You are on page 1of 5

# Graduate Institute of Ferrous Technology, POSTECH

## 6.1 Fick’s laws of diffusion

There are two modes of mass transfer: diffusion and fluid flow. Diffusion is
described by Fick’s law.

## Fick’s first law of diffusion describes diffusion flux in chemical inhomogeneous

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

## Figure 1. Steady state mass diffusion

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

## In three dimensional systems it takes

∂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 .

## For multiply component system, the governing equation for diffusion is

(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.

## For a multicomponent and multiphase system, the free energy density is

(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)

(6.9)
where
Graduate Institute of Ferrous Technology, POSTECH

## By including the effect of the cumulative volume change of mixing in a volume-

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)

## Figure 2. Schematic equilibrium phase diagram

Graduate Institute of Ferrous Technology, POSTECH

## Consider a solid-liquid interface to move toward right with a constant speed R,

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)

## The boundary condition is:

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 

## The solute profile in front of solid-liquid interface is demonstrated in figure 3.

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

## Figure 3. Solute profiles at different interface migration rate.

Graduate Institute of Ferrous Technology, POSTECH

## Rongshan Qin (R. S. Qin)

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.

REFERENCES