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Калай Калай (от турски kalay) е химичен елемент от главната подгрупа на четвърта група, пети период на периодичната таблица на Менделеев. Обозначава се със символа Sn (на латински: Stannum), а атомният му номер е 50. Отнася се към групата на леките метали. Калаят има две алотропни модифицации: устойчив под 13,2 °C a-калай с кубична кристална решетка и устойчивият над 13,2 °C B-калай с тетрагонална кристална решетка. Има общо 10 стабилни изотопа. Поради много слабата си оксидация се използва да покрива други метали и да ги предпазва от корозия. Поради ниската си токсичност се използва при изработване на консервни кутии и други контейнери. Една от първите сплави, изработена от хората, е бронзът, който представлява сплав на мед и калай. Съдържание История[редактиране | edit source] Добивът и употребата на калай могат да бъдат проследени чак до началото на бронзовата ера — около 3000 г. пр.н.е., когато е наблюдавано, че мед с различни концентрации на други метали има различни характеристики.[1] Най-ранните бронзови предмети съдържат калай или арсен по-малко от 2% и по тази причина се счита, че са случайно попаднали в сплавта от медните руди[2] Прибавянето на арсен или калай към медта я прави по-твърда и прави леенето и коването значително по-лесно. Това води до революционизиране на техниките за направа на метални предмети и извежда човечеството от медната до бронзовата епоха около 3000 пр.н.е.[2][3] Първото доказателство за използване на калай при направата на бронз датира от 3000 г. пр.н.е. и идва от Близкия изток и Балканите.[2] Все още не е ясно къде за първи път е започнал да се добива калаят, тъй като мините са рядкост и са на големи разстояния. Първата мина в Европа изглежда е била на границата между Германия и Чехия около 2500 г. пр.н.е. и оттам калаят е пренесен до Балтийско и Средиземно море. Около 2000 г. пр.н.е. калаят е разпространен в цяла Европа.[2] Минното дело е в разцвета си по време на Римската империя - 300 г.пр.н.е. до 100 г.[4] Търсенето на калай става значително и търговията с него сред срдиземноморските държави става една от най-важните.[5][6] По време на средновековието Иберия и Германия загубват значението си в добива на калай, докато Корнуол и Девън започват да доминират европейския пазар.[4] В Далечния изток, от Китай до Малайзия, калаят започва да се добива между 3-тото и 2-рото хилядолетие преди новата ера, като най-добре разработените залежи са в Юнан, но тяхната експлоатация започва около 700 г. пр.н.е., както свидетелстват запазени документи от династиите Хан, Сун и Тан.[7] В останалите части на света добивът на калай започва значително по-късно. Така например в Африка народите банту добиват и използват калая между 11-ти и 15-ти век,[2] в Америка добивът му започва около 1000 година, а в Австралия - около 17-ти век. В днешно време след срива на пазара през октомври 1985 година, цената на калая става наполовина.[8] Характеристики[редактиране | edit source] Физични свойства[редактиране | edit source] Калаят е сребристобял, мек и ковък метал с кристална структура. Съществува в 2 алотропни модификации - белият (метален) калай при ниски температури се превръща в прах - сив калай. Когато парче калай се извие, се чува пукане, известно като „плачът на калая“[9]. B-калай (метална форма), която съществува при стайна температура и по-високи температури, е мек и ковък, a-калай (неметална форма) се образува, когато се охлади под 13,2 °C и е крехък. Той има диамантена кристална структура, подобно на диамант, силиций или германий. a-калаят има само неметални свойства. Той е сив прахообразен материал, без обща употреба, само с няколко специализирани полупроводникови приложения.[9] a-калай и B-калай са по-известни като сив калай и бял калай съответно. Още две алотропни форми, Y и σ, съществуват при температура над 161 °С и налягане над няколко GPa.[10] Макар a-B трансформацията да става при температура 13,2 °C, примеси (напр. Al, Zn и т.н.), снижават температурата на прехода под 0 °С и при добавянето на Sb или Bi преобразуването може изобщо да не се прояви, което повишава издръжливостта на калая.[11] Това преобразуване е известно като калаена болест или калаена чума. То представлява особен проблем в северната част на Европа през 18-ти век, когато тръбите на органи от калаена сплав понякога се повреждат по време на дълги студени зими. Някои източници също твърдят, че по времето на Наполеон и Руската кампания от 1812 г., температурите стават ниски и е толкова студено, че калаените копчетата на войнишките униформи се разпадат постепенно, което допринася за разгрома на Великата армия.[12] Търговският калай (99,8%) устоява на тези трансформации поради действието на малки количества от бисмут, антимон, олово, сребро и други примеси. Сплавни елементи като мед, антимон, бисмут, кадмий и сребро увеличават твърдостта на калая, който като правило, обикновено доста лесно образува твърди, крехки интерметални фази, които често са нежелани. Химични свойства[редактиране | edit source] Калаят реагира с халогени и сяра. Устойчив е на корозия от всякакъв вид вода - морска, питейна, дестилирина, но може да бъде атакуван с киселини и някои киселинни соли. Той може да бъде полиран до съвършенство и се използва като защитно покритие на други метали, за да се предотвати корозия и други химични реакции. Калаят може да играе роля на катализатор при наличие на кислород в разтвора.[9] Изотопи[редактиране | edit source] Калаят е елемент с най-голям брой стабилни изотопи - десет, като те включват всички с атомните маси между 112 и 124, с изключение на 113, 121 и 123. От тях най-разпространените са 120Sn (почти една трета от всичкия калай), 118Sn и 116Sn , а най-слабо разпространеният е 115Sn. Калаят, с трите си най-разпространени изотопа 115Sn, 117Sn и 119Sn, е сред най-лесните за откриване и анализиране елементи с помощта на ЯМР (ядрен магнитен резонанс)спектроскопия .[13] Този голям брой стабилни изотопи се смята за пряк резултат от факта, че калаят има атомно число 50, което се счита за „магическо число“ в ядрената физика. Има още 28 допълнителни известни нестабилни изотопи, които включват всички останали с атомни маси между 99 и 137. Почти всички радиоактивни изотопи имат период на полуразпад по-малък от една година.[14] Разпространение, добив и приложение[редактиране | edit source] Добива се от минералите каситерит и станин, които се срещат в природата. Получаване: SnO2 + 2C → Sn + 2CO Употребата му се състои в калайдисване на консервени кутии (метално покритие против корозия), а също така участва при направата на припой (тинол) за запояване, както и на бронз. Източници[редактиране | edit source] - ↑ The "Bronze Age tin mines in Central Asia. // The Problem of Early Tin. Oxford, Archaeopress, 2003. - ↑ а б в г д Penhallurick, R.D.. Tin in Antiquity: its Mining and Trade Throughout the Ancient World with Particular Reference to Cornwall. London, The Institute of Metals, 1986. - ↑ The development of the usage of tin and tin-bronze: some problems. // The Search for Ancient Tin. Washington D.C., A seminar organized by Theodore A. Wertime and held at the Smithsonian Institution and the National Bureau of Standards, Washington D.C. - ↑ а б Gerrard, S.. The Early British Tin Industry. Stroud, Tempus Publishing, 2000. - ↑ The problem of early tin from the point of view of Nuragic Sardinia. // The Problem of Early Tin. Oxford, Archaeopress, 2003. - ↑ The cargo of the Uluburun ship and evidence for trade with the Aegean and beyond. // Italy and Cyprus in Antiquity: 1500–450 BC. Nicosia, The Costakis and Leto Severis Foundation, 2001. - ↑ Murowchick, R.E.. The Ancient Bronze Metallurgy of Yunnan and its Environs: Development and Implications. Michigan, Ann Arbour, 1991. - ↑ Thoburn, John T.. Tin in the World Economy. Edinburgh University Press, 1994. - ↑ а б в Holleman, Arnold F. и др. Tin. // Lehrbuch der Anorganischen Chemie. 91–100. Walter de Gruyter, 1985. - ↑ Molodets, A. M. и др. Thermodynamic Potentials, Diagram of State, and Phase Transitions of Tin on Shock Compression. // High Temperature 38 (5). 2000. - ↑ Schwartz, Mel. Tin and Alloys, Properties. // Encyclopedia of Materials, Parts and Finishes. 2nd. CRC Press, 2002. - ↑ Le Coureur, Penny и др. Napoleon's Buttons: 17 Molecules that Changed History. New York, Penguin Group USA, 2004. - ↑ Interactive NMR Frequency Map. - ↑ Walker, Phil. Doubly Magic Discovery of Tin-100. // Physics World 7 (June). 1994.
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Tin sources and trade in ancient times Tin is an essential metal in the creation of tin bronzes and its acquisition has been an important part of Bronze Age and later cultures throughout ancient history. Its use began in the Near East and the Balkans around 3000 BC. Tin is a relatively rare element in the Earth's crust, with approximately 2 ppm (parts per million), compared to iron with 50,000 ppm, copper with 70 ppm, lead with 16 ppm, arsenic with 5 ppm, silver with 0.1 ppm, and gold with 0.005 ppm (Valera & Valera 2003, p. 10). Ancient sources of tin were therefore rare, and the metal usually had to be traded over very long distances to meet demand in areas which lacked tin deposits. Known sources of tin exploited in ancient times include: the southeastern tin belt running from Yunnan province in China down the Malaysian Peninsula, Devon and Cornwall in England, Brittany in France, the border between Germany and Czech Republic, Spain, Portugal, Italy, and Central and Southern Africa (Wertime 1979, p. 1; Muhly 1979). Other minor sources of tin have been suggested in Iran, Syria, and Egypt, but the archaeological evidence is inconclusive. Contents Early use[edit] Tin extraction and use can be dated to the beginnings of the Bronze Age around 3000 BCE, when it was observed that copper objects formed of polymetallic ores with different metal contents had different physical properties (Cierny & Weisgerber 2003, p. 23). The earliest bronze objects had tin or arsenic content of less than 2% and are therefore believed to be the result of unintentional alloying due to trace metal content in the copper ore (Penhallurick 1986). The addition of a second metal to copper increases its hardness, lowers the melting temperature, and improves the casting process by producing a more fluid melt that cools to a denser, less spongy metal (Penhallurick 1986, pp. 4–5). This was an important innovation that allowed for the much more complex shapes cast in closed molds of the Bronze Age. Arsenical bronze objects appear first in the Near East where arsenic is commonly found in association with copper ore, but the health risks were quickly realized and the quest for sources of the much less hazardous tin ores began early in the Bronze Age (Charles 1979, p. 30). This created the demand for rare tin metal and formed a trade network that linked the distant sources of tin to the markets of Bronze Age cultures. Cassiterite (SnO2), the tin oxide form of tin, was most likely the original source of tin in ancient times. Other forms of tin ores are less abundant sulfides such as stannite that require a more involved smelting process. Cassiterite often accumulates in alluvial channels as placer deposits due to the fact that it is harder, heavier, and more chemically resistant than the granite in which it typically forms (Penhallurick 1986). These deposits can be easily seen in river banks as cassiterite is usually black, purple or otherwise dark in colour, a feature exploited by early Bronze Age prospectors. It is likely that the earliest deposits were alluvial in nature, and perhaps exploited by the same methods used for panning gold in placer deposits. Archaeological importance[edit] The importance of tin metal to the success of Bronze Age cultures and the scarcity of the resource offers a glimpse into that time period’s trade and cultural interactions, and has therefore been the focus of intense archaeological studies. However, a number of problems have plagued the study of ancient tin such as the limited archaeological remains of placer mining, the destruction of ancient mines by modern mining operations, and the poor preservation of pure tin objects due to tin disease or tin pest. These problems are compounded by the difficulty in provenancing tin objects and ores to their geological deposits using isotopic or trace element analyses. Current archaeological debate is concerned with the origins of tin in the earliest Bronze Age cultures of the Near East (Penhallurick 1986; Cierny & Weisgerber 2003; Dayton 1971; Giumlia-Mair 2003; Muhly 1979; Muhly 1985). Ancient sources[edit] Europe[edit] Europe has very few sources of tin. It was therefore of extreme importance throughout ancient times to import it long distances from known tin mining districts of antiquity, namely Erzgebirge along the border between Germany and Czech Republic, the Iberian Peninsula, Brittany in France, and Devon and Cornwall in southwestern England (Benvenuti et al. 2003, p. 56; Valera & Valera 2003, p. 11). Another minor source of tin is known to exist at Monte Valerio in Tuscany, Italy. This source was exploited by Etruscan miners around 800 BCE, but it was not a significant source of tin for the rest of the Mediterranean (Benvenuti et al. 2003). The Etruscans themselves found the need to import tin from the northwest of the Iberian Peninsula at that time and later from Cornwall (Penhallurick 1986, p. 80). It has been claimed that tin was first mined in Europe around 2500 BCE in Erzgebirge, and knowledge of tin bronze and tin extraction techniques spread from there to Brittany and Cornwall around 2000 BCE and from northwestern Europe to northwestern Spain and Portugal around the same time (Penhallurick 1986, p. 93). However, the only Bronze Age object from Central Europe whose tin has been scientifically provenanced is the Nebra sky disk, and its tin (and gold, though not its copper), is shown by tin isotopes to have come from Cornwall (Haustein, Gillis & Pernicka 2010). In addition, a rare find of a pure tin ingot in Scandinavia was provenanced to Cornwall (Ling et al. 2014). Available evidence thus points to Cornwall as the sole early source of tin in Central and Northern Europe. Brittany has significant sources of tin which show evidence of being extensively exploited after the Roman conquest of Gaul during the first century BCE and onwards (Penhallurick 1986, pp. 86–91). Brittany remained a significant source of tin throughout the medieval period. Iberian tin was widely traded across the Mediterranean during the Bronze Age, and extensively exploited during Roman times, but its tin deposits were largely forgotten throughout the medieval period and only rediscovered in the 18th century and only re-gained importance during the mid 19th century (Penhallurick 1986, pp. 100–101). Devon and Cornwall were important sources of tin for Europe and the Mediterranean throughout ancient times, and may have been the earliest sources of tin in Western Europe, but within the historical period they only dominated the European market from late Roman times in the 3rd century CE with the exhaustion of many Spanish tin mines (Gerrard 2000, p. 21). Cornwall maintained its importance as a source of tin throughout medieval times and into the modern period (Gerrard 2000). Asia[edit] Western Asia has very little tin ore; the few sources that have been found recently are relatively small and too insignificant to have played a major role during most of ancient history (Cierny & Weisgerber 2003, p. 23). However, it is possible that they were exploited at the very onset of the Bronze Age and are responsible for the development of early bronze manufacturing technology (Muhly 1973; Muhly 1979). Though there are much older bronze objects in both the Balkans and in the Near East that must have been produced from tin, the oldest direct evidence of pure tin is a tin ingot from the 1300 BCE Uluburun shipwreck off the coast of Turkey [1] While there are a few sources of cassiterite in Central Asia, namely in Uzbekistan, Tajikistan, and Afghanistan that show signs of having been exploited starting around 2000 BCE (Cierny & Weisgerber 2003, p. 28), there is disagreement between archaeologists as to whether they were significant sources of tin for the earliest Bronze Age cultures of the Near East (Dayton 2003; Muhly 1973; Maddin 1998; Stech & Pigott 1986). In Northern Asia the only tin deposits considered exploitable by ancient peoples occur in the far eastern region of Siberia (Dayton 2003:165). This source of tin appears to have been exploited by the Eurasian Steppe people known as the Turbino culture of the Middle Bronze Age (1000 BCE) as well as northern Chinese cultures around the same time (Penhallurick 1986, p. 35). Eastern Asia has a number of small cassiterite deposits along the Yellow River which were exploited by the earliest Chinese Bronze Age culture of Erlitou and the Shang Dynasty (2500 to 1800 BCE). However, the richest deposits for the region, and indeed the world, lie in Southeastern Asia, from Yunnan Province in China down the Malaysian Peninsula. The deposits in Yunnan province were not mined until around 700 BCE, but by the Han Dynasty had become the main source of tin in China according to historical texts of the Han, Jin, Tang, and Song dynasties (Murowchick 1991, pp. 76–77). Other cultures of Southeast Asia exploited the abundant cassiterite resources sometime between second and third millennia BCE, but due to the lack of archaeological work in the region little else is known about tin exploitation during ancient times in that part of the world. Tin was used in the Indian subcontinent starting in the second half of the second millennium BCE (i.e. between 1500 and 1000 BCE) (Hedge 1979, p. 39; Chakrabarti & Lahiri 1996). While India does have some small scattered deposits of tin, they were not a major source of tin for Indian Bronze Age cultures as shown by their dependence on imported tin. Africa[edit] While rich veins of tin are known to exist in Central and South Africa, whether these were exploited during ancient times is still debated (Dayton 2003, p. 165). However, the Bantu culture of Zimbabwe are known to have actively mined, smelted and traded tin between the 11th and 15th centuries CE (Penhallurick 1986, p. 11). Americas[edit] Tin deposits exist in many parts of South America, with minor deposits in southern Peru, Colombia, Brazil, and northwestern Argentina, and major deposits of exploitable cassiterite in northern Bolivia. These deposits were exploited as early as 1000 CE in the manufacture of tin bronze by Andean cultures, including the later Inca culture who considered tin bronze as the "imperial alloy". In North America, the only known exploitable source of tin during ancient times is located in the Zacatecas tin province of north central Mexico which supplied west Mexican cultures with enough tin for bronze production (Lechtman 1996, p. 478). Australia[edit] The tin belt of Southeast Asia extends all the way down to Tasmania, but metals were not exploited in Australia until the arrival of Europeans in the 18th century. Ancient trade[edit] Due to the scattered nature of tin deposits around the world and its essential nature for the creation of tin bronze, tin trade played an important role in the development of cultures throughout ancient times. Archaeologists have reconstructed parts of the extensive trade networks of ancient cultures from the Bronze Age to modern times using historical texts, archaeological excavations, and trace element and lead isotope analysis to determine the origins of tin objects around the world (Valera & Valera 2003; Rovira & Montero 2003; Maddin 1998). Mediterranean[edit] The earliest sources of tin in the Early Bronze Age in the Near East are still unknown and the subject of much debate in archaeology (Dayton 1971; Dayton 2003; Maddin 1998; Muhly 1973; Penhallurck 1986; Stech Pigott 1986; Kalyanaraman 2010). Possibilities include minor now-depleted sources in the Near East, trade from Central Asia (Muhly 1979), Sub-Saharan Africa (Dayton 2003), Europe, or elsewhere. It is possible that as early as 2500 BCE, Erzgebirge had begun exporting tin, using the well established Baltic amber trade route to supply Scandinavia as well as the Mediterranean with tin (Penhallurick 1986, pp. 75–77). By 2000 BCE, the extraction of tin in England, France, Spain, and Portugal had begun and tin was traded to the Mediterranean sporadically from all these sources. Evidence of tin trade in the Mediterranean can be seen in a number of Bronze Age shipwrecks containing tin ingots such as the Uluburun off the coast of Turkey dated 1300 BCE which carried over 300 copper bars weighing 10 tons, and approximately 40 tin bars weighing 1 ton (Pulak 2001). While Sardinia does not appear to have much in terms of significant sources of tin, it does have rich copper and other mineral wealth and served as a centre for metals trade during the Bronze Age and likely actively imported tin from the Iberian Peninsula for export to the rest of the Mediterranean (Lo Schiavo 2003). By classical Greek times, the tin sources were well established. Greece and the Western Mediterranean appear to have traded their tin from European sources, while the Near East acquired their tin from Central Asian sources through the Silk Road (Muhly 1979, p. 45). For example, Iron Age Greece had access to tin from Iberia by way of the Phoenicians who traded extensively there, from Erzgebirge by way of the Baltic Amber Road overland route, or from Brittany and Cornwall through overland routes from their colony at Massalia (modern day Marseilles) established in the 6th century BCE (Penhallurick 1986). In 450 BCE, Herodotus described tin as coming from Northern European islands named the Cassiterides along the extreme borders of the world, suggesting very long distance trade, likely from Britain, northwestern Iberia, or Brittany, supplying tin to Greece and other Mediterranean cultures (Valera & Valera 2003, p. 11). It should be noted that the idea that the Phoenicians went to Cornwall for its tin and supplied it to the whole of the Mediterranean has no archaeological basis and is largely considered a myth (Penhellurick 1986, p. 123). The early Roman world was mainly supplied with tin from its Iberian provinces of Gallaecia and Lusitania and to a lesser extent Tuscany. Pliny mentions that in 80 BCE, a senatorial decree halted all mining on the Italian Peninsula, stopping any tin mining activity in Tuscany and increasing Roman dependence on tin from Brittany, Iberia, and Cornwall. After the Roman conquest of Gaul, Brittany’s tin deposits saw intensified exploitation after the first century BCE (Penhallurick 1986, pp. 86–91). With the exhaustion of the Iberian tin mines, Cornwall became a major supplier of tin for the Romans after the 3rd century CE (Gerrard 2000). Throughout the medieval period, demand for tin increased as pewter gained popularity. Brittany and Cornwall remained the major producers and exporters of tin throughout the Mediterranean through to modern times (Gerrard 2000). Asia[edit] Near Eastern development of bronze technology spread across Central Asia by way of the Eurasian Steppes, and with it came the knowledge and technology for tin prospection and extraction. By 2000 to 1500 BCE Uzbekistan, Afghanistan, and Tajikistan appear to have exploited their sources of tin, carrying the resources east and west along the Silk Road crossing Central Asia (Cierny & Weisgerber 2003, p. 28). This trade link likely followed an existing trade route of lapis lazuli, a highly prized semi-precious blue gemstone, and chlorite vessels decorated with turquoise from Central Asia that have been found as far west as Egypt and that date to the same period (Giumlia-Mair 2003, p. 93). In China, early tin was extracted along the Yellow River in Erlitou and Shang times between 2500 and 1800 BCE. By Han and later times, China imported its tin from what is today Yunnan province. This has remained China’s main source of tin throughout history and into modern times (Murowchick 1991). It is unlikely that Southeast Asian tin from Indochina was widely traded around the world in ancient times as the area was only opened up to Indian, Muslim, and European traders around 800 CE (Penhallurick 1986, p. 51). Roman trade to India is well known from historical texts such as Pliny’s Natural History (book VI, 26), and tin is mentioned as one of the resources being exported from Rome to Southern Arabia, Somaliland, and India (Penhallurick 1986, p. 53; Dayton 2003, p. 165). See also[edit] - Cassiterides - Stannary - Tin pest - Tin mining in Britain - Mining in Cornwall and Devon - Dartmoor tin mining References[edit] - ^ Liz Burlingame (Aug 23, 2013). "Sunken Treasures: The World's Most Valuable Shipwreck Discoveries". 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