Recent developments on the Kirkendall effect

Ti w
800 °C
72 hrs
Ni

Sometimes seems to be a strange behavior of the Kirkendall marker was

noticed, as explained in the Ni/Ti diffusion couple.

W marker was found at two different places. Result was reported but no
further analysis was done

Met. Trans. 5 (1974) 1817-26


Again strange behavior was noticed when Shimozaki et al. coupled Au with
the Au0.64Zn alloy of the γ phase.

This is explained in the next slide based on the diffusion couple.

Shimozaki et al, Defects and diffusion forum, 95-98 (1993) 629

 Scratch

W-Wire

Au Au-0.64 Zn
Pore Marker
Au-0.64 Zn
Anneal

Marker Zn-rich
β’-AuZn

Au-rich

Pore

Au

Shimozaki et al, Defects and diffusion forum, 95-98 (1993) 629


To make the diffusion couple first flat pieces of Au and the Au0.64Zn
were taken for further grinding and polishing.

Even after polishing treatment some scratches might be present on

the surface, as shown by the white lines.

Following wires, as Kirkendall markers, were placed on one of the

bonding surfaces.

So the scratches can be considered as the negative surface and after

the interdiffusion also these may stay as diffusion cannot happen
through these.

In general these also move with the markers.

That is why many times although markers are not used, line of pores
might indicate the location of the Kirkendall marker plane.

However, Shimozaki et al. noticed a strange behavior.

They found the markers along one line and the pores along another
line.

Now we know that this is not a strange behavior.

Many unknown behavior of markers are found recently.

One stable marker in a system, which is known to be very common was found in Ni-
Pd system.

However, in the Fe-Pd system, thoria particles used as markers are found to be
spread over the interdiffusion zone, as if the inert particles have lost and do not know
where to go.

Acta Materialia, 48 (2000), 385-396


Experiments were repeated in the Au/Zn system again and the markers were
found at two different planes. That means the markers were bifurcated into two
different planes.

The same was found in the Ni-Al system also.

Both the phases have wide homogeneity range over the 50:50 stoichiometric
composition.

Note that two marker planes were found in the single phase only: one plane in the
Au or Ni rich side and another plane in the Zn or Al rich side of the phase.

Philosophical Magazine A 82 (2002) 943-954 and Acta Materialia, 52 (2004), 4041-4048


Bifurcation was also found in Ag-Zn system, however, marker planes were found
in two different phases.

Zeitschrift fuer Metallkunde, 95 (2004) 258-260


We have previously shown that the marker velocity can be expressed by two
different relations.
∂C B
v = VB ( D B − D A )
∂x

Different planes in an interdiffusion zone have a particular composition. Every
composition has a particular intrinsic diffusion rate.

If these are known, then the velocity of different planes can be calculated using
the calculated concentration gradients over the whole interdiffusion zone.

Further the marker velocity can be directly calculated from the initial contact
plane, where markers were located before the annealing process and the marker
plane position after the interdiffusion process by

v K = ( x K − xo ) / 2t = x K / 2t

It is shown that the gradient of the velocity curve plotted using the first relation at
the marker plane location (where the straight line expressed by the second
equation intersects) indicate the nature of the Kirkendall marker plane.

∂v / ∂x ≤ 0 when the slope is less than or equal to zero it shows a

stable marker plane

∂v / ∂x 〉 0 when the slope is greater than zero it shows an unstable

marker plane.

Multifoil diffusion couple experiments were
conducted to determine intrinsic diffusion
coefficients over the whole composition range from a
single experiment.

Following the concentration gradient was

calculated from the diffusion couple below from the
measured concentration profile.

Following it was noticed that the gradient of the

velocity curve is negative when it shows the presence
of a stable Kirkendall marker plane.

∂v / ∂x〈0

Acta Materialia, 48 (2000), 385-396


Following similar procedure it was shown that the gradient is positive in the
Fe-Pd system, where unstable Kirkendall marker plane is found.

∂v / ∂x〉 0

Acta Materialia, 48 (2000), 385-396


Suppose there is a phase, where in one side of the stoichiometry one species and
another side of the stoichiometry another species is faster.

Then the velocity curve can take this shape, where at one part the velocity is
negative and at another part it is positive

Then different kinds of marker behavior can be found depending on where the
straight line intersects this curve.

The location of the intersection can be changed by changing the end member
compositions that is the initial contact plane.
Philosophical Magazine A 82 (2002) 943-954

In the β phase of Au-Zn in the Au rich side Au is the faster diffusing species and in
the Zn rich side Zn is the faster diffusing species.

In the diffusion couple below it shows a stable Kirkendall marker plane since it
intersects the velocity curve where it has negative gradient.

Philosophical Magazine A 82 (2002) 943-954


When the composition of the right hand side of the end member composition is
changed such that the initial contact plane moves towards the left side, the straight
line intersects at the velocity curve where it has a positive gradient and we find
unstable marker plane.

Au40Zn60

Au70Zn30

Philosophical Magazine A 82 (2002) 943-954


The composition of the end members is changed in such a way that the straight
line intersects the velocity curve at two points where it has a negative slope and in
the middle at one point where it has a positive slope.

Instead of three marker planes it gives two stable marker planes, since the
markers get attracted by the stable marker planes at the start of the annealing
process only. Philosophical Magazine A 82 (2002) 943-954