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constitutional supercooling

constitutional supercooling

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v

C L z C0L CiL C0L exp z

D

(1)

where z is a distance from the interface1 , D is the diffusion coefficient of the solute in the liquid

phase, v is the interface velocity, C0L is an initial concentration of the solute in the melt prior to

solidification, and CiL is the concentration of the solute in the liquid phase at the interface.

Figure 1 a) gives you a fairly good idea about the shape of the dependence (1). Please realize that

the situation shown in this figure corresponds to the case when keff 1 .

C

CiL

CL

C0L

0

CS

z0

a)

T sol

b)

T liq

Tm

Figure 1

Figure 1 b) establishes a correspondence between C0L and CiL , on one hand, and between

liquidus and solidus temperatures, on the other hand. It should be clear that temperature at the

moving interface is to be associated with the solidus temperature, T sol , corresponding to the

given overall composition. When we move from the interface into the liquid phase, the

concentration of solute is decreasing, which means that we are getting closer and closer to the

component A. This, in turn, means that temperature is gradually increasing from T sol to the

liquidus temperature T liq . This is clarified in Figure 2 (bold black lines).

Actual temperatures

resulted from different

solidification conditions

T

Case I

Case II

liq

T

for the

given C0L

T liq z

T sol

z

The region of

constitutional

supercooling

Figure 2

Imagine yourself sitting at the interface and looking straight into the liquid phase along the z

axis. In the case of Case I, you see liquid, which temperature is always greater than the

equilibrium liquidus temperature. It can be conjectured that the interface remains flat. In the

second case, Case II, you see a certain region within which the actual temperature is less than the

equilibrium liquidus temperature. This region is known as the region of constitutional

supercooling. Within it, a morphological instability of the S/L interface can be expected, but not

necessarily occur.

What is the fundamental difference between Case I and Case II?

dT liq

dz z 0

dT

dz z 0

G L temperature gradient

in the liquid phase near

the interface

dT liq

dz z 0

dT

dz z 0

(2)

G L temperature gradient

in the liquid phase near

the interface

dT liq

dT liq dC L

C L z 0 dz z 0

dz z 0 d

(3)

liquidus slope

liquidus slope

It is equally easy to calculate dC L dz

z 0

T sol T liq

T liq T sol

CiL C0L

CiL C0L

(4)

Differentiation gives:

dC L

v

v L

v

L

L

L

Ci C0 exp 0 Ci C0

D

D

D

dz z 0

(5)

dT liq

T liq T sol

L

Ci C0L

dz z 0

v T liq T sol

v L

L

D Ci C0

D

(6)

From (2) and (6) it is clear that the constitutional supercooling may occur if the following

criterion is satisfied:

v T liq T sol

D

GL

G L T liq T sol

v

D

(7)

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