Folks,
Readers may remember that I have had an interest in tin pest for some time. Tin pest can occur if nearly-pure tin is exposed to cold temperatures (<13.2oC) for long periods of time. At the end of this post, I provide a short summary of the tin pest phenomenon. See this striking time lapse video of tin pest forming; I assume the time period is over many months.
The reason for this post is that a medieval scholar, Beata Lipi?ska, from Poland is studying tin pest and its effects on medieval culture, most notably in church organ pipes. She has contacted me to see if I can help her find papers that discuss tin pest from a historical point of view. If readers have any references that could help Beata, please contact her directly at [email protected].
What is Tin Pest?
Tin is a metal that is allotropic, meaning that it has different crystal structures under varying conditions of temperature and pressure. Tin has two allotropic forms. “Normal” or white beta tin has a stable, tetragonal crystal structure with a density of 7.31g/cm3. Upon cooling below 13.2oC, beta tin slowly turns into alpha tin. “Grey” or alpha tin has a cubic structure and a density of only 5.77g/cm3 . Alpha tin is also a semiconductor, not a metal. The expansion of tin from white to grey causes most tin objects to crumble.
The macro conversion of white to grey tin takes on the order of 18 months. The photo, which is likely the most famous modern photograph of tin pest, shows the phenomenon quite clearly.
This photo is titled “The Formation of Beta-Tin into Alpha-Tin in Sn-0.5Cu at T <10oC” and is referenced from a paper by Y. Karlya, C. Gagg, and W.J. Plumbridge, “Tin Pest in Lead-Free Solders,” in Soldering and Surface Mount Technology, 13/1 [2000] 39-40.
This phenomenon has been known for centuries and there are many interesting, probably apocryphal, stories about tin pest. Perhaps the most famous of stories is that of the tin buttons on Napoleon’s soldiers’ coats disintegrating from tin pest while on their retreat from Moscow. Another common anecdotal story during the middle ages was that Satan was to blame for the decline of the tin organ pipes in Northern European churches, as tin pest often looks like the tin has become “diseased”.
Initially, tin pest was called “tin disease” or “tin plague”. I believe that the name “tin pest” came from the German translation for the word “plague” (i.e., in German, plague is “pest”).
To most people with a little knowledge of materials, the conversion of beta to alpha tin at colder temperatures seems counter-intuitive. Usually materials shrink at colder temperatures; they do not expand. Although it appears that the mechanism is not completely understood, it is likely due to the grey alpha tin having a lower entropy than white beta tin. With the removal of heat at the lower temperatures, a lower entropy state would likely be more stable.
Since the conversion to grey tin requires expansion, the tin pest will usually nucleate at an edge, corner, or surface. The nucleation can take 10’s of months, but once it starts, the conversion can be rapid, causing structural failure within months.
Although tin pest can form at <13.2oC, most researchers believe that the kinetics are very sluggish at this temperature. There seems to be general agreement in the literature that the maximum rate of tin pest formation occurs at -30o to -40oC.
Cheers,
Dr. Ron