Module 5

Determination of different kinds of diffusion parameters

Previously we discussed the Fick’s laws of diffusion and the solutions

for constant diffusion coefficient.

In substitutional diffusion this in fact is interdiffusion coefficient. It

does not explain anything about the intrinsic diffusion of elements.

Further, in most of the systems, interdiffusion coefficient is not constant

and we need to derive relations to calculate these parameters.

We also need to develop the relation to calculate intrinsic diffusion

coefficients.

In this module, we shall derive the relations following which we

calculate different kinds of diffusion parameters.
 Matano-Boltzmann Analysis

Limitations of error function analysis:

We derived the relation for error function analysis considering diffusion

coefficient as constant.

This relation can be used for both interstitial and substitutional diffusion to
determine the diffusion parameters.

In interstitial diffusion, it is actually the diffusion coefficient of C in the host

element.

In substitutional diffusion, it is actually the interdiffusion coefficient, which is a

kind of average of intrinsic diffusion coefficients of the elements.
~

If, D is not constant then the Fick’s second law can be written as
~
∂C ∂  ~ ∂C  ∂D ∂C ~ ∂ 2C
= D = +D 2
∂t ∂x  ∂x  ∂x ∂x ∂x
~
∂D

Here problem is with the term and solution of this equation is not possible
∂x
 Variation of diffusion coefficients with composition

β
B2/β

In reality diffusion coefficient changes with composition in most of the cases

and error function can not be used for the analysis.

Note the dramatic change of interdiffusion coefficient in B2 NiAl phase with
composition.

Error function is mainly used to analyze interstitial diffusion for example
carburization of steel, since diffusion coefficient does not change much with
concentration.

Matano with the help of Boltzmann parameter solved Fick’s second law to
develop a relation for the interdiffusion coefficient.

Here onwards we shall consider substitutional diffusion unless mentioned

although note that the outcome of Matano-Boltzmann analysis can also be used to
calculate diffusion coefficient where interstitial diffusion mechanism is operative.

Boltzmann parameter can be expressed as

x − x0 x
λ = λ (CB ) = 1/ 2
= 1/ 2
; x0 = 0 is the initial contact or bonding plane
t t

This parameter indicates that every concentration in a particular diffusion

couple will have a fixed value of λ, which is expressed in the relation above.

This indicates that every concentration

1/ 2 in the interdiffusion zone will move with
annealing time such a way that x / t will have a constant value.

Note that this relation is developed based on the experimental finding.

This is further explained with the help of schematic concentration profile in the
next slide.

If the concentration C * moves x1 to x2
B
after annealing time from t1 to t 2 ,
following Boltzmann parameter, then

x1 − x0 x2 − x0
λ = λ (C ) = λ (C B* ) = =
(t1 )1/ 2
(t2 )1/ 2

This relation is based on experimental results and it is found to be true, as can
be seen in Ni/Ni-Pd diffusion couple

It can be seen that every concentration corresponds to one particular λ value.

It is the same even for different annealing times.

Acta Materialia 51 (2003) 2905–2919


Let us consider a diffusion couple between two alloys, CB− and CB+ in the A-B binary
system.

Suppose our aim is to calculate the interdiffusion coefficient,

~ at one particular
D
composition, CB* after the annealing time, t1 .

Note that it is necessary that the ends of the diffusion couple are still unaffected.

Initial boundary condition, since at annealing time t = 0 materials are not
affected, can be written as
C B = C B− for x 〈 0 at t = 0
C B = C B+ for x 〉 0 at t = 0

Fick’s second law in terms of interdiffusion coefficient can be written as

∂C ∂  ~ ∂C 
= D 
∂t ∂x  ∂x 

Now we use the Boltzmann parameter to replace the variables t and x with λ.
1
λ = λ (C B ) = x / t 2

∂C B ∂C B ∂λ 1 x ∂C B
= =− 3 C = C B− for λ = −∞
∂t ∂λ ∂t 2 t 2 ∂λ
C = C B+ for λ = +∞
∂C B ∂C B ∂λ 1 ∂CB
= = 1
∂x ∂λ ∂x t 2 ∂λ
∂x
∂λ =
t1 / 2

Replacing these in the Fick’s second law we get
1 x ∂CB ∂  ~ 1 ∂C B 
− 3 = 1 D 1 
2 t ∂λ t ∂λ  t ∂λ 
2 2 2

1 x  ~ ∂C 
− 1 ∂C B = ∂ D B  using the Boltzmann parameter
2 t2  ∂λ 
1  ~ ∂C 
− λ∂C B = ∂ D B 
2  ∂λ 
*

Since we are interested to calculate the interdiffusion coefficient at C B , we need to
integrate from CB− to C B*
C B* C B*
1 ~ dC B
−
2 ∫ λdC B = D
dλ C B−
C B−
C B* C B*
1 ~ dC B
2 C∫−
− xdC B = D t using the Boltzmann parameter
dx C B−
B

C B*
1 ~  dC  since derivative at unaffected part of
− ∫ xdCB = Dt  B  −
the interdiffusion zone, C B is zero
2 C−
B
 dx  CB*
C B*
1  dx 
~
( )
D C B* = − 
2t  dC B
 ∫ xdC B
 C B* C −
B
 C B*
~ 1  dx 
( ) 2t  dC B  C * C∫−
D C B* = −   x dC B
B B

x = x − xo since xo = 0

So first we need to find the position of the initial

contact plane xo , which is also known as the Matano
plane

The initial contact plane position can be found by
equalizing the areas P and Q.

However, we need to change the variable for
integration in terms of distance, x, which is rather
easy to handle.
 ∫

After integration by parts ( udv = uv − vdu ) ∫
 x* 
1  ∂x 
~
( )
D C B* = − 
2t  ∂C B


(
* *
) ∫(
− −
)
 x C B − C B − C B − C B dx 

 C B*  −∞ 
-A B

The terms inside the bracket are denoted by M and N in the figure in previous slide

~ 1  ∂x 
( )
D C B* =   [A + B ]
2t  ∂C B  C *
B

Note: negative sign is cancelled because of consideration of sign of the areas.