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History of aluminium

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Extrusion billets of aluminium

Aluminium in its metallic form is comparatively new in human applications. Its source ore, alum, has been known since the 5th century BCE, and was extensively used by the ancients for dyeing and city defense; the former usage was more important in medieval Europe. Scientists of the Renaissance believed that alum was a salt of a new earth; during the Age of Enlightenment, it was established that the earth was an oxide of a new metal. Discovery of this new metal was announced in 1825 by Danish physicist Hans Christian Ørsted, whose work was greatly extended by German chemist Friedrich Wöhler.

Pure aluminium metal was difficult to refine and thus rare. Soon after its discovery, its price exceeded that of gold; the price was only reduced after the first industrial production was initiated by French chemist Henri Étienne Sainte-Claire Deville in 1856. Aluminium became much more available to the general public with the Hall–Héroult process developed by French engineer Paul Héroult and American engineer Charles Martin Hall in 1886, and the Bayer process developed by Austrian chemist Carl Joseph Bayer in 1889. These methods have been used for aluminium production up to the present day.

Since these methods were applied for mass production of aluminium, the metal has been extensively used in industry and everyday lives. Aluminium has been used in aviation, architecture, and packaging. Its production grew exponentially in the 20th century and it became an exchange commodity in the 1970s. In 1900, production was 6,800 metric tons; in 2015, it was 57,500,000 tons.

Early history

The history of aluminium has been shaped by usage of alum. The first written record of alum, made by Ancient Greek historian Herodotus, was in the 5th century BCE.[1] The ancients used alum as dyeing mordants and as astringents for dressing wounds; alum was also used in medicine, as a fire-resistant coating for wood (which protected fortresses from enemy arson attempts), and in chemical milling.[2] Aluminium metal was unknown to them. Roman historian Pliny the Elder recorded a story about a metal that was bright as silver but much lighter, which was presented to the Emperor Tiberius (reigned 14–37 CE), who had the discoverer killed in order to ensure the metal would not diminish the value of his gold and silver assets.[a] Some sources suggest a possibility that this metal was aluminium;[b] this claim has been disputed.[5] It is possible that the Chinese were able to produce aluminium-containing alloys during the reign of the first Jin dynasty (265–420).[c]

After the Crusades, alum was a subject of international commerce;[7] it was indispensable in European fabric industry.[8] Alum was imported to Europe from the eastern Mediterranean until the mid-15th century, when the Ottomans greatly raised export taxes. Some small alum mines were worked in Catholic Europe. When Giovanni da Castro, godson of the Pope Pius II, discovered a rich source of alum at Tolfa near Rome in 1460, he reported excitedly to his godfather, "today I bring you victory over the Turk".[d]

Establishing the nature of alum

Antoine Lavoisier established that alumina was an oxide of an unknown metal.

The nature of alum remained unknown. Around 1530, Swiss physician Paracelsus identified alum as separate from vitriole (sulfates), suggesting it was a salt of an earth of alum.[10] In 1595, German doctor and chemist Andreas Libavius demonstrated that alum and green and blue vitriole were formed by the same acid but different earths;[11] for the undiscovered earth that formed alum, he proposed the name "alumina".[10] In 1702, German chemist Georg Ernst Stahl stated that the unknown base of alum was of the nature of lime or chalk; this mistaken view was shared by many scientists for another half a century.[12] In 1722, German chemist Friedrich Hoffmann announced his belief that the base of alum was a distinct earth.[12] In 1728, French chemist Étienne Geoffroy Saint-Hilaire suggested that alum was formed by an unknown earth and sulfuric acid;[12] he mistakenly believed that burning of that earth yielded silica.[13] In 1739, French chemist Jean Gello proved the equivalence between the earth in clay and the earth resulting from the reaction of alkali on alum.[14] In 1746, German chemist Johann Heinrich Pott showed that the precipitate obtained when an alkali is poured into a solution of alum is different from lime and chalk.[15]

In 1754, German chemist Andreas Sigismund Marggraf synthesized the earth of alum by boiling clay in sulfuric acid and adding potash.[12] He realized that adding soda, potash, or alkali to a solution of the new earth in sulfuric acid yielded alum.[16] He described the earth as alkaline, as he had discovered it can dissolve in acids when dried. Marggraf also described salts of the earth of alum: the chloride, the nitrate, and the acetate.[14] In 1758, French chemist Pierre Macquer wrote that alumina[e] resembled a metallic earth.[17] In 1767, Swedish chemist Torbern Bergman published an article describing crystallization of alum from a solution obtained from boiling alunite in sulfuric acid followed by addition of potash. He also synthesized alum as a reaction product between sulfates of aluminium and potassium, demonstrating that alum was a double salt.[10] In 1776, German pharmaceutical chemist Carl Wilhelm Scheele demonstrated that both alum and silica originate from clay and that alum does not contain silicon.[18] Geoffroy's mistake was only corrected in 1785 by German chemist and pharmacist Johann Christian Wiegleb who determined that contrary to contemporary belief, the earth of alum could not be synthesized from silica and alkalies.[19]

Swedish chemist Jöns Jacob Berzelius suggested in 1815[20] the formula AlO3 for alumina.[21] The correct formula, Al2O3, was established by German chemist Eilhard Mitscherlich in 1821; this helped Berzelius determine the correct atomic weight of the metal, 27.[21]

Synthesis of metal

In 1760, French chemist Theodor Baron de Henouville declared he believed alumina was a metallic earth and first attempted to reduce it to its metal, at which he was unsuccessful. His method was not reported but he claimed he had tried every method of reduction known at the time. It is probable that he mixed alum with carbon or some organic substance, with salt or soda for flux, and heated as highly as possible in a charcoal fire.[17] In 1782, French chemist Antoine Lavoisier wrote that he considered alumina was an oxide of a metal which had an affinity for oxygen so strong that no known reducing agents could overcome it.[22]

In 1790, Austrian chemists Anton Leopold Ruprecht and Matteo Tondi repeated Baron's experiments, significantly increasing the temperatures; they found small metallic particles, which they believed to be the sought-after metal, but later experiments by other chemists showed these were iron phosphide from impurities in charcoal and bone ash. German chemist Martin Heinrich Klaproth commented in an aftermath, "if there exists an earth which has been put in conditions where its metallic nature should be disclosed, if it had such, an earth exposed to experiments suitable for reducing it, tested in the hottest fires by all sorts of methods, on a large as well as on a small scale, that earth is certainly alumina, yet no one has yet perceived its metallization."[23] Lavoisier in 1794[24] and French chemist Louis-Bernard Guyton de Morveau in 1795 melted alumina to a white enamel in a charcoal fire fed by pure oxygen but found no metal.[24] American chemist Robert Hare in 1802 melted alumina with an oxyhydrogen blowpipe, also obtaining the enamel, but still found no metal.[23]

Friedrich Wöhler, usually credited as the discoverer of aluminium metal

In 1807, British chemist Humphry Davy successfully electrolyzed alumina with alkaline batteries, but the metal formed contained the alkali metals potassium and sodium and Davy had no means to separate the desired metal from them. He then tried to heat alumina with potassium metal; some potassium oxide was formed, but he was unable to find the sought-after metal.[23] In 1808, Davy set up a different experiment on electrolysis of alumina; he experimentally established that alumina was subject to decomposition in the electric arc, but he was unable to separate the metal from iron, with which it alloyed.[25] Finally Davy tried yet another electrolysis experiment, seeking to collect the metal on iron, but was again unable to separate the two.[23] During his experiments, Davy suggested the metal be named alumium in 1808[26] and aluminum in 1812, thus producing the modern name.[25] Other scientists used the spelling aluminium; the former spelling regained usage in the United States in the following decades.[27]

In 1813, American chemist Benjamin Silliman repeated Hare's experiment and obtained small granules of the sought-after metal, which almost immediately burned.[23]

Production of the metal was claimed in 1824 by Danish physicist and chemist Hans Christian Ørsted. He reacted anhydrous aluminium chloride with potassium amalgam, yielding a lump of metal that looked similar to tin.[28][29] He presented his results and demonstrated a sample of the new metal in 1825. In 1826, he wrote that "aluminium has a metallic luster and somewhat grayish color and breaks down water very slowly"; this suggests that he had obtained an aluminium–potassium alloy rather than pure aluminium.[30] Ørsted was not convinced that he had obtained aluminium[31] and gave little importance to his discovery;[32] a different source suggests he was unable to continue his research for financial reasons.[6] As a result, and because he published his work in a Danish magazine unknown to the general European public, he is often not credited as the element's discoverer;[31] some earlier sources went further and claimed Ørsted had not in fact isolated aluminium.[33]

Berzelius attempted to isolate the metal in 1825; he carefully washed the potassium analog of the base salt in cryolite in a crucible. He had correctly identified the formula of this salt prior to the experiment as K3AlF6. He found no metal, but his experiment came very close to succeeding, and was successfully reproduced many times later. Berzelius's mistake was in using an excess of potassium, which made the solution too alkaline and dissolved all the newly formed aluminium.[34]

In 1827, German chemist Friedrich Wöhler repeated Ørsted's experiments but did not identify any aluminium. (Wöhler later wrote to Berzelius, "what Oersted assumed to be a lump of aluminium was certainly nothing but an aluminium-containing potassium".)[f] He then conducted a similar experiment, mixing anhydrous aluminium chloride with potassium, and produced a powder of aluminium.[29] He continued his research and in 1845, he was able to produce small pieces of the metal and described some of its physical properties. Wöhler's description of the properties indicates that he had obtained impure aluminium.[36] Wöhler's—and other scientists'—failure to reproduce Ørsted's experiment only contributed to the non-recognition of Ørsted as the discoverer of aluminium metal and Wöhler was credited as the discoverer of aluminium following the success and descriptive details of his 1845 experiment.[37] The reason for the inconsistency between Ørsted's and Wöhler's experiments was only discovered in 1921 by Danish chemist Johan Fogh, who demonstrated that Ørsted's experiment was successful thanks to the use of a large amount of excess aluminium chloride and an amalgam with low potassium content.[36]

Rare metal

As Wöhler's method could not yield large amounts of aluminium, the metal remained rare; its cost exceeded that of gold.[32]

The 100 ounces (2.8 kg) capstone of the Washington Monument (Washington, D.C., United States) was made in 1884 from aluminium. At the time, it was the largest piece of aluminium ever cast.[38]

French chemist Henri Étienne Sainte-Claire Deville announced an industrial method of aluminium production in 1854 at the Paris Academy of Sciences.[39] Aluminium trichloride could be reduced by sodium, a metal more convenient and less expensive than potassium, which had been used by Wöhler.[40] Subsequently, bars of aluminium were exhibited for the first time to the general public at the Exposition Universelle of 1855.[41] The metal was presented there as "the silver from clay", and this name was soon widely used.[42] Napoleon III of France subsidized Deville's research, which cost about 20 times the annual income of an ordinary family.[43] Prior to the exposition, Napoleon is reputed to have held a banquet where the most honored guests were given aluminium utensils, while the others made do with gold.[32] From 1855 to 1859, the price of aluminium dropped by an order of magnitude, from US$500 to $40 per pound.[44] Even then, aluminium was still not of great purity and produced aluminium differed in properties by sample.[43]

In 1856, Deville along with partners established the world's first industrial production of aluminium at a smelter in Rouen.[39] Deville's smelter moved in 1856–1857 to La Glacière, Nanterre, and finally to Salindres. The smelter was soon acquired by the French company Pechiney and the Compagnie d’Alais et de la Camargue, which later became world's largest in chemical aluminium production. The technology at the factory continued to improve, and the output in Salindres in 1872 exceeded that in Nanterre in 1857 by 900 times.[42] The factory in Salindres used bauxite as the primary aluminium ore;[45] some chemists, including Deville, sought to use cryolite, but none surpassed the existing techniques.[46] British engineer William Gerhard set up a plant with cryolite as the primary raw material in Battersea, London, in 1856, but technical and financial difficulties forced closure of the plant in three years.[47]

Other chemists also sought to industrialize production of aluminium. British ironmaster Isaac Lowthian Bell started producing aluminium in 1860, continuing until 1874. During the opening of his factory, he waved to the crowd with a unique and costly aluminium top hat.[48] British engineer James Fern Webster launched industrial production of aluminium by reduction with sodium in 1882; his aluminium was much purer than Deville's. Several other production sites were set up in the 1880s. All were made obsolete by electrolytic production.[49]

At the next fair in Paris in 1867, the visitors were presented with aluminium wire and foil; by the time of the next fair in 1878, aluminium had become a symbol of the future.[50]

Electrolytic production

Aluminium factory in Griesheim, Hesse, Germany, constructed in 1915

Aluminium was first synthesized electrolytically in 1854 independently by Deville and German chemist Robert Wilhelm Bunsen. Their electrolysis methods did not become the basis for industrial production of aluminium because electrical supplies were inefficient at the time; this only changed with the invention of the dynamo by Belgian engineer Zénobe-Théophile Gramme in 1870 and the three-phase current by Russian engineer Mikhail Dolivo-Dobrovolsky in 1889.[51]

The first industrial large-scale production method was independently developed by French engineer Paul Héroult and American engineer Charles Martin Hall in 1886; it is now known as the Hall–Héroult process. Electrolysis of pure alumina is impractical given its very high melting point; both Héroult and Hall realized its melting point could be significantly lowered by presence of molten cryolite. Héroult long could not find enough interest in his invention as demand for aluminium was still small and the factory in Salindres did not wish to improve the process they employed. Héroult and his companions founded Aluminium Industrie Aktien Gesellschaft in 1888. That year, they started industrial production of aluminium bronze in Neuhausen am Rheinfall in 1888. This production was only active for a year; but during that time, Société électrométallurgique française was founded in Paris. The society purchased Héroult's patents and appointed him to the position of director of a smelter in Isère, which would produced aluminium bronze on a large scale at first, and pure aluminium in a few months.[52][53]

German aluminium 50 pfennig coin, 1920

At the same time, Hall produced aluminium by the same process in his home at Oberlin,[54] and successfully tested it at the smelter in Lockport. He then sought to employ it for a large-scale production. For that, the existing smelter would have to radically change their production methods, which they were not willing to do in part because a mass production aluminium would immediately drop the price of the metal; the company's president closely considered purchasing Hall's patent to ensure that the competitors would not make use of the invented process. Hall founded the Pittsburgh Reduction Company in 1888 and initiated mass production of aluminium. In the coming years, this technology was improved on and new factories were constructed.[55]

The Hall–Héroult process converts alumina into the metal; Austrian chemist Carl Joseph Bayer discovered a way of purifying bauxite to yield alumina in 1889, now known as the Bayer process. Bayer sintered bauxite with alkali and leached it with water; after stirring the solution and introducing a seeding agent to it, he found a precipitate from that solution, and that precipitate was pure aluminium hydroxide, which decomposes to alumina on heating. In a few years, he discovered that the aluminium contents of bauxite dissolved in the alkaline leftover from isolation of alumina solids; this paved the way for the industrial employment of this method.[56]

Modern production of the aluminium metal is based around the Bayer and Hall–Héroult processes. The Hall–Héroult process was further improved in 1920 by a team led by Swedish chemist Carl Wilhelm Söderberg. Previously, anode cells were made from pre-baked coal blocks, which quickly corrupted and needed to be replaced often; the team introduced continuous electrodes made from a coke and tar paste in a special reduction chamber. This greatly increased the world output of aluminium.[57]

Mass usage

Give me 30,000 tonnes of aluminium, and I will win the war.

— Soviet leader Joseph Stalin in writing to U.S. president Franklin Roosevelt in 1941[58]
During World War II, the British collected aluminium utensils from households. The aluminium was made into aircraft.[59]

Prices of aluminium dropped, and aluminium had become widely used in jewelry, many everyday items, eyeglass frames, and optical instruments by the early 1890s. Aluminium tableware began to be produced in the late 19th century and gradually supplanted copper and cast iron tableware in the first decades of the 20th century. Aluminium foil was popularized at that time. Aluminium is soft and light, but it was soon discovered that alloying it with other metals could increase its hardness while preserving its low density. Aluminium's ability to form alloys with other metals found many uses in the late 19th and early 20th centuries. For instance, aluminium bronze is applied to make flexible bands, sheets, and wire and is widely employed in the shipbuilding and aviation industries.[60] During World War I, major governments demanded large shipments of aluminium for light strong airframes. They often subsidized factories and the necessary electrical supply systems.[61] Aviation during that time used a new aluminium alloy, duralumin, invented in 1903.[62] Likewise, the civil aviation industry has used aluminium for airframes as well.[63] Aluminium recycling started in the early 20th century and has been used extensively since[64] as aluminium is not impaired by recycling and thus can be recycled repeatedly.[65] Overall production of aluminium peaked during the war: while the world production of aluminium in 1900 was 6,800 metric tons, annual production first exceeded 100,000 tons in 1916. This peak was followed by a decline, then a swift growth.[66]

During the first half of the 20th century, the real price for aluminium continuously fell from $14,000 per metric ton in 1900 to $2,340 in 1948 (in 1998 United States dollars) with some exceptions such as the sharp price rise during World War I.[66] By the mid-20th century, aluminium had become a part of everyday lives, becoming an essential component of houseware.[67] Aluminium freight cars first appeared in 1931. Their lower weight allowed them to carry more cargo.[63] Aluminium's corrosion resistance established it as a construction material for boats during the 1930s; it received wide recognition in the early 1950s.[68] During the 1930s, aluminium emerged as a civil engineering material, with buildings using it for both basic construction and interior,[69] and advanced its use in military engineering, for both airplanes and tank engines.[58] During World War II, production peaked again: world production first exceeded 1,000,000 metric tons in 1941. The United Kingdom started an ambitious program of aluminium recycling; the Minister of Aircraft Production appealed to the public to donate any household aluminium for airplane building.[59] The Soviet Union received 328,000 metric tons of aluminium with the Lend-Lease policy;[70] this aluminium would be used in aircraft and tank engines.[71] Without these shipments, the efficiency of the Soviet aircraft industry would have fallen by over a half.[72] Production fell after the war but then rose again.[66]

Exchange commodity

In the beginning of the second half of the 20th century, the Space Race began. Earth's first artificial satellite, launched in 1957, consisted of two joint aluminium semi-spheres and all subsequent space vehicles have been made of aluminium.[57] The aluminium can was invented in 1956 and employed as a storage for drinks in 1958.[73] In the 1960s, aluminium was employed for production of wires and cables.[74] Since the 1970s, high-speed trains have commonly used aluminium for its lightness. For the same reason, the aluminium content of cars is growing.[63]

By 1955, the market had been mostly divided by the Six Majors: Alcoa (successor of Hall's Pittsburgh Reduction Company), Alcan (originated as a part of that company), Reynolds, Kaiser, Pechiney (successor of Pechiney and the Compagnie d’Alais et de la Camargue that bought Deville's smelter), and Alusuisse (successor of Héroult's Aluminium Industrie Aktien Gesellschaft), with their combined share of the market equaling 86%. From 1945, aluminium consumption grew by almost 10% each year for nearly three decades, gaining ground in building applications, electric cables, basic foils, and the aircraft industry. In the early 1970s, an additional boost came from the development of aluminium beverage cans.[75] Real prices continued to decline until this time as extraction and processing costs were lowered over technological progress and increased production of aluminium,[76] which first exceeded 10,000,000 metric tons in 1971.[66]

World production of aluminium since 1900

In the 1970s, the increased demand for aluminium made it an exchange commodity; it entered the London Metal Exchange, world's oldest industrial metal exchange, in 1978.[57] Since aluminium became an exchange commodity, it has been traded for United States dollars and its price fluctuated along with the exchange rates of the currency.[77] The need to exploit lower-grade poorer quality deposits and the use of fast increasing input costs (above all, energy) increased the net cost of aluminium;[76] the real price began to grow in the 1970s with the rise of energy cost.[78]

The increase of the real price and changes of tariffs and taxes started redistribution of the world producers' shares: while the United States, the Soviet Union, and Japan accounted for nearly 60% of world's primary production in 1972 (and their combined share of consumption of primary aluminium was also close to 60%),[79] their combined share only slightly exceeded 10% in 2012.[80] Production moved from the United States, Japan, and Western Europe to Australia, Canada, the Middle East, Russia, and China, where production was cheaper.[81] Production costs in the late 20th century changed because of advances in technology, lower energy prices, exchange rates of the United States dollar, and alumina prices.[82] The BRIC countries' combined share grew in the first decade of the 21st century from 32.6% to 56.5% in primary production and 21.4% to 47.8% in primary consumption.[83] China is accumulating an especially large share of world's production thanks to abundance of resources, cheap energy, and governmental stimuli;[84] it also increased its consumption share from 2% in 1972 to 40% in 2010.[85] The only other country with a two-digit percentage was the United States with 11%; no other country exceeded 5%.[86] In the United States, Western Europe, and Japan, most aluminium was consumed in transportation, engineering, construction, and packaging.[86]

The world output continued to grow: in 2013, annual production of aluminium exceeded 50,000,000 metric tons. In 2015, it was record 57,500,000 tons.[66]

Notes

  1. ^ "One day a goldsmith in Rome was allowed to show the Emperor Tiberius a dinner plate of a new metal. The plate was very light, and almost as bright as silver. The goldsmith told the Emperor that he had made the metal from plain clay. He also assured the Emperor that only he, himself, and the Gods knew how to produce this metal from clay. The Emperor became very interested, and as a financial expert he was also a little concerned. The Emperor felt immediately, however, that all his treasures of gold and silver would decline in value if people started to produce this bright metal of clay. Therefore, instead of giving the goldsmith the regard expected, he ordered him to be beheaded."[3]
  2. ^ Deville had established that heating a mixture of sodium chloride, clay, and charcoal yields numerous aluminum globules. This was published in the Proceedings of the Academy of Sciences but eventually forgotten.[4] French chemist André Duboin discovered that heating a mixture of borax, alumina, and smaller quantities of dichromate and silica in a crucible formed impure aluminium. Boric acid is abundant in Italy. This hints at the possibility that boric acid, potash, and clay under the reducing influence of coal may have produced aluminium in Rome.[4]
  3. ^ Alumina was plentiful and could be reduced by coke in the presence of copper, giving aluminium–copper alloys. The Chinese did not have the technology to produce pure aluminium and the temperatures needed (around 2000 °C) were not achievable.[6]
  4. ^ "Today, I bring you the victory over the Turk. Every year they wring from the Christians more than three hundred thousand ducats for the alum with which we dye wool. For this is not found among the Latins except a very small quantity. [...] But I have found seven mountains so rich in this material that they could supply seven worlds. If you will give orders to engage workmen, build furnaces, and smelt the ore, you will provide all Europe with alum and the Turk will lose all his profits. Instead they will accrue to you..."[9]
  5. ^ The terms "earth of alum" and "alumina" refer to the same substance. German-speaking authors used "earth of alum" (Alaun-Erde), while the French authors used "alumina" (alumine).
  6. ^ "Was Oersted für einen Aluminiumklumpen hielt, ist ganz gewiß nichts anderes gewesen als ein aluminiumhaltiges Kalium."[35]

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Bibliography

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