Ternary and multicomponent diffusion

The interdiffusion flux of an ith element in a multicomponent system can be

written as ~ n −1
~ ∂C j
J i = −∑ Dijn
j =1 ∂x

In a ternary system, it can be written as
~ 2
~ ∂C j
J i = −∑ Dij3
j =1 ∂x

That means
~ ~ ∂C1 ~ 3 ∂C2 ~ ~ 3 ∂C1 ~ 3 ∂C2
J1 = − D113 − D12 J 2 = − D21 − D22
∂x ∂x ∂x ∂x

As derived previously in binary system, the interdiffusion flux of element 3 can

be calculated from
~ ~ ~
V1 J1 + V2 J 2 + V3 J 3 = 0

Here third or the nth element is the dependent variable. It comes from the fact
that in a system of n elements we need to determine the parameters for n-1
elements because

N1 + N 2 + ......... + N n = 1

This is the reason that in a ternary system, we can determine the flux of the
third element from calculated flux of two elements, as expressed above.
 ~

D113 and D~223 are the main or direct interdiffusion coefficients, which represent the
influence of concentration gradient of one element on the diffusion rate of the same
element in the presence of the third element.
~3 ~3

D12 and D21 are the cross or indirect interdiffusion coefficients, which represent the
influence of concentration gradient of one element on the diffusion rate of other
element in the presence of a third element.

So unlike binary system, we need two diffusion parameters for the calculation of
flux in a ternary system.

In most of the ternary systems, we do not have the knowledge of molar volume
and we consider a constant value. That means the partial molar volume of the
elements at any composition are also the same.

So we can rewrite the equations as

~ ~ ∂N1 ~ 3 ∂N 2
Vm J1 = − D113 − D12
∂x ∂x
~ ~ 3 ∂N1 ~ 3 ∂N 2
Vm J 2 = − D21 − D22
∂x ∂x
~ ~ ~
J1 + J 2 + J 3 = 0

Now question is that which element should be considered as dependent or the
third element. It is shown mathematically that for correct third element the
relations below should fulfill.

~ ~3
D113 + D 22 >0
~ ~3 2 ~ ~3 ~ ~3
( D113 + D 22 ) ≥ 4( D113 D 22 − D123 D 21 )

~ ~3 ~3 ~3
( D113 D22 − D12 D21 ) ≥ 0

In general it is a practice to consider the element with highest concentration as

host or dependent element, especially if it is measured in a particular
composition range.

However, many times it is measured over the whole composition range and one
can consider any of the elements if it fulfills the condition.

It is also possible that all the three elements fulfill the condition and any element
can be considered for this.

Overall these parameters are important to explain the flux or the elemental
distribution and discussion can be done with any of the possible ways.

Further from the standard relations below we can determine other
interdiffusion coefficients, if interested

~ ~ ~
D112 = D113 − D123
~ ~
D132 = − D123
~ ~3 ~3 ~3 ~3
D312 = D22 + D12 − D11 − D21
~ ~3 ~3
D332 = D22 + D12
~1 ~3 ~3
D22 = D22 − D21
~1 ~3
D23 = − D21
~1 ~ ~3 ~3 ~3
D32 = D113 + D21 − D22 − D12
~1 ~ ~3
D33 = D113 + D21

Transactions of the Metallurgical society of AIME 242 (1968) 1370


In a binary system, we have seen before that we can determine the interdiffusion
coefficient over the whole composition range from a single composition profile only,
since it needs only one interdiffusion coefficient to relate the flux and the
concentration gradient.

However, in a ternary system, four interdiffusion coefficients are required to relate

the fluxes and the concentration gradient.

That means, we need at least two profiles intersecting each other to calculate the
diffusion parameters at that point only, as shown below, for example at point 1, 2 or 3.

So we need first to calculate the interdiffusion flux with respect to the elements
1 and 2 from the respective composition profiles.

We need the relation to calculate the flux directly from the composition profiles.

From the Fick’s second law
~
∂C i ∂J i
=−
∂t ∂x

Now we follow the same treatment like Matano-Boltzmann as shown previously.
Boltzmann parameter is
x − xo x
λ = λ (ci ) = =
t1 2 t1 2

After partial differentiation with respect to t and x and then using these in the
Fick’s second law we get
~ 1x
∂J i = ∂C i
2t

For constant volume

~
∂J i =
1 x
∂N i =
∆N i x
∂Yi since
(
Yi = N i − N i− ) (N i
+
− N i− )
2Vm t 2Vm t ( )
∂Yi = ∂N i N i+ − N i− = ∂N i ∆N i

Integration by parts gives
~
∆N i  * * 
J i* Yi* x *
~ ∆N i
J i* = ∫ ∂J = ∫−∞x∂Y = 2tVm  x Yi − −∫∞Yi dx 
*

0
2tVm  

Following Den Broeder’s graphical approach as discussed previously

 
*
x +∞
~ ∆N i
J i* = − ( 1-Yi ) ∫ Yi dx + Yi ∫ (1 − Yi ) dx  where ∆N i = N i+ − N i−
* *

2tVm  −∞ x* 

So the flux can be calculated for elements 1 and 2 and then four diffusion
parameters should be calculated.
 -5
1.5x10 ~
Co(25Pt)-Ni Co(25Pt)-Ni JNi
100 ~
1.0x10
-5
JCo
at. % Ni ~
80 JPt
at. % Co -6
Composition (at.%)

5.0x10
at. % Pt

J (mol /m -sec)
60
0.0

2
40
-6
-5.0x10
20

~
-5
-1.0x10
0
-5
-1.5x10
0 50 100 150 200 250 300 0 50 100 150 200 250 300
distance (µm) distance (µm)

This is one example of the ternary diffusion couple between Co(25Pt)/Ni

annealed at 1200 ºC for 25 h.

Co and Ni diffuse from right to left they have positive sign in flux. Since Pt
diffuses from left to right it has negative sign in flux.

Further the summation of flux will be equal to zero, as expressed earlier.