2017 Spring

“Calculation and Applications Phase Equilibria”

Principles Solidification

05. 11. 2017

Eun Soo Park

Office: 33-313
Telephone: 880-7221
Email: espark@snu.ac.kr
Office hours: by appointment 1
 Solidification: Liquid Solid
1) Pure Metals: Nucleation and Growth (thermally activated process)
a) homogeneous Nucleation or Heterogeneous Nucleation • Undercooling ΔT
b) Growth of solid • Interfacial energy
Kinetic roughening γSL / S(θ) wetting angle

No compositional change
during solidification

Liquid α
Fig. 4.19 A hypothetical phase diagram.
 “Alloy solidification”
1. Solidification of single-phase alloys

• Three limiting cases

1) Equilibrium Solidification: perfect mixing in solid and liquid

2) No Diffusion on Solid, Diffusional Mixing in the Liquid

3) No Diffusion in Solid, Perfect Mixing in Liquid

- Planar S/L interface → unidirectional solidification

- Superheated liquid

- Cellular and Dendritic Solidification

- Supercooled liquid
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 1) Equilibrium Solidification : perfect mixing in solid and liquid

T1-ΔT
Xs = kXL X0+α

kX0+α

T2
AL
AS
Conservation of solute requires
the two shaded areas to be equal.
AS = AL
* Equilibrium solute concentration
kX0 ≤ Xs ≤ X0
X0 ≤ XL ≤ X0/k < XE T3+ΔT X0/k-α

X0-α

Liquid α Compositional change

during solidification
 2) Mixing in the liquid by diffusion only: No diffusion in the solid

* 1) Equilibrium Solidification ⇔ Opposite extreme of perfect mixing in solid and

liquid (solute or solvent) does not move → no mixing in either the solid or the liquid
→ L→S without composition change:“diffusionless solidification” of this kind may take
place locally when the liquid is sufficiently supercooled. = “polymorphic transformation”

* 2) For example, DS << DL

(DS ignored, DL~normally_all diffusion
in the liquid is to the interface)
In the case of Equilibrium solidification
V (speed of advance of interface)= very slow ↔ The amount of solute
but in this case Vinterface = R cm/sec If CS=C0, taking part in the diffusion
process is constant.
CS/Ca = k0 → not change as the
interface moves to the right
C0_initial composition of liquid
kE = CS/C0

Here, Ca=solute concentration in the → If composition of solid=C0, “steady state condition”

liquid at the interface Fig. 5.6. Distribution of solute during uniaxial solidification
2) No Diffusion on Solid, Diffusional Mixing in the Liquid
: high cooling rate, no stirring→ diffusion

- Solute rejected from solid

→ diffuse into liquid with limitation
- Rapid build up solute in front of the solid
→ rapid increase in the comp. of solid forming
(initial transient)
- if it solidifies at a const. rate, v, then
a steady state is finally obtained at T3
- liquid : C0/k0, solid: C0

local equil. at S/L interface

Composition profile
at T2 < TS/L < T3?

Steady-state profile at T3?

at TE or below ? 6
 Cs = k0CL

Interface temperature

* Steady-state at T3. The composition

solidifying equals the composition of
liquid far ahead of the solid (X0).
2) No Diffusion on Solid, Diffusional Mixing in the Liquid

① During steady-state growth,

(Interface →liquid: Diffusion rate)

Rate at which solute diffuses down the concentration gradient away from the interface
= Rate at which solute is rejected from the solidifying liquid
(Solid→Liquid from solidification: solute rejecting rate )
If CS=C0,

(X’= distance from the interface at

which the concentration is CL)
( CL decreases exponentially from C0/k0 at x=0, the interface, to C0 at large distances
from the interface. The concentration profile has a characteristic width of D/R. )

- Liquid distribution: “characteristic distance” given by D/R; that is, the

distance in which the excess concentration falls to 1/e of its initial value.
 Fig. 5.10. distribution of solute during initial transient.
No Diffusion on Solid,
Diffusional Mixing in the Liquid Initial stage

② Initial Transient
(a) First solid to form from C0 liquid: k0C0
→ Steady state condition, in which the concentrations
of L and S at the interface are C0/k0 and C0, will not
Intermediate stage
be reached until the solidification has proceed far
enough for a substantial amount of solute to have
been rejected.
(b) Two shaded area (deficit of solute in solid, excess
in liquid, compared with C0) ~ “equal”

(c) Tiller et al: CS = as a function of the distance Intermediate stage

k0=0.33
(exp. Approach not quite correct, and that an exact solution is)

* CS values calculated by these two methods → “similar”

Steady state stage
* Characteristic distance
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 2) No Diffusion on Solid, Diffusional Mixing in the Liquid

③ Terminal Transient
(a) Steady state condition: No hindrance of solute diffusion & R remain constant.
But, former condition ceases when the boundary of the liquid is approached (Figure 5.11.)

(b) Concentration of solid = C0 ↑ (∵excess solute must all appear in the terminal region)

(c) Characteristic distance for the diffusion zone (initial transient= D/k0R, steady state
condition = D/R) → terminal transient zone occupies a shorter distance, by a factor k0 ,
than the initial zone (concentration change in terminal transient zone_Chapter 8)

Fig. 5.11. distribution of solute during terminal transient. Fig. 5.12. concentration in initial and terminal transient.
“Alloy solidification” - Solidification of single-phase alloys
* No Diffusion on Solid, Diffusional Mixing in the Liquid

D/k0R
When the solid/liquid interface is within ~D/R of the end of the bar the bow-wave
of solute is compressed into a very small volume and the interface composition 11
rises rapidly leading to a final transient and eutectic formation.
2) No Diffusion on Solid, Diffusional Mixing in the Liquid

Cs = k0CL

Fig. Planar front solidification of alloy C0 in upper

figure assuming no diffusion in solid and no
stirring in the liquid.
(a) Composition profile when S/L temperature is
between T2 and T3 in upper figure.
(b) Steady-state at T3. The composition solidifying
equals the composition of liquid far ahead of
the solid (C0).
(c) Composition profile at TE and below, showing
the final transient.
D/R 12
2) No Diffusion on Solid, Diffusional Mixing in the Liquid

④ Change of speed
(a) When R~const, excess solute ahead of the interface = the area under the diffusion curve
→ characteristic distance D/R & solidification rate ~ 1/R
∴ The solid that is formed immediately after a change of speed must have a concentration
that differs from C0.
(b) If R ↑, D/R ↓, the amount of Solute ↓, the solid must have a higher concentration
during the transition from steady state at lower R to steady state at higher R.

(C) If R ↓, solid concentration is less than C0 as shown in Fig. 5.13.

Fig. 5.13. solute distribution following changes in speed of solidification (A) Increase; (B) Decrease.
2) No Diffusion on Solid, Diffusional Mixing in the Liquid

⑤ Effect of curvature of the interface

(a) Steady state condition (Cs=C0, TI=TS) is valid only if the interface is planar.

(b) If it is convex (center of curvature in the solid), then the solute is not conserved
within a cylindrical volume of the solidifying liquid (see Fig. 5.14)
→ Solute concentration is less than C0 / Liquid concentration adjacent to the interface is
less than C0/k0. / Temp. of Interface is above the solidius temp. for the original liquid.

Fig. 5.14. Solute diffusion ahead of a convex interface

(c) If concave, (1) Solid concentration > C0

(2) solidify at a temp. below that of the initial solidus
2) No Diffusion on Solid, Diffusional Mixing in the Liquid

⑥ Influence of liquid fluid motion: Convection

(a) Assumption of mixing by only diffusion ~ not realistic → ∵a liquid in which ΔT exist
is likely to be subject to convection.
(b) Only case for no convection → density gradient in the liquid is everywhere vertical

(c) If (1) in addition to density gradient caused by ΔT,

(2) density gradients resulting from compositional variation caused by rejection of solute,
the problem of achieving a completely non‐convection system becomes even more difficult.
(d) It is therefore necessary to consider the extent to which convection, resulting from density
gradients that arise from non‐uniformity of temperature or of composition, will affect
the redistribution of solute during solidification. →”Effect of mixing by fluid motion”

(f) Thickness of the “Stagnant” layer is sufficient to

include nearly the whole of the diffusion zone, the
analysis that ignores fluid motion is valid.
But, R is very small or liquid motion is more violent,
the stagnant layer is not thick enough.

(g) Diffusion limits the motion of solute btw interface

and the point T, beyond which the liquid is mixed and
has C0 < CP, which increases as solidification process.
Fig. 5.15. Effect of stirring on the diffusion zone.
“Alloy solidification” - Solidification of single-phase alloys
* No Diffusion on Solid, Diffusional Mixing in the Liquid

D/k0R
When the solid/liquid interface is within ~D/R of the end of the bar the bow-wave
of solute is compressed into a very small volume and the interface composition 16
rises rapidly leading to a final transient and eutectic formation.
3) No Diffusion in Solid, Perfect Mixing in Liquid
: high cooling rate, efficient stirring
- Separate layers of solid retain their original compositions
- mean comp. of the solid ( X S ) < Xs

Cs =ofksolid
- Separate layers 0CL retain
their original compositions
- mean comp. of the solid ( X S ) < Xs

T1-ΔT

T2 Liquid Primary α + Eutectic

solid  xs  xs liquid  X 0 k  X E T3 TE
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Mass balance: non-equilibrium lever rule (coring structure)

When cooled by dT from any arbitrary T,

determine the followings.

solute ejected into the liquid = ?

→ solute increase in the liquid

Ignore the difference in molar volume

between the solid and liquid.
fs: volume fraction solidified

solute ejected into the liquid=? → proportional to what? dfs (CL – CS)
solute increase in the liquid=? → proportional to what? (1-fs) dCL

( X L  X S )dfS  (1  fS )dX L Solve this equation.

when fS = 0 → CS, CL? CS = k0C0 and CL = C0

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Initial conditions
 fS dfS XL dX L XL dX L XL dX L
 0 1  fS
  X0 XL  XS
  X0 X L  kX L
  X0 X L (1  k )
fS XL
0
(1  k )( 1) d ln(1  f S )   d ln X L
XO

XL
ln  (k  1) ln(1  f S )
XO

( k 1)
∴ L
X  X f
O L

 k 1
X S  kX O 1  fS 
: non-equilibrium lever rule
(Scheil equation)
→ quite generally applicable even for nonplanar solid/liquid interfaces provided
here, the liquid composition is uniform and that the Gibbs-Thomson effect is negligible.
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If k<1: predicts that if no diff. in solid, some eutectic always exist to solidify.
 3) Complete or partial mixing of liquid: no diffusion in solid
: high cooling rate, efficient stirring
(a) Variation of CS/C0 with g (fs) is shown in Fig. 5.16
for values of kE from 0.01 to 5.

(b) There is no steady state region!

→ rejected solute : mix with liquid &
whole of the liquid is changed continuously.

(c) Solidification speed does not appear explicitly

→ kE depends on the speed.

∴ a) very low speed: kE = k0,

if speed ↑, diffusion zone ~ more important

& kE → 1 (steady state region of “diffusion

controlled” case)

(d) Calculation of the value, kE :

→ Why? d = thickness of boundary layer through
solute diffusion
Value of d is limited by the velocity of the
liquid parallel to the interface, & depends
on the velocity of liquid.
Fig. 5.16. Curves for normal freezing
10-3 cm < d < 10-1 cm (liquid completely mixed at all times).
Very vigorous stirring Natural convention C0 is 1 for all curves.
 3) Complete or partial mixing of liquid: no diffusion in solid
: high cooling rate, efficient stirring
(e) k0 ≤ kE ≤1
Process is so slow or Bulk liquid ~ C0
the mixing so effective composition due to no
that the whole of the mixing
liquid had the same
composition.

(f) If effectiveness of mixing is increased,

kE→k0 / R ↓ / d ↓ / D ↑
R → Rd/D
(actual growth velocity) (normalized growth velocity)

Fig. 5.16. Curves for normal freezing

(liquid completely mixed at all times).
C0 is 1 for all curves.
- Fig. 5.17 shows how kE varies with
normalized growth velocity (Rd/D)
for values of k0 from 0.1 to 0.9.

Fig. 5.17. Dependence of effective distribution coefficient

on normalized growth velocity (From Ref. 9, p. 14)
 Fig. 5.18. solute distribution after uniaxial solidification. (앞서 고려한 모두를 정리)
(a) Complete diffusion in solid and liquid, (b) mixing by diffusion only, (c)
complete mixing in liquid (kE=k0), (d) partial mixing in liquid [kE = (1+k0)/2].

* Comments: Solidus temperature of an alloy

TL: Solidification start → supercooling → TL (recalesence)→ TS: Solidification finish
Phase diagram → determined from cooling curve ∴TL satisfactory, TS large errors
When a single-phase solid is formed, the last liquid always solidifies at a temperature
below the solidus for the original liquid (of composition C0) some times by a large 23
amount→ Please check “Zone refining”.
Concentration profiles
in practice
: exhibit features
between two cases

Zone Refining
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5.4 Zone Refining
: A crystal growing from a solution usually rejects either the solute or the solvent → “Purifying Crystalline”

(a) Distribution coefficient of any solute, k0 ~ very small (< 10-6 )

→ Importance of R/ d/ D ↓ → Purity ↑ by multi-stage process

(b) Distribution coefficient k0 ~close to 1,

→ Purity ↑ by multi-stage process
→ possible, but not practical
∴ Each successive stage would provide less material of high purity.

Zone melting or Zone refining – W.G. Pfann Invention ~ various extension and
modifications (see Pfann’s book: Zone melting, John Wiley & Sons New York, 1958)
Ring heater

The form of a bar

& Held in suitable
container

Fig. 5.19. Zone melting, schematic. (From Ref. 9, p. 24.)

 (a) Fig. 5.20. Distribution of solute after passage of one molten zone;
initial concentration C0. (From Ref.9, p. 25)

* Concentration distribution :
except terminal transient region

(b) Concentration gradients after multi-pass in the same direction as first:

further transfer of solute from left to right
(c) Effect of kE on purification: low kE (left) : small # of pass → large decrease of solute concentration
kE ~ 1 (next page): requires a very large # to produce a comparable effect

① kE = 0.1 ② kE = 0.25

Fig. 5.21. Solute concentration against distance

(in zone lengths) after passage of n zones

Fig. 5.22. Solute concentration after n zones

for kE = 0.1.
(c) Effect of kE on purification: low kE (left) : small # of pass → large decrease of solute concentration
kE ~ 1 : requires a very large # to produce a comparable effect

③ kE = 0.9524

28
Fig. 5.23. Solute concentration for kE = 0.95.
 Figure 5.24 Limiting distribution which is approached after passage of many zones;
Length of ingot is 10 zone lengths. (From Ref. 9, p. 41)

(a) How the ultimate distribution (i.e. when a steady state has been
reached) varies with the value of kE for a bar 10 zones in length.

Assumption : - Impurity to be removed have distribution coefficient less than 1.

- Solutes are rejected by growing crystals and accumulate in the terminal region.

But, (b) some solute are preferentially accepted by growing crystal, and therefore, 29
have distribution coefficients greater than 1& accomulate in the first part to solidify
* A comparison of separation obtained with kE =0.7 and 1.2 is shown in Fig. 5.25, where a bar ten zones
in length L/l=10 is subjected to various number of passes.

① kE = 0.7 ② kE = 1.2
* When purifying through zone refining, metals with high reactivity and high Tm should
be carefully considered for contamination especially from containers.→ This problem is
minimized by using the various floating zone methods described below.

Single Crystal Growth: c) Float-zone (FZ) method

; high purity, expensive
The maintenance of the molten zone is possible by
the combined force of surface tension or stress
induced by surface tension and electromagnetic.

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* Cellular and Dendritic Solidification
Fast Solute diffusion similar to the conduction of latent heat in pure metal,
possible to break up the planar front into dendrites.
→ complicated, however, by the possibility of temp. gradients in the liquid.

What would be “Te“ along the

steady-state solidification
at a planar interface concentration profile ahead
of the growth front during
steady-state solidification?

TL’
Te
temp. gradients in the liquid

32
* Constitutional Supercooling No Diffusion on Solid, Steady State
Diffusional Mixing in the Liquid

* Actual temperature gradient in Liquid

TL’
At the interface,
* equilibrium solidification temp. change
TL = Te (not TE) = T3
Te

TL' > (T1-T3)/(D/v) : the protrusion melts back - Planar interface: stable
33