The intrinsic diffusion coefficients:

Darken analysis and the van Loo relation

From Kirkendall’s experiment it was clear that one has to determine the
diffusion parameters of both the species.

We have seen before that interdiffusion coefficient (or flux) is measured with
respect to fixed initial contact plane, xo.

However, intrinsic diffusion coefficient (flux) should be measured on the
continuously moving marker plane, xK only, since marker plane measures the
relative movement of flux of the species A and B.
 − +

In the example given in the previous slide, NB is A rich and NB is B rich alloys in
the system of A-B. Kirkendall markers movement indicates that B is faster diffusing
species than A through the product layer.

Marker plane moves parabolically with time, from the initial contact plane.

We can measure the intrinsic diffusion coefficients only at the plane

corresponding to the Kirkendall markers, because, this is the only plane which
gives the idea on the relative mobilities of the species.

Following the Fick’s first law the intrinsic flux and the intrinsic diffusion
coefficients at the marker plane can be expressed as

 ∂C 
J A = − DA  A 
 ∂x  K
 ∂C 
J B = −DB  B 
 ∂x  K

Darken developed empirical relation between the interdiffusion and intrinsic
fluxes as
~
J A = J A + vK C A
~ Here vK is the velocity with which the marker plane moves.
J B = J B + vK CB

Following Boltzmann variable, we can write
xK − xo xK
λK = λ (C K ) = 1 = 1
t 2
t 2

d  λ K t 2 
 1

dx   λK x
vK = K = = 1 = K
dt dt 2t 2 2t

So the velocity of the Kirkendall marker plane can be calculated using the above
mentioned relation from the known annealing time.

Interdiffusion flux of A and B can be related as

~ ~ ∂C  V ~ ∂C ~ V ~ ~
J A = − D A  = B D B = − J B B ⇒ VA J A + VB J B
 ∂x  VA ∂x VA
Since following the standard thermodynamic relation VA dC A + VB dCB = 0

From the relations between the interdiffusion and intrinsic fluxes as shown in the
previous slide

− VA J A + VAC AvK − VB J B + VB C B vK = 0
 ∂C 
vK = −(VB J B + V A J A ) = VB (DB − DA ) B 
 ∂x  K

Relation derived in the previous slide is another way to relate the marker plane
shift to the intrinsic diffusion coefficients.

Now we shall derive the relation between the interdiffusion and the intrinsic
diffusion coefficients.
~
J B = J B + vK CB

From the expression of the marker velocity
~ ∂C ∂C B ∂C
− D B = − DB + C BVB (DB − D A ) B
∂x ∂x ∂x
~ ∂C ∂C B ∂C
− D B = −(1 − C BVB )DB − C BVB DA B
∂x ∂x ∂x
NA N V

Further C AVA + C BVB = VA + B VB = m = 1
Vm Vm Vm
~ ∂C ∂C

So we can write − D B = −(C AV A DB + C BVB DA ) B
∂x ∂x
~
D = VAC A DB + VB C B DA
~
D = N A DB + N B D A For VA=VB=Vm

The last relation was derived by Darken

It can be seen that interdiffusion coefficient is a kind of average (not direct) of
intrinsic diffusion coefficients.
~

Further, D ≈ DB when NA →1
~
D ≈ DA when NB → 1

This indicates that interdiffusion coefficient near pure A depends on the intrinsic
diffusion of B.

This sounds reasonable because interdiffusion depends on the intermixing of

the elements.
Determination of intrinsic diffusion coefficients by van Loo relation

N B − N B−
Y= +
N B − N B−

P Q
~ * Vm  ∂x   
x* +∞
Y * 1− Y
( )
DY =   (1 − Y ) ∫ dx + Y ∫
2t  ∂Y Y K 
*

V Vm
dx 
−∞ m x* 
P Q
 xK
Y
∞
(1− Y ) 
 NB
∫ ∫ dx 
+ −
dx − N B
DB VB  V
−∞ m xK
V m 
=  
DA VA  xK
Y
∞
(1− Y ) 
∫ ∫
+ −
− N A dx + N A dx 
 V
−∞ m xK
V m 
P Q
~
D = VAC A DB + VB C B DA

In the previous slide, the relation for the ratio of diffusivity derived by van Loo is
shown.

Following, the interdiffusion coefficient should be calculated at the same

Kirkendall marker plane.

Then intrinsic diffusion coefficients can be calculated using the relation that
relates the intrinsic and the interdiffusion coefficients.

As explained in the previous slide, composition profile measured is converted to

Y vs. x, Y/Vm vs. x and (1-Y)/Vm vs. x plot.

For example Ni/Pd diffusion couple is
annealed at 1100 oC for 196 hrs.

The variation of molar volume is
calculated from the lattice parameter data
available.

Composition profile is measured after
the annealing.

The marker plane composition was detected by the presence of thoria powder
(at 40.3 at.%Ni) x
 + KY ∞
(1 − Y ) dx   xK Y 
 N Ni ∫ dx − N Ni ∫  ∫ dx 
−

DNi VNi  −∞
V m xK
V m  VNi  −∞Vm  = VNi P
= =V
DPd VPd  xK
Y
∞
(1 − Y )  ∞ (1 − Y )  V Q
 − N Pd
+
∫V dx + N −
Pd ∫ Vm  dx  Pd
∫ dx  Pd

 −∞ m xK   xK Vm 

since N Ni− = 0, N Ni+ = 1, N Pd

− +
= 1, N Pd =0

So after calculating the partial molar volume, the ratio of diffusivities can be
calculated using the above relation. After calculating the interdiffusion coefficient,
using the ratio of diffusivities and the interdiffusion coefficient, the intrinsic
diffusion coefficients are calculated as
DNi = 4.9·10-14 m2/s DPd= 6.5·10-14 m2/s