Letter 0740

Tin Pest

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Summary of this thread: Started in 1997 and continuing to 2005, this inquiry is about "tin pest" or "tin disease" -- which is the rather disastrous phenomena where metallic tin can turn to dust in very cold temperatures, as is reputed to have happened to the buttons on the clothing of Napoleon's troops. The thread contains some references to "tin whiskers", which is an entirely different phenomena, probably because some readers assumed that "tin disease" referred to tin whiskering.

The thread was found by students and soon focused more on schoolwork on the subject than the industrial implications of the issue.
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We are looking for detailed information regarding a phenomenon called "tin pest", or "tin disease". This occurs mainly at specific temperature ranges when the pure tin plating spontaneously transforms from one crystalline form to another and flakes off. Any help you can be will be much appreciated. I believe this was first observed at NASA Goddard, but I'm not sure. This effect has rendered pure tin unacceptable for space use under certain conditions and I need to know exactly what conditions will precipitate this phenomena. Thanks.

Bob Denney
avionics - Tampa, FL

Dear Bob,
I learned about this phenomenon many years ago, I only know that it exists if pure tin is exposed to temperatures below appr. 10 degrees Celcius and that the presence of "tin-pest" is a possible threat for non-infected tin. The phenomenon was also observed for Tin-craftmanswork which deteriorated to powder. I think your best chance to find more is the ASTM-database. Success.

Harry van der Zanden
- Den Bosch, Netherlands

Try "Tin in Cold Service" Leaflet No. 55 published by the Tin research Association at Tin Research inc Columbus Ohio (Though they might have moved it's an old leaflet I've got).

If you have problems getting it I could fax you a copy.

Regards

Richard Guise
- Suffolk, UK

Ed. note: We found the International Tin Research Institute at http://www.itri.co.uk

We plate alkaline tin (dull) that contains a percentage of bismuth for collins rockwell that serves the same purpose you are trying to solve. It works for them. We plate on aluminum, steel, copper, stainless steel.

Todd Huehn Spec Plating Corporation    Minneapolis, Minnesota

I am doing a lab report for my chemistry class. The extension question is as follows:

Sometimes extreme physical changes result in permanent changes in the nature of a substance. Investigate the phenomenon of tin pest. What causes this physical change?

Could anyone help me out? I am desperate!

Jen B.
student

I was looking for 'tin pest' on the web because I have a very old tin teapot (I guess about 150 plus years old) and it lost its shiny tin cover. Lately it was sort of vibrating and my wife mentioned it to my father, who has graduated from a Dutch Nautical Institute before WW2. He was the one who mentioned the words 'tin pest' to me and this is why I looked it up. Please note that this teapot has never been in temperatures below 10 degrees Celsius and still it was subject to flaking, etc. It is just very old. Maybe this knowledge is of help.

Siets Jan Meijer -
- Maturin, Monagas, Venezuela

It was vibrating!? I think your teapot has a special variety of tin pest closely related to the larva worms in jumping beans, Siets

Ted Mooney, P.E. 
finishing.com
Brick, NJ

So sorry, just vibrating, no larvae or jumping beans =). Siets Meijer

Siets Meijer
- Maturin, Venezuela

I am doing extra credit for my chemistry class and my assignment was to investigate "tin pest". To find out what it is or whatever. If anyone can give me a website or if someone can tell me I would be very appreciative. Thanks so much,

Lacey L.
student - Falls Church, Virginia

Help I need to know about Tin Pest! For one of my classes! Please help!

April P.
student - Oil City PA

Napoleon, during his advance on Moscow during the severe Russian winter experienced this "disease", (or rather his poor squaddies). The soldiers' buttons, made of tin, crumbled to dust. This is because Tin goes through a change in crystal form at low temperatures to a less crystalline (more amorphous) form.

ROSS MACDONALD

Hello, I'm doing the same lab as Jen, and I could find little information on tin pest.

The question is as follows: "Sometimes extreme physical changes result in permanent changes in the nature of a substance. Investigate the phenomenon of tin pest. What causes this physical change?"

If anyone at all would please point me towards the correct direction as to where I could find information on this online - or what it is for that matter .... Thank you in advance.

Aeone S.
student - Chicago, IL

Tin is stable in the beta form (allotrope) at room temperatures but will change to the alpha form at low temperatures (actually below 13.2 deg C, though much lower temperatures are needed for observable transition, the lower the temperature the faster the transition). The alpha form has a much weaker structure, hence the buttons of Napoleon's troops turning to dust in the harsh Moscow winter. When the temperature rises the situation becomes worse (for buttons) because the transition back to the beta form introduces crystalline faults. "Chemistry of the Elements", Greenwood and Earnshaw, will explain further.

Angie Jamison
- uk

I am a student at Chamblee High School in Georgia. I have a Chemistry question for you. I was wondering if you could help me with it. The question is Sometimes extreme physical changes result in permanent changes in the nature of a substance. Investigate the phenomenon of tin pest. What cause this physical change? Would you please help me in I really could use it Thanx P.S. If possible can email me back tomorrow or ASAP. Thank You.

Aisha T.
- Lithonia, Ga

Uh . . . Aisha . . . now I understand why some teachers ask us to please respond to all student questions with: "Do your own homework!" :-)

You googled and found this, and haven't vested yourself deeply enough to even read this one page! Instead, you ask someone to e-mail you your homework assignment for gosh sakes.

Ted Mooney, P.E. 
finishing.com
Brick, NJ

i am also a student at chamblee high and from the information i have gathered i think tin pest is that when pure tin is exposed to temperatures below 10 degrees Celsius it deteriorates or flakes off into a powder.

n. y.
- stone mountain, ga

I just wanted to thank you for providing me with info. on the tin pest. I, like the other 20 high school students who sent in a question, had the same exact chemistry lab question regarding tin pest, and unlike them, I took the time to read through this web site and gather my answer that way. It was a great help, and thank you again.

Emily D.
Cincinnati, Ohio USA

Thanks for taking the time to write, Emily! It is great to hear that people's efforts weren't wasted :-)

Ted Mooney, P.E. 
finishing.com
Brick, NJ

This has been a helpful site to me and many other friends of mine who were struggling to do that same darn chemistry lab question. All we had to really do is investigate the phenomenon. We just combined the info around this site, to get a good, almost-precise answer.

Ben C.
- Los Angeles, California USA

Hi, guess what, I had the exact same chemistry question. (I guess chemistry teachers are big on sharing.) Anyway this site helped a lot. Thankee kindly.

Elenor D.
- Pasedena, California

wow!, this question about tin pest on chemistry labs seems to be a pretty popular question.. i myself had the same exact question to answer. I was able to gather just about all the info i needed from this site. Well, i would just like to say thanks to all those experts out there willing to share their time to help out us students. Thanks guys!

Mike A.
- King of Prussia, Pa

This Site was a great help with my research on Tin Pest. I like the plethora of others had this question on my lab sheet. So thanks for the help. This site was a great source.

Mike W.
- Bremerton, WA, USA

I just think it's funny how we all have the same question. I sure hope you all are right, though. If all the teachers can conspire against us to give us this lab, we can conspire with them and share answers! B.T.W., wasn't that a fun lab!!! Anyone have any accidents with the silver nitrate?

Matthew H.
student - Cedar Bluffs, NE, U.S.

I, just like every other student who took time to read this page, not only had fun reading the redundancy of fellow students, but learning the answer to a much-asked question. Thank you for your information, and good luck to other high school chemists!

Thanks again, Meg

P.S. Does anybody else think they should update the questions is text books?!?

Meg E.
student - Rhode Island, USA

Ed. note: nah.....

I think it's cool how everyone has the same lab book! This page was really helpful.

Now i know why Napoleon never reached Moscow. His troops couldn't fight AND hold up their buttonless britches!

Science and History class come together!

Tiff G.
student - St. Mary Academy BayView, R.I.

Tin pest, as many people have said above, is caused by a change of state in the tin. The tin we all know and love is normally bright silver and crystalline. If you get a piece of pure tin and bend it, it will give out a noise. This is called "tin crying" and is caused by the tin crystals distorting against each other.

However, if tin is exposed to low temperatures the silver grey metal changes from the beta state (or crystal form) to the alpha state (or crystal form). This theoretically occurs at about 18C, but the impurities in the tin force this temperature down - the more impurities, the lower the temperature. It is very difficult to get pure tin, most commercial tin is about 99.5% pure and this is enough to drop the transition temperature to quite low levels. Alpha tin is a manky grey powder. There is a story, which I cannot confirm, that at the end of the C19th a Russian Czar had a shipment of tin sent across Russia and when it arrived it was the horrible grey type. The Czar's officials thought the man who transported it had robbed the Czar and he was put to death. It is also claimed that Napoleon's troops suffered from tin pest when the buttons on their tunics fell to pieces because of the very low temperatures. I cannot confirm this because I wasn't around then!

I hope this is of interest and helps anyone who is eager to improve their continued education.

Trevor Crichton R&D practical scientist - UK

Tin pest has been well know in the north of Sweden as the Sami peoples spin thread from it to decorate their clothes with. The tin of today can take -40 degrees or more (that the same on both F. and C. scales) The tin is first purified and then a couple of percent of pure silver is added. This information comes from a book called "TENNTRADSBRODERIER" by Mona Callenberg. She claims that tin has a tetra cristalen above 13 degrees C. and s cubical cristalen form.

Tim Honn
- Str–msund, Sweden

Monmouth Academy's Junior Chemistry Class was lucky enough to have that same text book that is so often mentioned throughout this website. I too scanned the internet in search of information on Tin Pest, and was thrilled to find a single site that completely answered my question! I appreciate everything you've provided and hope that you understand how much you've helped high school students around the world!!

THANK YOU!

Rebecca E.
student - N. Monmouth, Maine, USA

I have a son in high school taking Junior chemistry too, Rebecca. Won't it be funny if he gets the same question and hits the 1-1/2 billion pages of the world wide web looking for the answer, only to find it on his father's site :-)

Ted Mooney, P.E.  finishing.com Brick, NJ

I have found some interesting and similar stuff about solders and soldering in "how to do" type literature published by Johnson Mathey Metals (dating from the 1950's). It seems that a little silver will improve things greatly. The consequences of what might happen to a space satellite going into earth shadow when cheap solder has been used hardly bear thinking about!

David Benyon
- Bude, Cornwall, England

Hello all!

I am a high school student doing research of my own on Tin. I just thought I would add that other sources have stated that tin changes colour at about 13.2 degrees Celsius. Also, here is another interesting fact - in Medieval Europe, when tin organ pipes turned colour because of temperature change, it was thought to be the "devil's work." Keep up the great work and thanks for a great website!

Sarah F.
student - Listowel, Ontario, Canada

I have a copy of "Tin: Its Mining, Production, Technology & Applications," copyright 1949 by C. L. Mantell

The author devoted several paragraphs to tin pest. White tin (tetragonal) is stable down to 18°C. Below that, the stable phase is gray tin (cubic). The transformation is very slow, so tin objects do not spontaneously crumble into gray powder. The transformation begins to accelerate rapidly at -20°C, peaking at -45°C. The implications are large for electronic devices used in cold climates. Old solders were tin-lead, while recent solders are either tin-antimony or tin-silver.

Joseph Greene
heat treating furnaces - Cherry Valley, IL

To add on to an earlier comment, the book Napoleon's Buttons goes on to say that the story is difficult to confirm for two reasons. First, people in Napoleon's time were well aware of tin disease, and Napoleon probably would not have permitted pure tin buttons on his army's uniforms. Second, tin does not disintegrate rapidly when exposed to cold--it's a slow process, even at the freezing cold temperatures in Russian in 1812.

Noel Lee
- Portland, OR, USA

Ed. note: True or not, it is a cute story and it inspires interest in students, so let's keep the story alive :-)

Hey y'all I just wanted to say that I am so greatly amazed by the majority of questions based on the same lab that we have all encountered. It's reaaaaaallly funny, though, that the question is verbatim. Thanx FINISHING.COM! All your answers really helped!

~*~zee~*~

Zeinab Z.
student - Kissimmee, Florida, USA

Hey guys,

I am doing the same exact lab right now. with the same exact extension.... the following website was where I found why the tin disintegrates

http://palimpsest.stanford.edu/byform/mailing-lists/cdl/1998/1218.html

Hope it helps

Meg M.
student - East Greenwich, RI

Very interesting discussion. I have been involved in the soldering industry for 30 years and have some experience of the problem in the electronics arena. Certainly NASA did report this problem back in the sixties which lead to antimony being made a requirement in the then federal QQS solder specifications even though the alloy used was not pure tin but 60/40 Sn/Pb. Adding between 0.2 and 0.5%Sb made the alloys much less prone tin pest. I am sure it didn't prevent it totally but delayed the onset to a lower temperature. With the global transition to lead free solders the likelihood of tin pest occurring could increase. Space applications will continue to use lead containing solders for the foreseeable future though.

Chris Ward
- London, UK

As mentioned in an earlier posting, there has been published a fairly popular book called "Napoleon's Buttons: How 17 Molecules Changed History", by P. Couteur and J. Burreson of British Columbia. In this book they make, or remake the claim, that one of the reasons for the defeat of Napoleon's Grande Armeé in Russia was that his solders had tin buttons. The argument is that in the cold of the Russian winter the normal, white tin turned to gray tin (tin pest), which has no structural integrity and as a result the solders could not keep their coats closed and this facilitated their freezing to death.

This scenario is highly unlikely for at least a couple of reasons. First, most of Napoleon's armies (not his Egyptian expedition at least) had previously spent considerable amounts of time in temperatures below 13.2C, the transition temperature of tin. Even if one makes the argument that tin pest is more likely to occur at around -30C, certainly several of Napoleon's armies spent considerable time slogging through the Alps and other mountains of Europe for weeks or months on end. No mention of this supposed problem has come to light from these forays into cold climates.

Virginia Shaw Medlen in her history of the Irish volunteer unit of Napoleon's forces "Legion Irlandaise (Napoleon's Irish Legion) 1803 – 1815" states: "Buttons were gold for officers and brass for other ranks." Some brasses contain tin (1% tin is common for certain types), but they were certainly did not contain 100% tin or even the tin concentration levels of modern lead-free (SnAgCu) alloys, all of which contain at least 85% tin.

Also, the following quote [P. Britten-Austin, "Napoleon's Lost Army: The Soldiers Who Fell", BBC History Webpage] has been found: "Now, 183 years later, the splendid museum in Vilnius displays many objects relating to the Napoleonic adventure. What's this button, made of an alloy of COPPER AND TIN (CAPITALS added by me), stamped '61? It comes from a blue uniform jacket, almost certainly that of a Dutchman. For the 61st Line Regiment was made up largely of (mostly unwilling) conscripts from the Netherlands."[sic]

The following materials and conditions have been found to favor the condition:
Si, Al, Ge, Mg, Zn, Co, Mn, Te, As, SAND, InSb, CdTe, Cold working the tin, Reactor irradiation and Certain solutions.

The following materials and conditions have been found to NOT favor the condition:
Bi, Sb, Pb, Au, Cd, Ag, Ti, In, Surface oxidation, Annealing, High pressure (90 Atm.) and Slow growth of initial white tin crystal.

I have tried producing gray tin by keeping 4 9's tin, tin/zinc eutectic, and tin/silver/copper eutectic at RT, 4C, -4C and -42C either as-is, bent, some materials impregnated with diamond dust (cubic structure like gray tin) and some impregnated with elemental silicon powder. ONLY the latter at -42C has produced gray tin, which we have confirmed by x-ray diffraction. This took somewhere between 15 and 96 days.

Beverley Christian
- Waterloo, Ontario, Canada

Hi guys, thanks for the very helpful website. I, a student, took the time to read through this and have finally answered the elusive "Sometimes physical changes result in permanent changes in the nature of a substance..." question. However, I'm a little confused on what an allotrope is. On other sites, allotropes are defined confusingly or are not mentioned at all. Is an allotrope just the beta state of tin?

Elizabeth S
Maumee Valley Prep School - Pittsburgh, Penn., USA

Thanks for the kind words, Elizabeth. A student should keep a dictionary at the ready, because you lose continuity and focus jumping all over the web. If you look this word up you will find that an allotrope is: "each of two or more different physical forms in which an element can exist. Graphite, charcoal, and diamond are all allotropes of carbon." Hopefully this 'permanent changes in the nature of a substance', and Napoleon's buttons turning to dust in the cold, and allotropes, all come together and make sense?

Ted Mooney, P.E. 
finishing.com
Brick, NJ

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