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- Fick's Law and Diffusion
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There are two modes of mass transfer: diffusion and fluid flow. Diffusion is

described by Fick’s law.

domain. For one dimensional binary system the solute diffusion flux is given by

∂C

J = −D (6.1)

∂x

where J is the diffusion flux, D is the diffusion coefficient or diffusivity, C is the

concentration, and x is the position. D depends on the temperature, viscosity of

the fluid and size of the particles. At melting temperature, diffusivity of carbon in

liquid steel is about 4x10-9 m2/s.

L

C1

C2

Fick’s second law of diffusion is derived from Fick’s first law of diffusion and

continuum equation. In one dimensional binary system, it has

∂C ∂ ∂ ∂C

=− J = D (6.2)

∂t ∂x ∂ x ∂ x

Graduate Institute of Ferrous Technology, POSTECH

∂C

= ∇ ⋅ (D∇C ) (6.3)

∂t

Assuming the diffusivity D to be constant one has

∂C

= D∇ 2C (SL3)

∂t

Equation (6.3) is called Fick’s second law of diffusion. The steady state solute

distribution, as illustrated in figure 1, is obtained for 1D system when ∂C / ∂t = 0 .

(6.4)

α α

where cn represents the concentration of element n in α phase, Dnm is the

diffusion coefficient. Now we derive the equation (6.4) from second law of

thermodynamics. The details can be found in ref 1.

(6.5)

The total free energy of the system is the integration of the free energy density

across the space

(6.6)

From mass conservation one has

(6.7)

For the process where only diffusion takes place, the second law of

thermodynamics demands that

(6.8)

which leads to the

(6.9)

where

Graduate Institute of Ferrous Technology, POSTECH

fixed frame, i.e. allowing for changing in partial molar volumes, the following

condition applies

(6.10)

Equation (6.9) can be satisfied by various expressions, The simplese one is the

linear combination

(6.11)

with following sufficient condition

(6.12)

(6.13)

Graduate Institute of Ferrous Technology, POSTECH

solute distribution in a moving coordinate that originated at interface can be

obtained. The typical equilibrium phase diagram for binary system is illustrated in

figure 2. There are two sources to the solute change. One is due to the moving of

d 2C L

the interface R ⋅ dC L / d x . Another is solute distribution DL .

d x2

dC L d 2C L dC

= DL 2

+R L (6.14)

dt dx dx

At steady state ∂C / ∂t = 0 , the solution of equation (6.14) is

R

− x

DL

C L = A + Be (6.15)

CL x =0

= Ci and C L x =∞

= C0 (6.16)

Equation (6.15) and (6.16) derives

C − C − DR x

C L = C 0 1 + i 0

e L (6.17)

C

0

0.8

0.7

0.6

0.5

0.4

0.3

R=0.5D

0.2

R=5D

0.1 R=50D

0

-0.5 -0.25 0 0.25 0.5 0.75 1 1.25 1.5

Graduate Institute of Ferrous Technology, POSTECH

R=0.5D represents the case when interface moving speed is very small. Solute

diffusion is relative quick. The solute profile is almost like a straight line, similar to

the steady state solute distribution. R=50D represents the case when

solidification is going very fast. The diffusion layer is very thin. In many

engineering cases, the solute profile is in between.

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