Kirkendall effect, importance, and theory, its use

HISTORY:
The Kirkendall effect was discovered by Ernest Kirkendall and Alice Smigelskas in 1947, in the
course of Kirkendall’s ongoing research into diffusion in brass. The paper in which he
discovered the famous effect was the third in his series of papers on brass diffusion, the first
being his thesis. His second paper revealed that zinc diffused more quickly than copper in alpha-
brass, which led to the research producing his revolutionary theory.

INTRODUCTION:
The Kirkendall effect is the motion of the interface between two metals that occurs as a
consequence of the difference in diffusion rates of the metal atoms. The effect can be observed
for example by placing insoluble markers at the interface between a pure metal and an alloy
containing that metal, and heating to a temperature where atomic diffusion is possible; the
boundary will move relative to the markers.

Kirkendall's experiment:

A bar of brass (70% Cu, 30% Zn) was used as a core, with molybdenum wires stretched along
its length, and then coated in a layer of pure copper. Molybdenum was chosen as the marker
material due to it being very insoluble in brass, eliminating any error due to the markers diffusing
themselves. Diffusion was allowed to take place at 785°C over the course of 56 days, with
cross-sections being taken at six times throughout the span of the experiment. Over time, it was
observed that the wire markers moved closer together as the zinc diffused out of the brass and
into the copper. A difference in location of the interface was visible in cross sections of different
times. Compositional change of the material from diffusion was confirmed by x-ray diffraction.

IMPORTANCE:
Since the Kirkendall effect is related to the mass transport at the interface between different
solids, there is much possibility to control hollow nanostructures of a variety of alloys,
intermetallic compounds and mixed oxides. The Kirkendall-effect related processes have been
recognized as one of the useful methods for the fabrication of nanotubes of oxides, sulfides and
phosphides. The Kirkendall effect is related closely to the formation processes of oxide layers
on the several metals such as Cu, Ni and Fe; the rapid outward diffusion of metal ions rather
than inward oxygen ions through the oxide layers can induce the formation of vacancy clusters,
i.e., the Kirkendall voids at the metal sides. This makes it ideal for the fabrication of oxide
nanotubes via the oxidation of metal nanowires such as Cu, Ni and Fe, taking vacancy
clustering inside metal nanowires, due to the Kirkendall effect into consideration.
USES:
 Kirkendall effect can be used as a versatile route to fabricate hollow nanostructures with
different shapes, compositions and functionalities
 Oxy-nitride photo catalysts are a kind of promising material for solar energy conversion.
However, nanoscale design of hollow oxy-nitrides was difficult to achieve due to the thermal
instability of oxide precursors at high temperature. Here, single crystal zinc gallium oxy-nitride
nanotubes were successfully synthesized via the Kirkendall effect

REFRENCES:
1. https://www.intechopen.com/books/nanowires-implementations-and-applications/application-
of-the-kirkendall-effect-to-morphology-control-of-nanowires-morphology-change-from-metal
2. https://www.researchgate.net/publication/260008157_Role_of_Kirkendall_effect_in_diffusion_
processes_in_solids
3. https://pubs.acs.org/doi/10.1021/acs.jpcc.5b06000
4. https://www.intechopen.com/books/nanowires-implementations-and-applications/application-
of-the-kirkendall-effect-to-morphology-control-of-nanowires-morphology-change-from-metal
5. https://www.osti.gov/biblio/455186
6. https://scholar.google.com.pk/scholar?q=uses+of+kirkendall+effect&hl=en&as_sdt=0&as_vis=1
&oi=scholart
7. https://en.wikipedia.org/wiki/Kirkendall_effect#History