Tin Pest in Medieval Culture

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 beata.e.lipinska@gmail.com.

Figure 1. Tin pest forms in Sn .05 Cu alloy from Plumbridge. See the paper referenced below.

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

How Far Can We Go to Replace Lead?

The end is nigh for lead in solder, as our columnist Tim O’Neill writes this month in CIRCUITS ASSEMBLY.

Rules governing use of the materials — Directive 2015/863, aka RoHS 3 — are coming online and will be in full force by 2019.

Suppliers have until July 22, 2019 to meet the stricter provisions, which includes no more than 0.1% lead in medical devices, which are joining consumer, industrial and other electronics products on the effectively banned list.

The question Tim poses is, What comes next? Already, the future of commonplace unleaded alloys such as SAC is being questioned. As Tim writes, “It is even feasible SAC 305 will be dislodged by a new de facto alloy that better serves the needs of the market.”

A Norwegian scientist believes he may have the answer. As noted in Phys.org this week, Dr. Henrik Soensteby of the University of Oslo is working on an alternative alloy that contains nothing but common — and essentially benign — elements. In conjuring up his alloy, Soensteby is mixing sodium, potassium and oxygen with niobium, a very strong metal typically used in steel. While niobium dust is reported to cause eye and skin irritation, it reportedly is nontoxic, at least in the volumes used.

It’s not so clear yet how much niobium would be needed. Brazil is the biggest supplier of niobium, producing more than 85% of it each year. Other sources include Zaire, Russia, Nigeria and Canada. World production is relatively light: around 25,000 tonnes per year. Some scientists believe there are ample supplies still in the ground. There’d better be: Some 5 million tonnes a year of lead ores are mined each year, although obviously not all that goes into electronics.

Soensteby is optimistic he can use atomic layer deposition (ALD), a vapor phase method that uses gas at controlled temperatures to stimulate a reaction with the substrate; the output is thin films. It is an emerging technology in semiconductor manufacturing. There are many, many questions, of course. First and foremost, does the alloy actually, you know, work? Also, ALD typically involves higher temperatures than are used in electronics assembly: Would it work with today’s packaging? Will other technologies such as 3D printing or Joe Fjelstad’s solderless Occam process supplant the need for solder in any form?

Still, materials science is the most exciting area of electronics today. We may make fun of folks who walk around with smartphones seemingly permanently tethered to their ears, but we also have them to thank.

 

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Electricity Use in Pb-Free

Folks,

An obvious disadvantage of lead-free electronics soldering assembly is that the oven must be hotter and therefore will use more electricity (versus SnPb37 soldering). But is the extra amount of electricity significant?

KIC’s Brian O’Leary claims that a typical SMT oven uses $7,000 worth of electricity a year at $0.072/Kilowatt hour (Kwh) or about 100,000 Kwh. That number strikes me as about right, as a household uses about 5-20,000 Kwh per year.

In the late 1990s there were 35,000 SMT lines in the world. At a 3% growth rate that would be about 50,000 lines now. So worldwide SMT reflow oven use would be about 5E9 KWhr (50,000 ovens x 100,000 Kwh/per year) worldwide.

With most heat loss be due to convection, the increase in energy use will be approximately proportional to the difference between the oven temperature and the room temperature (25°C). An oven processing tin-lead solder would run at about 210°C versus lead-free’s 250°C. So the added energy for a lead-free oven would be about (250-25)/(210-25), or about 22% more. So if all assembly lines in the world are SMT the added energy use would be about 0.22x 5E9 Kwh = 1E9 Kwh. The cost of this extra electricity would be about $100 million at $0.10/ Kwh. The electronics industry generates about $1.5 trillion in sales. So this added cost would be about 0.0067% of sales. Since world electrical use is about 150,000 E9 Kwhr per year, this increase is about 1/150,000 of all of the electrical use or 0.00067%.

So although more electricity is used, the increase is not significant to the value of the electronics sold or the total world use of electricity.

Best Wishes,

Dr. Ron