Effect of molar volume in a hypothetical diffusion couple

Let us consider a hypothetical phase diagram, in which three compounds, α, β and

γ are present.

Stoichiometric composition of these phases are, NB = 0.25, 0.6 and 0.75.

α = A0.75B0.25

β = A0.4B0.6

γ = A0.25B0.75

Let us consider the molar volume of the phases, α and γ are 1 and 2 units,
respectively.

If molar volume varies ideally, it can be shown that the molar volume of the β
phase will be 1.7 units.

Let us consider that we make a diffusion couple of α and γ, where the β phase
grows in the interdiffusion zone.

Further let us consider that 0.6 moles of α and 1.4 moles of γ gets consumed to
produce 2 moles of β. In terms of reaction equation, it can be written as

0.6A 0.75 B0.25 (α ) + 1.4A 0.25 B0.75 (γ ) = 2A 0.4 B0.6 (β )

Correctness of the equation should be checked by equalizing total number of

elements in the left and right hand side of the equation.

We consider a unit cross section of the sample. So we can consider that 0.6 unit
length of α and 1.4x2=2.8 unit length γ get consumed to produce a total 2x1.7 unit
length of the β product phase.

0.6 × 1(α ) + 1.4 × 2 (γ ) = 2 × 1.7 (β ) = 3.4 units (In the ideal system)
 0.75

0.6
NB

0.25

-∞ 3.4 +∞
x

This is the composition profile of the diffusion couple.

Now we need to plot with respect to YB/Vm vs. x or (1-YB)/Vm vs. x.

 1 − YB− 1 1 − YBβ 0.3 1 − YB− 0
= = 1, = = 0.1765, = =0 For (1-YB)/Vm vs. x
Vm 1 Vm 1.7 Vm 2
YB− YBα 0 YBβ 0.7 YB+ YBγ 1
= = = 0, = = 0.412, = = = 0 .5 For YB/Vm vs. x
Vm Vm 1 Vm 1.7 Vm Vm 2

1 − YB P YB 0.5

Vm 0.1765
Vm S
R 0.412
Q 0
0
3.4 µm 3.4 µm
Distance, x Distance, x

Areas P and Q are equalized at X1 Areas R and S are equalized at X2

(1-0.1765)X1 = (0.1765)(3.4-X1) (0.412-0)X2 = (0.5-0.412)(3.4-X2)

X1 = 0.6 X2 = 0.6

So the location of the initial contact plane found following the YB/Vm vs. x or
(1-YB)/Vm vs. x plots is the same in the case of ideal variation of the molar volume,
which is in fact the actual initial contact plane before annealing of the diffusion
couple.

Now let us consider the non ideal system, where molar volume of the β phase
deviates positively and the molar volume is 1.85 units.

Again considering the unit cross section of the diffusion couple, we can say that
total 3.4 units of the α and γ phases get consumed to produce 2x1.85 unit of the
product β phase. In terms of reaction equation, it can be written as

0.6 × 1(α ) + 1.4 × 2 (γ ) = 2 × 1.85 (β ) = 3.7units

0.75
So there is an extension of 0.3 units of
0.6
NB the length of the diffusion couple after
the interdiffusion.

0.25

-∞ 3.7 +∞
x
 1 − YB− 1 1 − YBβ 0.3 1 − YB− YAγ 0
= = 1, = = 0.162, = = =0
Vm 1 Vm 1.85 Vm Vm 2
YB− YBα 0 YBβ YBβ 0.7 YB+ YBγ 1
= = = 0, = = = 0.378, = = = 0.5
Vm Vm 1 Vm Vm 1.85 Vm Vm 2

1 − YB YB
P 0.5
Vm Vm S
0.162
0.378
R
Q 0
0

3.7 µm 3.7 µm
Distance, x Distance, x

Areas P and Q are equalized at X1 Areas R and S are equalized at X2

(1-0.162)X1 = (0.162)(3.7-X1) 0.378X2 = (0.5-0.378)(3.7-X2)
X1 = 0.6 X2 = 0.9

In the case of deviation analysis gives two different values and the difference is
equal to the expansion. In real experiments, it is almost impossible to find the exact
location of the initial contact plane because the molar volume variation will not be
so simple as it is considered in this case. Actual plane is in fact somewhere in the
middle of these two values.