Introduction

The symbol in the title is the alchemical symbol for tin, the sign of Jupiter.

The word "tin" is cognate with the German "Zinn," describing a soft, white metal with a low melting
point. Its two main uses, both past and present, have been the coating of other metals, and in alloys.
The alloy with copper, bronze, is of outstanding significance. In Latin, copper or any of its alloys were
called aes. In Greek, the equivalent word was calkos. The essential thing was the ruddy color,
different from that of gold or the white metals. Tin itself was kassiteros in Greek, but in Latin it
was plumbum candidum, "white lead." Plumbum was the generic name for soft white metals with
low melting points. Lead proper was plumbum nigrum, "black lead," because of the dark streak it
gave when rubbed on something. The term stannum was mostly used for an alloy of lead and silver
obtained in the winning of silver. Not until the 6th century was it applied to tin, but thereafter was
commonly used in this sense.

The prettiest word for tin is the Spanish estao. It evolved from stannum by first becoming stanno
(the m never was strongly pronounced in Latin, and mostly nasalized the u). Then the Goths had
problems with "st" so it became estanno. Finally, the double n merged into when the spelling was
regularized, and we have the final form. Italian stagno suffered a similar transformation (gn = ). The
French tain is closer to the English (and Dutch) tin. Indeed, the second syllable would be
prounounced just as "tin" would be. In Russian, tin is lovo, while in Welsh it is alcam, truly different
sounds.

The chemical ideas of the time considered lead, tin and anything like them as flavors of one basic
substance. All you had to do was add the right spices to turn them into one another. The ores were
earth, and lacked fire to make them shiny. Ores absorbed the fire and became metals. This kind of
chemistry was worthless for metallurgy, but must be kept in mind when considering history. It was
not to change until around 1800, and even then the fundamental reasons (electrical forces) were not
known for another century. Our very useful knowledge of chemistry is a very recent development.

This article discusses the properties of tin, its uses in industry, and all the curious tin lore that could
be found.

Some Metallurgical History

Metals are important enough in the human story to be used to characterize eras of development:
Copper Age, Bronze Age, Iron Age. Nevertheless, relics are few, and our knowledge of the early
exploitation of metals is almost nonexistent. In such an exigency, Science fabricates stories that
seem plausible to plug the gap, and these are copied from author to author until they become a
solid part of the edifice of knowledge.

Some metals can be picked up off the ground in metallic form, and hammered into attractive
ornaments. Such native metals are gold (Au), silver (Ag), copper (Cu), platinum (Pt) and iron (Fe).
These occurrences are very rare, but once they are found, the area is combed over diligently for
more. How many nuggets have you discovered in your walks? None of these native metals are good
for much more than trinkets. Native iron, which occurs (very rarely) in the earth as well as in
meteorites, is very hard to work and would have to be admired as crusty lumps. In the New World,
there was no metallurgy; the gold found by Cortez and Pizarro had to be laboriously collected, the
copper ornaments were not coveted by the invaders, and everyone was unaware of the enormous
wealth in silver that lay concealed in the black sulphate.

In the Old World, all the early civilizations--in China, India, Mesopotamia and Egypt--arose without
metal, as Neolithic communities that settled, herded, farmed and built in mud brick. Copper, bronze
and iron then appeared in succession, each granting significant advantages in tools and weapons.
None of the appearances were random, and the techniques spread by diffusion, suggesting that the
developments were the product of ingenuity, not chance, and very hard-won.

The story is that some gormless hunters built a campfire on copper ore, and, lo, copper ran forth.
"By Orm, that's copper!" one exclaimed. Another hammered at it, enthusing "We've got copper,
copper galore!" Now, the usual campfire is not hot enough to melt copper, and building the
fire on the ore would not do much good, and besides copper ore does not present itself in large
areas good for campfire hearths. If it were produced, it would look like the rest of the black clinker in
the ashes. It is more likely (but we do not know) that the ore was thrown onto the fire because
someone wanted to see what would happen. You do not see many campers throwing stones or
earth (lumps of ore would be useless) on a fire, or combing through the ashes for valuable things.

Once you do start throwing crushed rocks on fires, there are many possibilities. Most of them do not
produce metals. The rocks have to be very carefully selected. However, if you are in the middle of a
mineralized area such as western Cornwall, many curious rocks are available, a good number of
which will give you metal. Many ores (an ore is a mineral from which a metal can be profitably
extracted) are sulphides, such as Cu2S, chalcocite. When you heat such a sulphide in air, the reaction
3Cu2S + 2O2 2Cu2O + 2SO2 takes place, creating cuprous oxide instead of cuprous sulphide. It is
best not to stand downwind. This is the process of roasting an ore to drive off the sulphur.

If we did this on a goodly fire, the heat would have driven the volatiles out of the fuel (wood),
leaving carbon, and then the air would have formed carbon monoxide: 2C + O2 2CO. Of course, in
the usual fire this monoxide would burn to carbon dioxide, but here it can react with the cuprous
oxide: Cu2O + CO Cu2 + CO2. It is said to reduce the copper to the metallic state, which is done by
adding electrons to it. This cannot happen unless the ore is finely enough divided for the monoxide
to get to it. This process is called smelting. If the fire is hot enough (1083C) the copper will melt and
run out. The early metallurgist, however, normally got his copper as a clinkery mass that had to be
hammered, annealed and rehammered before it looked like anything. This is said to have happened
in Mesopotamia and Cyprus (in the West) around 3500 BC, but the date cannot be trusted. How can
you date something when you really don't know what it was?

Although this looks easy, and we can understand it with our current knowledge of chemistry, in
practice it was not a simple operation and required experience and technique: it was, indeed, an art.
It is interesting that religion did not seem to play a very great role in creating metallurgy; only
afterwards did priests see an opportunity to profit from superstitious awe. Bloody sacrifices were
encouraged to prevent failures, and, of course, donations to priests would not be refused. The
uselessness of religion in metallurgy seems to have been realized at an early date, and in classical
times it played little role, in spite of the superstitious tendencies of the general population. In
medieval times, malicious spirits were blamed for making ores barren, and for ruining the product,
when the real problem was a useless theory of chemistry.

The campfire theory extends to the production of bronze. Now our worthy hunters build their fire on
a mixed copper and tin ore, and out pours bronze. "By Orm, look at this stuff! It's hard and would
take a good edge! We rule!" This is even less likely than the accidental discovery of copper, as was
pointed out by the Hoovers. Copper and tin ores do not usually occur in the same places (they do in
Cornwall, but bronze did not come from there). However, once you start throwing curious crushed
rocks on fires to see what happens, you are likely to see other metals, of which lead, tin and iron are
the most probable. Lead and tin will run out of any serious fire as liquids, surely making an early
metallurgist's day. Iron will remain as a black, spongy clinker, since the melting point of iron is
1535C, well above the capacities of any simple fire. In fact, when fires are blown by bellows (an
early invention) too vigorous blowing would melt the iron, and it would absorb impurities like
carbon, and so would be ruined. Iron is a special case, and its technique is complex.

Bronze weapons are said to have been found in Britain and dated from 1800 BC. This seems roughly
correct, but I would like to know what the "bronze" is, and how the date was determined. Impure
copper does not count as "bronze" in this respect. Bronze has to be made by design.

If you do this with mercury or zinc ores, the metal vaporizes instead, and you do not get any nice,
bright liquid metal. These metals were discovered a bit later, in classical times, when someone
examined the flues of furnaces that had been fed a suitable diet, and then the corresponding ores
were identified. In early times it is possible that copper, tin and lead were all known. Bronze was
probably always made deliberately by the addition of tin to molten copper. This required a bellows-
blown furnace that would reach white heat. The properties of bronze depend very sensitively on the
amount of added tin, so "accidental" alloys would not be very useful or promising.

From the beginnings of the use of metals from ores, then, the roasting and smelting processes have
been used, with carbon as the reducing agent. At first, the carbon was from the charcoal created in
the fire, but later it was always a purer product made by charcoal-burning. Metallurgy took place in
the woods and the hills, its secrets carefully guarded to preserve monopoly, just as in the present
day. Today, all the rich ores that taught mankind metallurgy are exhausted. If we had to start over
again, it could not be done, at least for several million years, to allow weathering to work its
wonders, or for new fluids to deposit primary ores.

Properties of Tin

Tin (Sn), atomic number 50, atomic weight 118.70, is a member of column IVA of the periodic table,
five elements whose outer electron configuration is s2p2. Its mates are carbon (C), silicon (Si),
germanium (Ge) and lead (Pb). These elements are remarkable in that they are commonly used in
the pure form. Carbon is found as graphite, charcoal and coal; silicon and germanium are
semiconductors, tin is found in tinplate, and lead as pipes and sheathing of electrical cables. Carbon
is extraordiarily important as the basis of organic compounds, since it can form long covalently-
bonded chains and rings. Carbon is nonmetallic, silicon and germanium intermediate, tin and lead
metallic. It is useful to compare tin with the other elements in its column.
Tin has the unusually low melting point of 231.85C, and the unusually high boiling point of 2260,
2270 or 2687C, according to different authorities. This great range makes it easy to form alloys
without loss in vaporization. Its latent heat of melting is 14.32 cal/g, its specific heat 0.055 cal/g-K,
and its thermal conductivity is 0.1528 cal/cm-s-K. The electrical resistivity of tin is 11.5 -cm. The
coefficient of linear thermal expansion is 16 x 10<sup-6< sup="">per C. Its tensile strength is low,
about 2000 psi, and its Young's modulus is 5.9-7.8 x 106 psi. It is quite soft, Mohs 1.8 or Brinell 5.0
(1000 kg, 10 mm).</sup-6<>

Tin exists in three allotropic forms. Below 18C, the stable form is -tin, or grey tin, with a diamond
structure (like carbon, silicon and germanium) and a density of 5.765 g/cc. The lattice constant a =
0.6942 nm, and the melting point is 230C. It is a semiconductor with a band gap of 0.08V. It is a
crumbly gray nonmetal. From 18C to 161C, the stable form is -tin, or white tin, a metal of
tetragonal crystal structure and a density of 7.2984. This is the normal appearance of tin. The
recrystallization to -tin is very slow unless the temperature is lowered to -40C or so, and then may
take place in days. When this destroyed Russian organ pipes, it was thought to be the work of the
"tin pest." Finally, from 161C to the melting point, -tin has about the same density, but rhombic
crystal form. Besides tin, only carbon (graphite and diamond), oxygen (oxygen and ozone) and
phosphorus (red and white) exist in allotropic forms.

When -tin is bent, it emits a sound called "tin cry" from the shearing movement between the
crystal grains. This can more often be sensed by touch as a kind of grating rather than as an actual
sound. Tin is remarkably lighter than the lead it resembles, which can be surprising when it is hefted.

Chemistry of Tin

Tin exhibits the oxidation states +2 and +4, like lead. In the +2 state, it is basic and behaves like a
metal. In the +4 state, it is amphoteric and can behave in an acidic manner in alkaline solution. The
oxidation state +2 is called stannous, and the +4 state is called stannic. Tin is soluble in dilute mineral
acids, and in hot potassium hydroxide, but is not attacked by food acids and alkalies. An acid solution
tends to preserve the stannous state, in which tin is a powerful reducing agent, happily furnishing
two electrons to anything that wants them. An alkaline solution generally results in hydrolysis, and
the formation of gelatinous hydrated oxides, such as Sn(OH)4, which can serve as a mordant, like the
aluminium hydroxides.

The chlorides are important compounds. Stannous chloride, SnCl2, is a reducing agent. Its hydrate,
SnCl2H2O, called "tin salt," forms Sn(OH)Cl on hydrolysis. Anhydrous stannic chloride, SnCl4 is a liquid
that boils at 114.1C, recalling carbon tetrachloride, but reacting quite differently because of the
amphoteric nature of tin. In water, the reaction is SnCl4 + 4H2O 4HCl + Sn(OH)4. Stannic chloride
can be made by treating tin cans with chlorine gas in the absolute absence of water. The chlorine
does not attack the iron. SnCl45H2O is called "butter of tin," but should not be spread on your toast.
Hydrochloric acid reacts with SnCl4 to form chlorostannic acid: 2HCl + SnCl4 H2SnCl6. This weak
acid can form salts, such as (NH4)2SnCl6, called "pink salt" although it is colorless.

Tin forms SnH4, stannane, after the example of methane. I can find no properties of this gas, only
mention of its mere existence, but it must be curious. As an acidic element, tin forms H2SnO3,
metastannic acid, and H2SnS3, thiostannic acid. A salt of thiostannic acid is important in qualitative
analysis, where the reaction SnS2 + Na2S Na2SnS3 is used to dissolve the sulphide so that tin can be
separated from the other cations in its group. Tin forms unstable nitrates, Sn(NO3)220H2O, with an
extraordinary amount of water of crystallization, Sn(NO3)4, that decomposes at 50C, and
SnOSn(NO3)2, which has the temerity to explode when heated.

Metallic tin can be regarded as safe, and presents no hazard of poisoning even when in contact with
food. There is no vapor to worry about. Soluble tin compounds are, like all soluble compounds of
heavy metals, not good snacks. Give warm soapy water or other emetic, and seek medical help.
Emetics are no longer as heartily advised as before, since some poisons can cause damage going
either way. This is not the case with most heavy metal poisons, however, which do not damage
tissue on contact. Epsom salts will do no good, since stannous sulphate is soluble.

Mineralogy and Production of Tin

The primary (that is, originally deposited) tin ore is probably stannite, a mixed sulphide, Cu2FeSnS4,
"tin pyrites," which is altered by supergene enrichment to cassiterite, SnO2, the heavy, dark
"tinstone" that is found in river gravels as well as in veins. Cornwall was a notable and historic source
of cassiterite, but the last mine has now closed in this small but interesting mining district. Much
larger amounts were found in the gravels of Malaysia, Indonesia and Thailand, which supply "stream
tin" or "Straits tin" from placer deposits. Until 1946, the Straits Settlements was the name of the
area that is now Malaysia, and long the chief source of tin. Bolivia and China also contain economic
deposits of vein ore, and Brazil and Russia have now become major producers as the traditional
sources become depleted. Southeast Asia now produces about 35%, South America 30%, China and
Russia 21% of the world's tin. Tin is rare, and will be long gone by the end of the century. The United
States has little tin ore of any kind, only traces, and now imports over 85% of its needs. This figure
would seem to be closer to 100%, but what is included is not specified in the statistics. In 1988, the
U.S. smelted 1467 metric tons of tin from imported ores, recovered 15,249 tons as secondary tin
(from tin cans), and imported 43,493 tons of metal. The average price was $4.41 per pound. The
world production is about 200,000 tons annually, and an approximately equal amount is held in the
U.S. strategic reserves.

The main suppliers of tin to the ancient world were the Phoenicians, who carried on a trade based
on their mines and smelters in the Iberian peninsula, and (traditionally) on trade with Cornwall.
Greek literature mentions the Cassiterides, the "tin islands," but just what these were is not clear.
Cornwall is not an island. The nearby Scilly Isles are isles, but have no tin. It was probably just a
mythological source for the tin brought by the Phoenicians. The Phoenician trade began before 1500
BC. It was probably the Phoenicians who spread tin, and with it bronze, around the Mediterranean.

The lean ores currently available must be treated to remove as much of the sulphides of lead,
bismuth, antimony, zinc, silver, copper and iron as possible. These sulphides cannot be eliminated
easily by gravity separation in water, since they are heavy like cassiterite. There has been some
success with differential flotation, however. The ore is roasted to eliminate sulphides, and leached
with hydrochloric acid to dissolve the iron, copper, bismuth and zinc impurities. Then it is treated
with chlorine to form chlorides of lead, bismuth, antimony and silver, which are leached out with
dilute acids.

The concentrated ore is then smelted in a blast furnace or a reverberatory furnace with coke or
anthracite screenings to produce liquid tin. The slags generally contain a goodly amount of tin, and
tin is lost in flue gases. The reverberatory furnace gives better recovery. The slag must be re-treated
to recover the 10% to 25% of tin that it contains. The tin is refined pyrolytically or electrolytically.
The electrolytic process was developed by Asarco after World War I, and resembles the refining of
copper.

The interruption of tin supplies early in World War II led to panicked construction of a tin smelter at
Texas City, Texas, the Longhorn Smelter, to use low-grade ore from Bolivia that was less subject to
interception. Construction began in October 1941, and the first ingots were poured in April, 1942.
The Texas site also had ample hydrochloric acid, a by-product of neighboring industries, and natural
gas for fuel. I do not know the current status of this smelter, but it would have been very difficult to
operate it economically after the war in the face of international competition. Bolivia has been able
to rely on cocaine in the absence of ore sales, so the U.S. supports it as a Good Neighbor either way.

Uses of Tin

The chief use of tin, by tonnage, was for years the manufacture of tin plate. This is thin sheet steel
with a coating of tin only about 2.3 m thick. The tin adheres strongly and uniformly to the steel,
protecting it from attack. A typical tin plate alloy is 88 Sn, 7.5 Pb, 4 Cu, 0.5 Sb. Cans made of tinplate
are used for food products, since the tin was not attacked by most foods in the absence of air (if it
were, glass jars or lacquer would have to be used). On examining modern cans, I find that other
coatings are now used in many cases, though tin is still found. If it is really tinplate, the individual
crystals can be seen in the coating, and the coating is white and attractive. I found that pineapple
comes in real tin cans. The tin used in tinplate is not lost, since it can be reclaimed using chlorine.
However, only a part of all cans can be recycled in this way, since the collection procedures in small
towns and the country are unsuitable. Tin plate is used in many ways, such as roofing and as the
"tin" or telltale in a squash court.

Tin plate was originally made by the "hot dip" process in which clean iron strip is passed through
molten tin. Practically all tin plate is now made electrolytically, since the thickness can be better
controlled. Tin is electrolytically plated from an acid solution of SnSO4, or from an alkaline solution of
a stannate. Tin does not give cathodic protection to steel, as zinc does, so it is very important that
the tin coating be continuous. Any pinholes will corrode easily. Fortunately, tin gives a very complete
cover. Although food acids will not attack tin in the absence of air, the presence of air may lead to
attack. This can often be seen if food is left in an open can for a while.
The thickness of tin plating is specified commercially by the weight of tin used per base box. A base
box consists of 112 sheets, 14" x 20", or 62,720 sq. in., counting both sides. One pound of tin per
base box corresponds to a thickness 0f 59 in. The usual tin plate is 1.0-2.5 lb. tin per base box.

Iron cannot be coated with lead by hot-dipping, since lead does not wet iron. A good coating does
result, however, if some metal is added that wets both iron and lead, such as tin, or if the steel is
given a thin coat of copper. This is also the reason why solder must contain tin, in addition to its
lowering of the melting point. Terne plate is a covering of tin and lead alloy, 75 Pb and 25 Sn a typical
composition. The metal covered is usually heavy-gauge steel, not the thin strip used for tinplate.
Lead gives good resistance against sulphuric acid. Tin plate can easily be given a coating of lead by
hot dipping.

A tinsmith is a worker in tinplate, who cuts, embosses and forms the metal, and solders seams in it.
He may also repair leaks in tinplate items by soldering, or by applying a patch with solder. Excellent
such work was done in colonial Mexico, together with silver work. We also have the tinker, which
may be related, but the Oxford Concise says etym. dub., unfortunately. A tinker makes small repairs,
which may include patching and soldering, which is called tinkering. The name has become attached
to the Irish travellers, of whom many are itinerant tinkers. The word is recorded from the 13th
century (early for English), and has no cognate in Dutch or German.

The Romans often dipped copper dishes into molten tin to give a better taste to the drinks taken
with the tinned items. Anyone who has drunk a Moscow Mule, vodka and ginger beer, in a copper
mug, will see the point. The metallic taste of copper is not always desired. Copper also reacts with
the fillings in your teeth, which are higher on the electrochemical scale.

Molten tin has been used to cast window glass, in the Pilkington float glass process. The glass is
poured out on the hot tin, which gives it a smooth surface. Tin is heavier than glass, has a high
boiling point, low vapor pressure, and does not react with the constituents of glass.

At the beginning of World War II, tin was not only widely used in tinplate, but as tinfoil and tin
collapsible tubes as well. The metal in this latter use could be an alloy, but it would be mainly tin. A
common tinfoil alloy was 92 Sn, 8 Zn. Cigarettes, sweets and chewing gum came wrapped in tinfoil,
while toothpaste was supplied in tin tubes. These were actually very good and attractive containers.
When the tin supply was threatened, these uses appeared nonessential, and a search was mounted
for substitutes. I cannot find the composition of the substitute alloy used for toothpaste tubes, but it
could well be a lead alloy, since the toothpaste would keep the lead in an insoluble form. Aluminum
foil has replaced tinfoil generally. It was almost as satisfactory, although not as pleasantly soft as
tinfoil, but could be rolled out as thinly. Metal toothpaste tubes were replaced by plastic (probably
in a lead scare), and they really do not do as well, refusing to stay compressed. The old metal tubes
rolled up nicely.

One encyclopedia says that tin is used in toothpaste. Probably the same way glass is used in jam.

The use of tin that was essential to the war effort was its use in alloys. It is in this use that there are
few alternatives to tin. A large amount of tin is used in solders, of which it is the principal ingredient,
typically 60 Sn 40 Pb. The phrase "to tin a soldering iron" means to flux it, apply solder, and wipe
until it is evenly coated. For more information on solders, see Lead. Pewter is an alloy ranging from
pure tin to 74 Sn, 20 Pb, 3 Cu, 3 Sb. Two popular alloys have 6 Sb, 2 Cu and 4 Sb, 2 Cu, with the rest
tin, or tin and lead. Pure tin is rather too soft, and the alloy hardens it a little. It is an easily workable
metal for pots, platters and plates, an inexpensive substitute for silver. At today's prices for tin, it is
not much less expensive than silver, however. Another important use is in bearing metals, for which
the same article should be consulted. However, the principal alloy of tin is its alloy with copper,
bronze. This was one of the first alloys used by man, and the first to be made on purpose to critical
specifications. We have already mentioned that it is very unlikely that bronze was discovered by
accident.

The strength of a bronze increases with the tin content, while its toughness and malleability
decrease. The strength is a maximum at about 30%, and rapidly decreases for more tin, but at this
point the bronze is hard and brittle. There is an intermetallic compound Cu3Sn that has something to
do with this. For coinage, 95 Cu, 5 Sn is a good alloy, still looking like copper, but with added
strength and hardness that allow it to stand up in circulation. The alloy 95 Cu, 4 Sn, 1 Zn is also used.
The U.S. large cents that were struck in 1808-1814 used a purer copper than those before and after,
and they wore noticeably badly. 90 Cu, 10 Sn makes a strong, tough alloy called "gun metal" from an
obvious application. With more tin than 85 Cu, 15 Sn, the bronze is called "bell metal" because its
hardness makes a live, resonant bell. The Liberty Bell, cast in London, cracked when rung in
Philadelphia, showing the drawbacks of high-tin bronze. My great-grandfather leaped over the
barrier and rang it again at the Centennial Exhibition in 1876, futher damaging it. 67 Cu and 33 Sn
give "speculum metal," a very hard white alloy (mainly Cu3Sn) that makes an excellent mirror when
polished. This is the range of useful bronze alloys, and shows the general trend of their properties.
The exact proportions of Cu and Sn in any particular alloy may vary from the numbers quoted, of
course. Bronze is significantly improved by small additions of phosphorus, which de-oxygenates the
alloy and cleans up the grain boundaries. This is the main effect of the addition, not any addition of
phosphorus to the alloy, which is deleterious. Phosphor bronze is an excellent bronze, often used for
springs. The very hard intermetallic compound Cu3P is formed with higher phosphorus content, and
makes a brittle bronze with only special uses. The term "bronze" is used for some alloys that contain
no, or very little, tin, to show that they have superior qualities. Aluminium bronze, 90 Cu, 10 Al is an
example (and a very good alloy, besides).

A typical bronze for English "copper" coins was 97 Cu, 2.5 Zn, 0.5 Sn. U.S. coins contained no tin,
unless the alloy for the early half-cents and cents, imported from England, contained a little tin.
English copper coins were traditionally the halfpenny and the farthing (1/4 penny). From 1684 to
1692 halfpennies and farthings were issued in tin, with the date and the legend "nummorum
famulus" ("servant of the coinage") on the rim. Some had a copper plug in the middle, to retain the
link with copper. This was the only use I can find of tin in coinage, since tin would not not be hard
enough for circulation, and it was also costly. Not even the Straits Settlements or Malaya has issued
tin coins. Incidentally, the penny was a silver coin down to 1797, when it became the familiar large
copper coin, last issued in 1967. The phrase "bright as a penny" referred to the small, shiny silver
penny, now only found in Maundy Money. It certainly does not refer to a copper penny or cent, and
especially not to the dingy zinc cents of today's U. S. money.

Tin is also preferred for organ pipes. It is said to give a better sound than aluminium or zinc. Cymbals
are made from a high-tin bronze, 80-85 Cu, 15-20 Sn, which is a bell metal and gives a bright sound.
Ancient Egypt was very poor in metals, which had to be imported or scratched from a few mines in
the Sinai. Copper weapons, hardened only by the impurities that happened to be in the metal, were
no match for the bronze weapons coming from Mesopotamia. The Second Intermediate Period,
1759-1539 BC, may have been a time of weakness in the face of the bronze of the Hyksos, who
established their capital in Avaris. Ahmose, King of Thebes and founder of the 17th dynasty finally
overcame Avaris in 1530 BC, perhaps with the new bronze weapons glittering in his army. The
Egyptian histories that I have say nothing about copper or brass, in spite of its undoubted
importance, though ceremonial weapons of gold and copper are pictured. These times are called
"Middle Bronze Age," though what this means in terms of Egypt is not clear. Archaeologists are not
very careful about their chemistry or metallurgy. It does seem to be the time that the Phoenician
trade in tin rose from obscurity. Tin was the secret weapon of the time, which could make hard,
sharp weapons. Homer's Trojan War was fought with bronze weapons and armor.

Bronze itself finally fell before the warlike iron of the Hittites and the Celts. Iron could be hardened
after the weapon was formed, and could make a weapon with a hard edge and a tough core, which
would shatter a bronze sword. The Dorian Greeks were armed with steel, which overcame the
bronze-wielding Mycenaeans. The properties of bronze were determined mainly by the alloy, and a
hard alloy like weapons bronze could not be work-hardened by hammering, as iron could. Copper
had been hardened in this way, but even so was no match for bronze or iron. Now bronze was
mainly used for statuary of high quality.

References
Properties of tin and its compounds are found passim in handbooks such as the Handbook of
Chemistry and Physics, Lange's Handbook of Chemistry, and Kent's Mechanical Engineer's
Handbook.

G. Agricola, De Re Metallica (1556). H. C. Hoover and L. H. Hoover, transl. (New York: Dover,
1950).

W. N. Jones, Inorganic Chemistry (Philadelphia: Blakiston, 1949), Chapter 31.

J. L. Bray, Non-Ferrous Production Metallurgy (New York: John Wiley & Sons, 1947), Chapter 23.

R. A. Higgins, Engineering Metallurgy, 3rd ed. (London: The English Universities Press, 1971).
What is tin?

Tin is a silvery white metal that lives in group IV of the periodic table of chemical elements. To look
at it, you'd never know that it was (according to archeologists) one of the earliest and most
important metals in human history!

It was the discovery of how tin and copper could be combined in an alloy called bronze (a much
stronger material than either metal alone) that ushered in one of the major eras of civilization: the
Bronze Age. The earliest evidence we have of people using tin is in bronze finds from 30003500BCE,
though it was apparently not widely used as a pure metal until several thousand years later
(probably c.600BCE).

Where does tin come from?

Although we think of tin as an everyday material, it's actually much less

common than comparable metals such as copper or zinc (according to the
US Geological Survey, copper is over 30 times and zinc about 50 times
more common than tin). In terms of abundance, tin is roughly halfway down
the list of chemical elements: the 49th most common in Earth's rocky crust,
existing in concentrations of about 2 parts per million (0.0002 percent). In
other words, if you dig up a tonne of rock, a measly 2 grams of it will be tin!

There are tin deposits right across the world, though most tin now comes
from the southern hemisphereand chiefly from south-east Asia. The most
important producer countries are now China, Indonesia, Peru, Bolivia, and
Brazil. England (Cornwall) is no longer the important producer it once was
and the United States, despite being the world's biggest consumer of tin,
has not (according to the US Geological Survey) mined any of the metal
since 1993.
Most tin is produced from an ore (raw rocky mineral) called cassiterite,
which is turned into tin by smelting. First, the ore is crushed to a powder
and washed free of impurities before being heated with carbon (in the form
of coal) and limestone in a giant furnace. Other metals, such
asiron, copper and zinc, separate out. Molten tin sinks to the bottom of the
furnace and is shaped into solid blocks known as ingots. Like most other
metals, tin can also be separated or purified using electrolysis (an
electrical-chemical process that works in the opposite way to a battery).

What is tin like?

There are two common forms (allotropes) of tin that look and behave
differently because of their quite different internal crystalline structures.
One is the familiar, silvery-white form called white tin or beta tin, which
has a body-centered tetragonal structure and predominates at everyday
temperatures. The other form, gray tin or alpha tin, is powdery, about two
thirds as dense, and appears spontaneously at low temperatures. It's less
useful because it's weaker and more brittle, with a face-centered
cubic crystalline structure. The sudden degradation of white tin into gray tin
is calledtin pest.
Physical properties

Tin is a typical metal inasmuch as it's extremely malleable (easy to work in

many different ways), ductile (easy to draw into wires), and readily forms a
grayish protective oxide on its surface, but it's much weaker than metals
such as iron so it's not used as a construction material. It has a relatively
low melting point (one of the reasons it's used as a component ofsolder),
but a relatively high boiling point, which means it's a liquid over a wide
range of temperatures and can be usefully employed as such in a number
of industrial processes.

Chemical properties

Tin has a valency (chemical combining power) of either two (II) or four (IV)
and accordingly forms two different forms of compounds: tin (II) compounds
(which used to be called stannous) and tin (IV) compounds (formerly called
stannic). Notable tin compounds include tin (II) chloride used in galvanizing,
dyeing, and perfume production; tin (II) fluoride, which provides the fluoride
in some toothpastes; and tin (IV) oxide, an industrial catalyst. Compounds
of carbon and tin include a number of important insecticides and
disinfectants.

Key data

Melting point: 232C (450F).

 Boiling point: 2270C (4100F).
Atomic number: 50 (the most common form of tin atom contains 50
protons, 70 neutrons, and 50 electrons).
Relative atomic mass: 118.69.
Density: White tin: 7.28 g/cc; gray tin: 5.75 g/cc.
Isotopes: Ten stable isotopes, the most common of which are tin-120
(~33%), tin-118 (24%), tin-116 (~15%), and tin-119 (~8.5%).

Photo: Tin surprise! Did you know that tin (II) fluoride puts the fluoride in toothpastes?

What do we use tin for?

Tin plating wasand remainsthe most important use of tin. It involves

applying a very thin protective coating of tin to other materials, such as
steel and copper, either by dipping them into molten tin or by electroplating.
The dull, tin oxide that forms on the surface of the tin plate protects both
the tin and the material it covers up. In the early decades of the 20th
century, most food cans were handmade this way and sealed up
by soldering. The tin rustproofed the steel cans and protected them from
acidic foods, and some tins cans also had an enamel coating inside to
protect the food from reacting with them. Now, plastic, board,
and composite containers and aluminum cans often do the job instead. Tin
is also used to rustproof such things as paperclips, hair grips, and safety
pins. Apart from tin plate, the next most important use for tin is the
production of many different alloys, including bronze, solders of various
kinds, babbitt metal, and pewter.