Tin Pest: A Forgotten Issue in Pb-Free Assembly?

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 about 13.2°C, beta tin turns extremely slowly into alpha tin. “Gray” 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 gray causes most tin objects to crumble.

The macro conversion of white to gray tin takes on the order of 18 months. The photo, likely the most famous modern photograph of tin pest, shows the phenomenon quite clearly.

”The


The photo at left 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 is of the tin buttons on Napoleon’s soldiers’ coats disintegrating while on their retreat from Moscow. Since tin pest looks like the tin has become diseased, many in the middle-ages attributed it to Satan as many tin organ pipes in Northern European churches fell victim to the effect.

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, not expand. Although it appears that the mechanism is not completely understood, it is likely due to gray alpha tin having 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 10s of months, but once it starts, the conversion can be rapid, causing structural failure within months.

Although tin pest can form at <13.2°C, 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 -30° to -40°C. How much of a worry is tin pest in practice? Probably not too much. Small amounts (0.01 to 0.1%) of some metals, most notably antimony and bismuth, inhibit the formation of tin pest, probably by solid solution strengthening. Because most tin will have such impurities, researchers have actually found it hard to produce tin pest in the lab. A concern, of course, is that these impurities are uncontrolled, leaving open the chance of tin pest showing up in some cold temperature applications. I have written a paper that discusses tin pest in more detail. If you are interested, send me a note and I will send it to you.

8 thoughts on “Tin Pest: A Forgotten Issue in Pb-Free Assembly?

  1. Dear Dr.Ron,

    When we have to storage an open solder paste jar for a long time (1-2 months) we place it in a fridge (at 5-7*C). Is the tin pest an issue in this case?

  2. Rosen,

    You have no concern. Tin Pest takes about 18 months to become noticeable. In addition, during reflow the solder would be melted, turning any unlikely tin pest back into tin.

    Cheers,

    Dr. Ron

  3. Sanjay,

    Tin pest is only an concern after assembly if the device is exposed continuously to temperatures colder than 10C for 18 months or more.

    Best wishes,

    Dr. Ron

  4. Doc Ron,

    Is the formation of grey tin an accumlative effect or does the 18 month timeframe restart after the tin is cycled above 18C? Living in the northern tundra (Minnesota) we will have months when we are below 18C but thankfully we bust the 18C thermal energy mark in April to May. Again does the cycling above 18C restart the timer?

    Daryl

  5. Daryl,

    Sadly, the tin pest formation effect is cumulative. It does not reset if the solder goes above approximately 10C. It can only be reset by melting the solder completely.

    Cheers,

    Dr. Ron

  6. Ron,
    A couple of things.

    1) The story about the French soldiers’ buttons is a myth. See my paper B. Christian, “Tin Pest – A Review”, IPC Works, 2006.

    2) When you say reset, you mean the tin does not retake the shape and solid form of the original item. Above the 12.3C the tin does indeed return to the metallic form, but just remains a pile of particles, if that is how far it had progressed in the gray tin phase.

    Bev Christian
    RIM

  7. Hello, I work in the field of automotive lighting and I got a question from a collegue why the bulbs on his privat car was failing. By his description of very thick “oxide” soft layers on the soldering of the signal lighting bulbs I come to think of tin pest and found this blog when I googled. Would it be possible for you to send me your paper?

    Best regards
    Niklas Blomqvist

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