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Kirkendall Effect

The Kirkendall experiment proved that the vacancy mechanism of diffusion is viable by demonstrating unequal diffusion rates between species in an alloy. They took a brass block with an embedded Mo wire and electroplated it with pure Cu. After annealing, the Mo wire shifted positions due to the faster diffusion of Zn compared to Cu, disproving the assumption that diffusion rates are always equal. The experiment conclusively showed vacancies must exist to explain the observed diffusion behavior.

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Sujoy Shivde
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303 views17 pages

Kirkendall Effect

The Kirkendall experiment proved that the vacancy mechanism of diffusion is viable by demonstrating unequal diffusion rates between species in an alloy. They took a brass block with an embedded Mo wire and electroplated it with pure Cu. After annealing, the Mo wire shifted positions due to the faster diffusion of Zn compared to Cu, disproving the assumption that diffusion rates are always equal. The experiment conclusively showed vacancies must exist to explain the observed diffusion behavior.

Uploaded by

Sujoy Shivde
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as ZIP, PDF, TXT or read online on Scribd
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• There was a common belief for a very long

time that both the species in a binary


diffusion couple will have the same
diffusion rate.
• Depending on that possible atomic
mechanism of diffusion was developed or
other phenomena which were controlled by
diffusion were explained
Kirkendall Effect
• Vacancy mechanism was not accepted
as a viable mechanism for a long time
because the concentration of
vacancies was intuitively perceived to be
too small to give perceptible diffusion.
• The Kirkendall experiment proves the
existence of vacancy diffusion in the vast
majority of metallic materials. This is a
remarkable example of an experiment
which is ingenious, simple and
conclusive.
Experiment

They took a rectangular block of brass, which


is a Cu-Zn alloy and wound with Mo wire.
Following, they electroplated the block with
pure Cu
Then this block was annealed at an elevated
temperature for different times.
To their surprise they found that Mo wires
moved inside from its original position.
With the increase in annealing time it moved
even more.
Kirkendall experiment
Experiment
•
If the diffusion rate of both the species are the same,
then amount of Cu transferred from Cu towards
brass and Zn transferred from brass towards Cu
should be the same.
•
Then Mo should not move from its original position.
Mo is actually inert to the system and moves
depending on the volume of the material
transferred.
•
Since Mo wire moves towards brass, it indicates that
Zn must be the faster diffusing species than Cu.
•
Movement of markers from the initial position was
parabolic with time.
•
This indicates the diffusion controlled process.
Conclusion

Two main conclusions were drawn from the


experiment conducted by Kirkendall and
Smigelkas.
1. The rate of diffusion of zinc is much greater than
that of copper in alpha brass.
2. When zinc diffuses more rapidly than copper in
alpha brass, the interface shifts to compensate at
least partially for the diffusion rate.
Interesting Effects
• Lower melting component diffuses much
faster
• Conformation of vacancy mechanism of
diffusion
• The rate at which the two types of atoms of a
binary solution diffuse is not the same.
• The extent of marker shift is proportional to
square root of the diffusion time

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