver) is relevant for
following solute
elements in steels :
- Ni Æ
- CÆ

Why ?
- Ni Æ
- CÆ

[KUR1986] 43

2.2.2 Validity of Scheil-Gulliver equation

* Conditions for neglecting
g g diffusion in the solid?
Ls : diffusion length in the solid: Ls Ds .T s

Ds: solute diffusion coefficient in the solid

șs: solidification time = time to transform the liquid (at TL) to solid (at TS or TE)

Ls has to be compared to the characteristic length of the solidif phase L :

Æ for dendrites : L = ½ (O2) with O2 : SDAS (secondary dendrite arm spacing)

Ds .T s
D
L2
• Į << 1: diffusion of solute in the solid is negligible Æ Scheil-Gulliver equation is relevant
• Į >> 1: backdiffusion of solute in the solid has to be taken into account
Æ use of "modified Scheil" equations : example : Brody & Flemings

k Xo
k.Xo
composition of solid @ S-L interface : X s* 1 k
ª f º
1 
«¬ 1  Į.k »¼

44
2.3 Diffusion layer in the liquid and
morphology of the liquid/solid interface

Hypothesis of the model:

• (H1) Limited diffusion of solute atoms in the
liquid Æ diffusion coefficient : Dl
• (H2) No convection in the liquid
• (H3) Negligilble diffusion in the solid
• (H4) Local equilibrium at the interface
• (H5) Constant rate of movement of the
interface Æ V

Æ a solute-rich
solute rich boundary layer builds up in
front of the growing interface (a)
Æ at steady state (b) the solid growths with
the composition X0
--> the interface temperature is Tsolidus

45

2.3.1 Diffusion layer in the liquid

CB
V
x : fixed axis
x’ : moving axis linked to the interface
CL*
Cs* : solid composition at interface [mol
[mol.m
m-33] Gc CL(x
(x’))
CL* : liquid composition at interface [mol.m-3] Co
Cs*
C0 : alloy composition [mol.m-3]
CL (x’) : liquid composition [mol.m-3]
x
V : interface moving rate
Gc : composition gradient in the liquid x’ = x – V.t
at interface

z Balance of solute flow across the interface : for a shift dx = V.dt

§ wC ·
C*L  C*S V dt  DL ¨ L ¸ dt
© wx ¹
mol m-3
mol. m m2.s
s-1 s
mol. m-4

solute flow rejected into solute flow transported

the liquid at interface by diffusion in the liquid

46
 § wC
¨
·
¸ V .( C *l  C *s )
Æ solute gradient at interface : Gc ¨
L
¸ 
© wx ¹ DL

+ local interface equilibrium : CS* k CL *

V .C L * ( 1  k )
Gc  general expression
DL

C0
* at steady state:C S * C0 and C L*
k
Æ interface temperature = Tsolidus

V § 1 k ·
Æ Gc  C0 .¨ ¸ solute gradient at interface
DL © k ¹ at steady state

47

z Concentration profile of B in the liquid (for 1-D problem)

Solving differential equation for solute flux in the moving coordinate system (x') :
2 sources : solute gradient (diffusion) + counter-flow from interface motion (shift)

V wC L CL unit J unit
J diff  DL !0
wx' at.m-3 at.m-2.s-1
Jdiff
J shift  V CL  0 mol.m-3 mol.m-2.s-1
CL(x’) Jshift
kg.m-3 kg.m-2.s-1

x'

ƒ In a volume element (dV) of surface (A) and thickness (x') Æ dV = A.dx'

with
ith composition CL(x')
( ') at t Æ CL + dCL at (t+dt)

Æ mass conservation
wC L wC L w § wC L ·
 ’J 0 ( source ) Æ  ’J  ¨  DL  VC L ¸
wt wt wx' © wx' ¹

Æ att steady
t d state
t t wCL w 2CL wCL
Æ if DL(x') constant 0 DL V
wt wx' 2 wx' 48
 w 2C L wC L
DL V 0 solution type : CL A exp ( D . x' )  B
wx' 2 wx'

3 boundaryy conditions : wC L
D A exp ( D . x' )
w x'

* for x' Æ f C L o C0 = B w 2C L
D 2 A exp ( D . x' )
C0 w x' 2
* for x' Æ 0 CL o =A+B
k
DL D 2 A  V D A 0
§ wC L · V 1 k
* for x' Æ 0 ¨ ¸ Gc  . C0 . D DL  V 0
© wx' ¹ x' 0 DL k
V
! D 
DL

Æ solute profile at steady state in the boundary layer :

1 k § x' ·
CL C0  C0 . exp ¨¨  ¸¸
k © DL V ¹
49

z solute profile at steady state 1 k § x' ·

C0 . exp ¨¨  ¸¸
in the boundary layer
1 k k © D L V ¹
( convection)
(no ti ) C0 .
k

Co
DL V x''
Ö length of initial transient

Tiller (1953) : Cs during initial transient Æ Cs ” 0.99 C0

§ kx ·
Cs ( x ) C0  C0 ( 1  k ) exp ¨¨  ¸
¸ L
© DL V ¹
solid liquid
q
mass conservation
ti (equal
( l areas))
C
Co / k diffusion
no convection

Co
* end of initial transient : ex Cs = 0.99 C0
kCo
 Dl 0.01
xtransient ln
kV 1 k
xtransient x or x'

50
 z Effect of convection in the liquid

 2.3.2 Effect of convection in the liquid

q : directional solidification of single
g
crystalline Si ingots for micro-electronic applications
2 processes are used for growing single crystals of Si
- Czochralski
C h l ki (Cz-Si)
(C Si)
- Floating-zone (FZ-Si)

Cz method Z Data : impurity partition coefficients (k0)

Impurity k0
seed B 0.8
SiO2 C 0.06
crucible
V P 0.35
Si
Sb 0.023
Ga 0.08
Liq-Si In 0.0004
O 1.4

Diffusivity of Sb atoms in liquid Si :

1 10-8 m2 s-1

51

Effects of limited diffusion + convection in the liquid

Assume: (i) constant growth rate (V) - (ii) steady-state growth (iii) a radially uniform 1D problem

z CL(x’) in the moving coordinate system is solution of : d 2C L dC L

DL 0 V
dx' 2 dx'
z Assuming that beyond a distance į in the fluid
fluid, the solute concentration is uniform
uniform, due to
convection, and roughly equal to C0, give the boundary conditions to solve the equation.

Æ show that C 0  C *S § G ·
p ¨¨ 
exp ¸¸ C
C *L  C *S © DL V ¹
Co / k G
CL*
z Due to limited diffusion in the liquid, the
effective p
partition coefficient is :
Co
C *S CS
k eff C *S
k eff
C0 kC
*
o C0
z Derive the relation between keffff and
k0 = CS*/CL* , DL , V, G Æ Burton-Prim-Schlichter equation (BPS)
z From fluid mechanics considerations, į can be expressed as : G 1 ,6 DL1 3 Q 1 6 Z  1 2
Data : typical values of DL = 5.10-5 cm2.s-1; Q = 2,5.10-3 cgs units and Ȧ = 100 to 1000 rpm (pulling rotation)

z Draw the variation of k with the growth rate, from 10-4 to 10-1 cm.s-1.
z Replacing k0 by keffff in the formula of the normal freezing (Scheil-Gulliver)
(Scheil-Gulliver), redraw
variations of Sb impurity (Cs/C0) in a Si monocrystal for 0 < f < 1 for the different boundary
values of k.
52
 2.4 Morphology of liquid/solid interface
V
heat flux
(a) plane front growth
solid liquid
(b) cellular growth
(c) dendritic growth
(a) (b) (c)

(a) Instability of the plane front

--> cells

(b) stability of the plane front

[KUR1989] 53

z Plane front to cells transition : constitutional supercooling criterion

T1
Te
'To
T3

G*th Gth
x'

X0 XL Xo / k

* ǻT0 : solidification interval of the alloy X0

supercooled liquid
* Te : equilibrium T° for liquid (comp. XL)
* Gth : thermal gradient in the liquid
[POR2001] Æ imposed by the process

* for Gth > Gth* : the liquid is stable (no driving force for solid formation ahead of S/L interface)
* for Gth < Gth* : there is a region in front of the S/L interface where the liquid is "supercooled"
refering to the equilibrium Te curve corresponding to the liquid compositions XL(x')
Æ constitutional supercooling
54
Æ constitutional supercooling : in the region where the liquid is supercooled, there is a driving
force to develop solid instabilities growing at the interface
Æ breakdown of planar front Æ cells or dendrites

z Constitutional supercooling criterion : PC transition (Plane front Æ Cells)

wTe wTe wC L Gth > GPC --> plane front stable

Gth* G PC
wx' wC L wx' Gth < GPC --> cells (dendrites)

liquidus slope = m Gc : concentration gradient at the interface

m .V .( C*L  C*S ) §G· m .( C*L  C*S )

G PC m .Gc  Ÿ ¨ ¸ 
DL © V ¹ PC DL

Constitutional supercooling criterion (during steady-state growth)

§G· m .C0 1 k 'T0 G §G·

!¨ ¸ -->
> plane front stable
¨ ¸ 
© V ¹ PC DL k DL V © V ¹ PC
G §G·
¨ ¸ --> cells (dendrites)
process alloy data (thermodynamic V © V ¹ PC
parameters and kinetic)

55

§G· m .C0 1 k 'T0

¨ ¸ 
© V ¹ PC DL k DL

¾ Effects of G and V
G/V (G/V)PC
plane plane
front front
low cells dendrites high
growth growth
rate rate
V
VPC Va

¾ if thermal gradient G is fixed

Ö p growth rates : V < VPC

plane front is stable at low g

G . DL
VPC
'T0
56
Ö Effects of growth rate (fixed thermal gradient)

low V Vn V nn high V

O O
S L O S L
S L S L

z minimum z kinetics of solute z kinetics Æ SL z Ȝ2 too small for a

interfacial energy transport across area must n significant effect on
interface becomes Ö dendrites kinetics .
- thermodynamics
limitant : SL area
us n Ö ce
must cells
s
z low surface for if V n Ö Ȝ2 p Ö for V > Va
solute transport
if V n Ö Ȝ1 p
- kinetics interfacial tension
from solid Æ liquid - kinetics stabilizes again the
/ kinetics z energy Asl. Jsl n planar interface
z energy Asl. Jsl n
(no problem) / thermodynamics - thermodynamics
/ thermodynamics

57

Ö Plane front growth at high growth rate : absolute stability DL 'T0

Va
k *
ǻT0 : equilibrium liquidus-solidus range at C0
* : Gibbs-Thomson parameter | 10-7 m.K

J sl
*
' sm
plane front

Jsl : interfacial energy

'sm : melting entropy
per unit volume

Effect of the thermal gradient G

andd th
the growthth rate
t V on th
the
morphology of the solid-liquid
interface.

VPC (G1)
[KUR1989] 58
 ‰ Example of transitions in laser traces
Laser surface melting / solidification
Top view
laser beam
x
Vscan melted zone
S Vscan
x y S
y
B
melted depth z
mz
transverse section

: vector normal to Solid-Liquid interface

: velocity of S
S-L
L interface //
: projection of on Longitudinal section

T = 0 --> VA = Vmax = Vscan

Æ Vscan
S
x &
n &
T n melting front
Transverse section solidification S
z front
solidification B
&
y front n
S T = S/2 --> VB = Vmin = 0
z
melting front
B
T = S/2 --> V = 0 59

C
PF

unmelted zone

Bottom of laser melted (+ Cr3C2 ) and

solidified 316L stainless steel : plane front
(PF) - cells (C) - dendrites (D) 60
 3
Laser superficial remelting of a cobalt-
2 based cast alloy (stellite F) : 38.5% Co
–25%
25% Cr – 23% Ni – 12% W – 1.5% 1 5% C
laser spot

1 L V
S
cast alloy
(transverse section)

cast alloy
heat flow

‰ low growth rate (1 μm/s) --> > plane front growth + macrosegregation
illustrating the solidification path :
(1) Liq --> J -(Co)
(2) Liq --> J -(Co) + M7C3
‰ high growth rate
(3) Liq --> J -(Co) + M7C3 + M6C 100 μm/s --> dendritic
growth ((finer scale /
g
casting process)

but same sequence of

phase formation
cast alloy
61

3. Solidification microstructures

3.1 Faceted and non-faceted growth morphologies

GFe dendrites in ferritic stainless steel Primary Si « dendrites » in Al-25 wt% Si

Anisotropy
y of g
growth rate for different crystallographic
y g directions:
• slight tendency to anisotropy : simple structures of metals D non-faceted growth
• complex crystal structures or directional bondings (Si, C) D faceted growth

for details, see "Growth Kinetics " part of ELAB-1 62

 Ö addition of tensioactive elements to the melt in order to promote a non-faceted growth
(ex : Na, Sr for silicon in Al-Si alloys)
Ö improvement of fracture toughness

x 100 (a) x 100 (b)

Optical micrographs of Al-5%Si-3%Cu alloy

(a) non-modified growth : silicon is needle-shaped Æ alloy is brittle
(b) growth modified by addition of 100 ppm of Na : silicon exhibits a more globular shape

63

3.2 - Dendritic growth

3.2.1- Dendrite arm spacings

Ö The size of the microstructure is related to the local conditions (G, V) during solidification
Ö size = cell / dendrite arm spacings
Ö this size decreases È when the growth rate incrasesÇ

Cross section of a Zn-4% Al

electrical connector produced by
pressure die-casting.
2 (1) rapid
id h
heatt extraction
t ti ffrom the
th
metallic mould leads to a fine
dendritic structure below the
surface
1 3 3 (2) gradual decrease of G and V
results in a more coarse structure
in the center
(3) conductive coating deposited
by chemical process

SEM-BSE image
g

64
 Ö Effects of G and V on the size of the dendritic (cellular) structure can be studied by
unidirectional solidification
- DS experiment : V and G controlled separately
T
T2
T
liquid
O1
T2 TL S/L interface
L dendrites

dÖG § wT · O2 (SDAS)
G ¨ ¸ TE
© wz
w ¹
S
T1 T1 solid

V z
heat V
extraction

Ö Secondary dendrite arm spacings Ȝ2 (SDAS) will be measured on a longitudinal

cross section
ti off the
th iingott and
d primary
i spacings
i Ȝ1 on a transversal
t l cross section
ti
65

z primary spacings (cells or dendrites)

Measurement of primary dendritic

spacings on a transversal cross section
off a steel
t l ingot
i t after
ft directional
di ti l
solidification :
V = 9 cm/h et G =300 K/cm
Ö O1 # 200 μm.

250 μm

Æ key parameters are : local solidification conditions (G, V) and composition of the alloy
(k 'T0, DL and
(k, d *))
k 'T0 DL * 1 / 4
[HUN77] O1 2.83
G1 / 2 V 1 / 4

'T0 DL * 1 / 4
[KUR89] O1 4.3
k1 / 4 G1 / 2 V 1 / 4

66
 z SDAS (O2)

1 mm

S/L interface

10 O2

SDAS measurement on a longitudinal

cross section of a steel ingot after
quenching during directional
solidification (QDS experiment) :
V = 9 cm/h / et G =300 K/cm
/
Ö O2 # 75 μm.

67

Æ same key parameters as for O1 : local solidification conditions (G, V) and composition of the
alloy (k, 'T0, DL and *)

$ local solidification time : Ts

'T0 'T0 'T0

Ts
wT wt T' G V

O2 B T sn 0.20 < n < 0.40

[ASK 94]

Ö Modeling [KUR89]
Data for various steel families
13
§ ·
¨ § Cliq
max ·
¸
¨ * DL ln ¨ ¸
li ¸
¨ ¨ C0 ¸ ¸
O2 5.5
¨
¨
© ¹ ¸
¸ Ts 1 3
¨m 1  k ( C0  C liqmax )¸
¨ ¸
¨ ¸
¨ ¸
© ¹

with (in most cases) Cliq max = Ceut

cooling rate T ' (K / s)

68
 plane front

T' = G * V = cte

VPC

G / V = cte
= (G/V)PC

[KUR1989]
69

$ effect of SDAS (O2) on properties

1
Hall-Petch Ve Vo  k d 2

d = grain size Æ here d { O2

* example : stellite Co base alloy

laser remelted alloy

cast alloy
O2 ~ 1 μm
O2 ~ 50 μm
hardness ~ 920 HV
hardness ~ 320 HV

70
 3.2.2- Microsegregation

Ö cells : solute is rejected between

primary arms

Ö dendrites: solute is rejected

between primary and secondary
arms, resulting in a "cored"
microstructure

71
[POR2001]

3.2.3- Micro-porosities : 2 origins

Ö gas dissolved in the liquid is rejected at S-L interface (partition coefficient k)
Ö microshrinkage in equiaxed solidification of "mushy freezing alloys"

Porosity in a Al-5%Cu alloy after casting

in a ceramic mould (SEM-SE image)
Top-risered
p casting g : ((a)) beginning
g g of equiaxed
q solidification
: solidification shrinkage is accounted for by movement of
both liquid and solid – (b) dendrites can no longer move but
feeding occurs by interdendritic flow - (c) isolated liquid will
lead to p porosities [[FLE 1974]]

In-situ solidification of Al-Cu alloy

ESRF ( ID 15 line )

72
3.3 - Eutectic solidification
3.3.1- Solute diffusion

Coupled growth of 2 solid phases a and b needs both longitudinal and lateral diffusion of
solute in the liquid ahead of S-L interface

Liq
D Liq
E Oe
D E
D B
'Tdiff
E xLE
B
D xLD
A
E

A xD xLE xLD xE (B)

xE
73

3.3.2- Eutectic spacing

E t ti spacings
Eutectic i resultlt ffrom a competition
titi between
b t :
* kinetics : when solidification rate V Ê Ö Oe Ì
* thermodynamics : minimization of interfacial energy Ö Ê Oe

$ Oe2 V C

3.3.3- Morphology of eutectics

* key factors
- volume fraction fE in the eutectic constituent :
0.3 < fE < 0.5 Æ lamellar eutectic
<0 3 Æ fibrous eutectic
fE <0.3
- faceted (non-faceted) growth of E
DE < 2 Æ regular eutectic
DE > 2 Æ irregular eutectic

[KUR 89]
74
 z eutectic microstructure in "grey" cast-iron Ceq = C + 1/3 (Si + P)

L + C (graphite)

L + Fe3C

J + C (graphite) or J+ Fe3C

eutectic primary phase: C D + C (graphite) D+ Fe3C

J+C

Optical micrograph of grey cast iron

Fe -3.8%C
-3 8%C -2.1%Si
-2 1%Si -0.47%
-0 47% Mn :

Æ graphite "flakes" (primary and eutectic graphite) form when

V [0001] < V [1010]
75

z eutectic microstructure in "white" cast-iron Ceq = C + 0.11 Si - 0.045 Mn

x150

eutectic primary phase Fe3C

J + Fe3C

Optical
p micrograph
g p of white cast iron :
Fe -4.26%C -0.20% Si -0.16% Mn -0.91% Cr Growth modes of austenite - cementite
Æ faceted growth of cementite M3C eutectic. from Hillert [HIL 60]

76
 3.4 - Peritectic solidification

Data : Microscopic examination of a Pb -20at% Bi ingot shows the presence
of the phases : Į(Pb), İ and İ+ȕ(Bi) eutectic

T(°C)
350
327°
300
271°
250
D
200
187°
187 29
22 38

150
H
40 125°
100
56 HE
Pb 10 20 30 40 50 60 70 80 90 at% Bi

77

(A) (1) Explain qualitativeley the experimental observation : "equilibrium" or "normal" freezing ?

(2) Calculate the solidified fraction at the beginning of growth of İ

(3) Same question for the growth of (İ-ȕ) eutectic

(B) - Suppose now that the solidification parameters (G,V) lead to cellular front growth.

( ) Draw a longitudinal cross-section off the ingot during unidirectional solidification

(4) f and locate
the isothermal planes : Tliquidus, Tperitectic, Teutectic.
Locate the regions corresponding to the different phases.
(5) Sketch 3 transversal cross-sections for following temperatures : 200°, 150°, 120°C
(6) Plot the concentration of Bi across 2 adjacent cells on a transversal cross-section for
T 25 C
T=25°C
(7) Describe the microstructure in the liquid region that has been quenched at the end of the
unidirectional solidification experiment.

78
  z peritectic microstructure in Mg - 20.8 at% Y (3.4 at% Mn )

SEM - BSE image of Mg -20.8

at% Y -3.4
3 4 at% Mn alloy cast in
a steel mould.

Æ Identify the different phases and describe the solidification path of the alloy on the basis
of the binary Mg-Y phase diagram [MAS 90], assuming negligible effect of the 3.4 at% Mn
on the
th liliquid-solid
id lid equilibria.
ilib i
79

 4. Solidification path in a ternary alloy (steel) : Fe - 1.7% C - 3.1% Cr (wt%)

ƒ partition coefficients :
ƒ Data : liquidus projection of Fe-Cr-C (Fe-rich part) kCr = 0.59 and kC = 0.40

Phases

BCC BCC : ferrite (G)

M7C3
FCC : austenite (J)
M7C3 : carbide (Cr, Fe)7C3
FCC
M3C : cementite ((Fe, Cr)3C

Invariant equilibria

P1 : 1210. 67°C
LIQ + Cgr + M7C3 --> M3C
peritectic

U2 : 1177.98°C
4.4 C – 7.7 Cr (wt%)
M3C LIQ + M7C3 --> FCC + M3C
quasi-peritectic

E1 : 1150.67°C
+ LIQ --> FCC + M3C + Cgr
eutectic

80
 (A) - Suppose that the diffusion rates of Cr and C in the primary solid phase are negligible.
Justify that the solidification path of the liquid can be expressed with :
0
X Cr X C0
L
X Cr X CL
( 1  kCr ) ( 1  kC )
( 1 f ) ( 1 f )

* Compute the solidification path for : f= 0 - 0.4

0 4 - 0.8
0 8 - 0.9
0 9 - 0.95
0 95 and report the results on the liquidus
projection. Which "minor" phase will appear at the end of solidification ? For which value of the solid
fraction f ? By which reaction ?

(B) - Suppose now that diffusion of Cr in the primary solid phase is still negligible,
negligible but that C atoms
diffuse very fast in the solid phase.
X C0
* Show that in this case : X CL
kC  ( 1 kC ) ( 1  f )

* Compute the solidification path for : f= 0 - 0.4 - 0.8 - 0.9 - 0.95 and report the results on the liquidus
projection. Which "minor" phase will appear at the end of solidification ? For which value of the solid
fraction f ? By which reaction ?

(C) - Suppose now that diffusion of Cr and C in the primary solid phase are both very fast.
*: Compute the solidification path for : f= 0 - 0.4 - 0.8 - 0.9 - 0.95 - 0.99 - 1 and report the results on the
liquidus projection.
projection Conclusion ?

(D) – For each case (A, B, C) : sketch the solidification microstructures and draw the evolution of the
solid composition as a function of the solid fraction

81

APPENDIX 1 : Solid-liquid interfacial energies (nucleation)

Metal Tf (°C) 'Hf (J.m-3 x Jsl ((J.m-2 x 10- 'T (deg) homogeneous
Data for metals 106) 3) nucleation
Ga 30 488 56 76
Bi 271 543 54 90
Pb 327 237 33 80
Ag 962 965 126 250
Cu 1085 1628 177 236
Ni 1453 2756 255 480
Fe 1538 1737 204 420

APPENDIX 2 : Electromagnetic stirring

promotes a central equiaxed zone in

continuous casting of steel
-->for isotropic properties

[BIR 1994]
82
References (books)

[ASK 94] D.H. Askeland and P. Phulé, "The Science and engineering of materials", ed. Chapman & Hall, 1994
[BIR 94] J.P. Birat et M. Larrecq, "La coulée et la solidification" in "Le livre de l’acier", ed. G. Béranger et al.,
Technique et documentation Lavoisier, Paris,1994
[[DUR 87]] F. Durand ed. "Solidification des alliages,
g , du procédé
p à la microstructure",, Editions de Physique,
y q , 1987
[DUR 97] M. Durand-Charre, "The microstructure of superalloys", Gordon& Breach Science Publ. , Amsterdam, 1997
[FLE 74] M.C. Flemings, "Solidification Processing", McGraw-Hill, New York (US) 1974
[KOU 03] S. Kou, "Welding Metallurgy 2nd ed.", John Wiley, 2003
[KUR 89] W. Kurz and D.J. Fisher, "Fundamentals
Fundamentals of solidification",
solidification , Trans. Tech. Publ., Switzerland, 1989
[LES 86-89] G. Lesoult, "Solidification" in "Techniques de l’Ingénieur", Métallurgie M1, M58 (1986), M59-M60(1989)
[MAS 90] T.B. Massalski, "Binary alloy phase diagrams", ASM International, 2nd edition (1990)
[POR 01] D.A. Porter and K.E. Easterling, "Phase transformations in metals and alloys" 3rd ed., Chapman & Hall,
London,, 2001

References (journals)

[[FLE 76]] M.C. Flemings,

g Scandinavian Journal of Metallurgy,
gy 5 ((1976)) ,1.

[GAU 97] M. Gäumann, P. Gilgien and W. Kurz, "La solidification des métaux traités par laser", Proceedins of
LASERAP’3 conference, 6-10 oct.1997, Les Hauts de Marquay, France, ed. by A.B. Vannes

[RAP 1989] M. Rappaz et al., "Recent Trends in Welding Science and Technology, Ed. David & Vitek, ASM (1989), 147

References (jwebsites)

http://soliditice.minatec.grenoble-inp.fr/

83