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History of aluminium

Aluminium (or aluminum) metal is very rare in native form, and the process to refine it from ores is complex, so for most of human history it was unknown. However, the compound alum has been known since the 5th century BCE and was used extensively by the ancients for dyeing. During the Middle Ages, its use for dyeing made it a commodity of international commerce. Renaissance scientists believed that alum was a salt of a new earth; during the Age of Enlightenment, it was established that this earth, alumina, was an oxide of a new metal. Discovery of this metal was announced in 1825 by Danish physicist Hans Christian Ørsted, whose work was extended by German chemist Friedrich Wöhler.

Extrusion billets of aluminium in Yugoslavia, 1968.

Aluminium was difficult to refine and thus uncommon in actual use. Soon after its discovery, the price of aluminium exceeded that of gold. It was reduced only after the initiation of the first industrial production by French chemist Henri Étienne Sainte-Claire Deville in 1856. Aluminium became much more available to the public with the Hall–Héroult process developed independently 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 processes have been used for aluminium production up to the present.

The introduction of these methods for the mass production of aluminium led to extensive use of the light, corrosion-resistant metal in industry and everyday life. Aluminium began to be used in engineering and construction. In World Wars I and II, aluminium was a crucial strategic resource for aviation. World production of the metal grew from 6,800 metric tons in 1900 to 2,810,000 metric tons in 1954, when aluminium became the most produced non-ferrous metal, surpassing copper.

In the second half of the 20th century, aluminium gained usage in transportation and packaging. Aluminium production became a source of concern due to its effect on the environment, and aluminium recycling gained ground. The metal became an exchange commodity in the 1970s. Production began to shift from developed countries to developing ones; by 2010, China had accumulated an especially large share in both production and consumption of aluminium. World production continued to rise, reaching 58,500,000 metric tons in 2015. Aluminium production exceeds those of all other non-ferrous metals combined.

Early history edit

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 ...

— Giovanni da Castro to his godfather Pope Pius II in 1461, after discovering a rich source of alum at Tolfa near Rome[1]
 
Crystals of alum, the naturally occurring form of which was known back to the ancients.

The history of aluminium was shaped by the usage of its compound alum. The first written record of alum was in the 5th century BCE by Greek historian Herodotus.[2] The ancients used it as a dyeing mordant, in medicine, in chemical milling, and as a fire-resistant coating for wood to protect fortresses from enemy arson.[3] Aluminium metal was unknown. Roman writer Petronius mentioned in his novel Satyricon that an unusual glass had been presented to the emperor: after it was thrown on the pavement, it did not break but only deformed. It was returned to its former shape using a hammer. After learning from the inventor that nobody else knew how to produce this material, the emperor had the inventor executed so that it did not diminish the price of gold.[4] Variations of this story were mentioned briefly in Natural History by Roman historian Pliny the Elder (who noted the story had "been current through frequent repetition rather than authentic")[5] and Roman History by Roman historian Cassius Dio.[4] Some sources suggest this glass could be aluminium.[a][b] It is possible aluminium-containing alloys were produced in China during the reign of the first Jin dynasty (266–420).[c]

After the Crusades, alum was a commodity of international commerce;[9] it was indispensable in the European fabric industry.[10] Small alum mines were worked in Catholic Europe but most alum came from the Middle East.[11] Alum continued to be traded through the Mediterranean Sea until the mid-15th century, when the Ottomans greatly increased export taxes. In a few years, alum was discovered in great abundance in Italy. Pope Pius II forbade all imports from the east, using the profits from the alum trade to start a war with the Ottomans.[1] This newly found alum long played an important role in European pharmacy, but the high prices set by the papal government eventually made other states start their own production; large-scale alum mining came to other regions of Europe in the 16th century.[12]

Establishing the nature of alum edit

I think it not too venturesome to predict that a day will come when the metallic nature of the base of alum will be incontestably proven.

— French chemist Théodore Baron d'Hénouville in 1760 at the Paris Academy of Sciences[13]
 
Antoine Lavoisier established that alumina was an oxide of an unknown metal.

At the start of the Renaissance, the nature of alum remained unknown. Around 1530, Swiss physician Paracelsus recognized alum as separate from vitriole (sulfates) and suggested it was a salt of an earth.[14] 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;[15] for the undiscovered earth that formed alum, he proposed the name "alumina".[14] German chemist Georg Ernst Stahl stated that the unknown base of alum was akin to lime or chalk in 1702; this mistaken view was shared by many scientists for half a century.[16] In 1722, German chemist Friedrich Hoffmann suggested that the base of alum was a distinct earth.[16] In 1728, French chemist Étienne Geoffroy Saint-Hilaire claimed alum was formed by an unknown earth and sulfuric acid;[16] he mistakenly believed burning that earth yielded silica.[17] (Geoffroy's mistake was corrected only in 1785 by German chemist and pharmacist Johann Christian Wiegleb. He determined that earth of alum could not be synthesized from silica and alkalis, contrary to contemporary belief.)[18] French chemist Jean Gello proved the earth in clay and the earth resulting from the reaction of an alkali on alum were identical in 1739.[19] German chemist Johann Heinrich Pott showed the precipitate obtained from pouring an alkali into a solution of alum was different from lime and chalk in 1746.[20]

German chemist Andreas Sigismund Marggraf synthesized the earth of alum by boiling clay in sulfuric acid and adding potash in 1754.[16] He realized that adding soda, potash, or an alkali to a solution of the new earth in sulfuric acid yielded alum.[21] He described the earth as alkaline, as he had discovered it dissolved in acids when dried. Marggraf also described salts of this earth: chloride, nitrate and acetate.[19] In 1758, French chemist Pierre Macquer wrote that alumina[d] resembled a metallic earth.[13] In 1760, French chemist Théodore Baron d'Hénouville expressed his confidence that alumina was a metallic earth.[13]

In 1767, Swedish chemist Torbern Bergman synthesized alum by boiling alunite in sulfuric acid and adding potash to the solution. He also synthesized alum as a reaction product between sulfates of potassium and earth of alum, demonstrating that alum was a double salt.[14] Swedish German pharmaceutical chemist Carl Wilhelm Scheele demonstrated that both alum and silica originated from clay and alum did not contain silicon in 1776.[22] Writing in 1782, French chemist Antoine Lavoisier considered alumina an oxide of a metal with an affinity for oxygen so strong that no known reducing agents could overcome it.[23]

Swedish chemist Jöns Jacob Berzelius suggested[24] the formula AlO3 for alumina in 1815.[25] 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.[25]

Isolation of metal edit

This amalgam quickly separates in air, and by distillation, in an inert atmosphere, gives a lump of metal which in color and luster somewhat resembles tin.

— Danish physicist Hans Christian Ørsted in 1825, describing isolation of aluminium at the Royal Danish Academy of Sciences and Letters[26]
 
Hans Christian Ørsted, discoverer of aluminium metal.

In 1760, Baron de Hénouville unsuccessfully attempted to reduce alumina to its metal. He claimed he had tried every method of reduction known at the time, though his methods were unpublished. It is probable he mixed alum with carbon or some organic substance, with salt or soda for flux, and heated it in a charcoal fire.[13] Austrian chemists Anton Leopold Ruprecht and Matteo Tondi repeated Baron's experiments in 1790, significantly increasing the temperatures. They found small metallic particles they believed were the sought-after metal; but later experiments by other chemists showed these were iron phosphide from impurities in the 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."[27] Lavoisier in 1794[28] 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.[28] American chemist Robert Hare melted alumina with an oxyhydrogen blowpipe in 1802, also obtaining the enamel, but still found no metal.[27]

In 1807, British chemist Humphry Davy successfully electrolyzed alumina with alkaline batteries, but the resulting alloy contained potassium and sodium, and Davy had no means to separate the desired metal from these. He then heated alumina with potassium, forming potassium oxide but was unable to produce the sought-after metal.[27] In 1808, Davy set up a different experiment on electrolysis of alumina, establishing that alumina decomposed in the electric arc but formed metal alloyed with iron; he was unable to separate the two.[29] Finally, he tried yet another electrolysis experiment, seeking to collect the metal on iron, but was again unable to separate the coveted metal from it.[27] Davy suggested the metal be named alumium in 1808[30] and aluminum in 1812, thus producing the modern name.[29] Other scientists used the spelling aluminium; the former spelling regained usage in the United States in the following decades.[31]

American chemist Benjamin Silliman repeated Hare's experiment in 1813 and obtained small granules of the sought-after metal, which almost immediately burned.[27]

In 1824, Danish physicist Hans Christian Ørsted attempted to produce the metal. He reacted anhydrous aluminium chloride with potassium amalgam, yielding a lump of metal that looked similar to tin.[26][32][33] He presented his results and demonstrated a sample of the new metal in 1825. In 1826, he wrote, "aluminium has a metallic luster and somewhat grayish color and breaks down water very slowly"; this suggests he had obtained an aluminium–potassium alloy, rather than pure aluminium.[34] Ørsted placed little importance on his discovery.[35] He did not notify either Davy or Berzelius, both of whom he knew, and published his work in a Danish magazine unknown to the European public.[35] As a result, he is often not credited as the discoverer of the element;[36] some earlier sources claimed Ørsted had not isolated aluminium.[37]

 
Friedrich Wöhler, pioneer researcher of the properties of aluminium.

Berzelius tried isolating the metal in 1825 by carefully washing the potassium analog of the base salt in cryolite in a crucible. Prior to the experiment, he had correctly identified the formula of this salt 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.[38]

German chemist Friedrich Wöhler visited Ørsted in 1827 and received explicit permission to continue the aluminium research, which Ørsted "did not have time" for.[35] 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 aluminium-containing potassium".)[39] He conducted a similar experiment, mixing anhydrous aluminium chloride with potassium, and produced a powder of aluminium.[33] After hearing about this, Ørsted suggested that his own aluminium might have contained potassium.[35] Wöhler continued his research and in 1845 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.[40] Other scientists also failed to reproduce Ørsted's experiment,[40] and Wöhler was credited as the discoverer for many years.[41] While Ørsted was not concerned with the priority of the discovery,[35][e] some Danes tried to demonstrate he had obtained aluminium.[35] In 1921, the reason for the inconsistency between Ørsted's and Wöhler's experiments was discovered by Danish chemist Johan Fogh, who demonstrated that Ørsted's experiment was successful thanks to use of a large amount of excess aluminium chloride and an amalgam with low potassium content.[40] In 1936, scientists from American aluminium producing company Alcoa successfully recreated that experiment.[42] However, many later sources still credit Wöhler with the discovery of aluminium, as well as its successful isolation in a relatively pure form.[43]

Early industrial production edit

My first thought was I had laid my hands on this intermediate metal which would find its place in man's uses and needs when we would find the way of taking it out of the chemists' laboratory and putting it in the industry.

— Preface of Aluminium, its properties, manufacture and applications, book written by French chemist Henri Étienne Sainte-Claire Deville in 1859[44]
 
Henri Étienne Sainte-Claire Deville was the first to establish a method to manufacture aluminium.

Since Wöhler's method could not yield large amounts of aluminium, the metal remained uncommon; its cost[f] had exceeded that of gold before a new method was devised. In 1852, aluminium was sold at US$34 per ounce.[45] In comparison, the price of gold at the time was $19 per ounce.[46]

French chemist Henri Étienne Sainte-Claire Deville announced an industrial method of aluminium production in 1854 at the Paris Academy of Sciences.[47] Aluminium chloride could be reduced by sodium, a metal more convenient and less expensive than potassium used by Wöhler.[48] Deville was able to produce an ingot of the metal.[49] Napoleon III of France promised Deville an unlimited subsidy for aluminium research; in total, Deville used 36,000 French francs—20 times the annual income of an ordinary family.[50] Napoleon's interest in aluminium lay in its potential military use: he wished weapons, helmets, armor, and other equipment for the French army could be made of the new light, shiny metal.[50] While the metal was still not displayed to the public, Napoleon is reputed to have held a banquet where the most honored guests were given aluminium utensils while others made do with gold.[51]

Twelve small ingots of aluminium were later exhibited for the first time to the public at the Exposition Universelle of 1855.[50] The metal was presented as "the silver from clay" (aluminium is very similar to silver visually), and this name was soon widely used.[50] It attracted widespread attention; it was suggested aluminium be used in arts, music, medicine, cooking, and tableware.[52] The metal was noticed by the avant-garde writers of the time—Charles Dickens, Nikolay Chernyshevsky, and Jules Verne—who envisioned its use in the future.[53] However, not all attention was favorable. Newspapers wrote, "The Parisian expo put an end to the fairy tale of the silver from clay", saying that much of what had been said about the metal was exaggerated if not untrue and that the amount of the presented metal—about a kilogram—contrasted with what had been expected and was "not a lot for a discovery that was said to turn the world upside down".[50] Overall, the fair led to the eventual commercialization of the metal.[53] That year, aluminium was put to the market at a price of 300 F per kilogram.[54] At the next fair in Paris in 1867, visitors were presented with aluminium wire and foil as well a new alloy—aluminium bronze, notable for its low cost of production, high resistance to corrosion, and desirable mechanical properties.[55]

 
20 French francs aluminium coin from 1857 featuring a portrait of Napoleon III of France, patron of research of aluminium production.

Manufacturers did not wish to divert resources from producing well-known (and marketable) metals, such as iron and bronze, to experiment with a new one; moreover, produced aluminium was still not of great purity and differed in properties by sample. This led to an initial general reluctance to produce the new metal.[50] Deville and partners established the world's first industrial production of aluminium at a smelter in Rouen in 1856.[47] Deville's smelter moved that year to La Glacière and then Nanterre, and in 1857 to Salindres. For the factory in Nanterre, an output of 2 kilograms of aluminium per day was recorded,[56] with a purity of 98%.[57] Originally, production started with synthesis of pure alumina, which was obtained from calcination of ammonium alum. In 1858, Deville was introduced to bauxite and soon developed into what became known as the Deville process, employing the mineral as a source for alumina production.[58] In 1860, Deville sold his aluminium interests to Henri Merle, a founder of Compagnie d'Alais et de la Camargue; this company dominated the aluminium market in France decades later.[59]

 
The 2.85-kilogram (6.3 lb) capstone of the Washington Monument (Washington, D.C.) was made from aluminium in 1884. At the time, it was the largest piece of aluminium ever cast.[60]

Some chemists, including Deville, sought to use cryolite as the source ore, but with little success.[61] 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 the closure of the plant in three years.[57] British ironmaster Isaac Lowthian Bell produced aluminium from 1860 to 1874. During the opening of his factory, he waved to the crowd with a unique and costly aluminium top hat.[62] No statistics about this production can be recovered, but it "cannot be very high".[63] Deville's output grew to 1 metric ton per year in 1860; 1.7 metric tons in 1867; and 1.8 metric tons in 1872.[63] At the time, demand for aluminium was low: for example, sales of Deville's aluminium by his British agents equaled 15 kilograms in 1872.[57] Aluminium at the time was often compared with silver; like silver, it was found to be suitable for making jewelry and objéts d'art.[55] Price for aluminium steadily declined to 240 F in 1859; 200 F in 1862; 120 F in 1867.[64]

Other production sites began to appear in the 1880s. British engineer James Fern Webster launched the industrial production of aluminium by reduction with sodium in 1882; his aluminium was much purer than Deville's (it contained 0.8% impurities whereas Deville's typically contained 2%).[65] World production of aluminium in 1884 equaled 3.6 metric tons.[66] In 1884, American architect William Frishmuth combined production of sodium, alumina, and aluminium into a single technological process; this contrasted with the previous need to collect sodium, which combusts in water and sometimes air;[67] his aluminium production cost was about $16 per pound (compare to silver's cost of $19 per pound, or the French price, an equivalent of $12 per pound).[68] In 1885, Aluminium- und Magnesiumfabrik started production in Hemelingen.[69] Its production figures strongly exceeded those of the factory in Salindres but the factory stopped production in 1888.[70] In 1886, American engineer Hamilton Castner devised a method of cheaper production of sodium, which decreased the cost of aluminium production to $8 per pound, but he did not have enough capital to construct a large factory like Deville's.[71] In 1887, he constructed a factory in Oldbury; Webster constructed a plant nearby and bought Castner's sodium to use it in his own production of aluminium.[65] In 1889, German metallurgist Curt Netto launched a method of reduction of cryolite with sodium that produced aluminium containing 0.5–1.0% of impurities.[72]

Electrolytic production and commercialization edit

I'm going for that metal.

— Purportedly, American student Charles Martin Hall in 1880, after hearing from his chemistry professor that an industrial production of aluminium would be a great good for humanity and a source of wealth for the discoverer[66]
 
Cover of the patent granted to Charles Martin Hall for his process of reducing aluminium by electrolysis. Hall applied for the patent two months after Héroult; as a result, it took him almost three years to prove the originality of his method and the patent was only granted in 1889.[73]

Aluminium was first produced independently using electrolysis in 1854 by the German chemist Robert Wilhelm Bunsen and Deville. Their methods did not become the basis for industrial production of aluminium because electrical supplies were inefficient at the time. This changed only with Belgian engineer Zénobe-Théophile Gramme's invention of the dynamo in 1870, which made creation of large amounts of electricity possible. The invention of the three-phase current by Russian engineer Mikhail Dolivo-Dobrovolsky in 1889 made transmission of this electricity over long distances achievable.[74] Soon after his discovery, Bunsen moved on to other areas of interest while Deville's work was noticed by Napoleon III; this was the reason Deville's Napoleon-funded research on aluminium production had been started. Deville quickly realized electrolytic production was impractical at the time and moved on to chemical methods, presenting results later that year.[66][75]

Electrolytic mass production remained difficult because electrolytic baths could not withstand prolonged contact with molten salts, succumbing to corrosion. The first attempt to overcome this for aluminium production was made by American engineer Charles Bradley in 1883. Bradley heated aluminium salts internally: the highest temperature was inside the bath and the lowest was on its walls, where salts would solidify and protect the bath. Bradley then sold his patent claim to brothers Alfred and Eugene Cowles, who used it at a smelter in Lockport and later in Stoke-upon-Trent but the method was modified to yield alloys rather than pure aluminium.[76] Bradley applied for a patent in 1883; due to his broad wordings, it was rejected as composed of prior art. After a necessary two-year break, he re-applied. This process lasted for six years, as the patent office questioned whether Bradley's ideas were original.[77] When Bradley was granted a patent, electrolytic aluminium production had already been in place for several years.[78]

The first 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 it could be greatly lowered by the presence of molten cryolite.[g] Héroult was granted a patent in France in April[80] and subsequently in several other European countries;[81] he also applied for a U.S. patent in May.[80] After securing a patent, Héroult could not find interest in his invention. When asking professionals for advice, he was told there was no demand for aluminium but some for aluminium bronze. The factory in Salindres did not wish to improve its process. In 1888, Héroult and his companions founded Aluminium Industrie Aktiengesellschaft and started industrial production of aluminium bronze in Neuhausen am Rheinfall. Then, Société électrométallurgique française was founded in Paris. They convinced Héroult to return to France, purchased his patents, and appointed him as the director of a smelter in Isère, which produced aluminium bronze on a large scale at first and pure aluminium in a few months.[82][83]

 
Statue of Anteros, Greek god of requited love, on Piccadilly Circus in London. This statue was erected in 1893 and is considered the first major work in aluminium.[84]

At the same time, Hall produced aluminium by the same process in his home at Oberlin.[85] He applied for a patent in July, and the patent office notified Hall of an "interference" with Héroult's application. The Cowles brothers offered legal support. By then, Hall had failed to develop a commercial process for his first investors, and he turned to experimenting at Cowles' smelter in Lockport. He experimented for a year without much success but gained the attention of investors.[h] Hall co-founded the Pittsburgh Reduction Company in 1888 and initiated production of aluminium.[87] Hall's patent was granted in 1889.[73][i] In 1889, Hall's production began to use the principle of internal heating.[j] By September 1889, Hall's production grew to 385 pounds (175 kilograms) at a cost of $0.65 per pound.[90] By 1890, Hall's company still lacked capital and did not pay dividends; Hall had to sell some of his shares to attract investments.[91] During that year, a new factory in Patricroft was constructed.[92] The smelter in Lockport was unable to withstand the competition and shut down by 1892.[93]

The Hall–Héroult process converts alumina into the metal. Austrian chemist Carl Josef Bayer discovered a way of purifying bauxite to yield alumina in 1888 at a textile factory in Saint Petersburg and was issued a patent later that year;[94] this is 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 of pure aluminium hydroxide, which decomposed to alumina on heating. In 1892, while working at a chemical plant in Yelabuga, he discovered the aluminium contents of bauxite dissolved in the alkaline leftover from isolation of alumina solids; this was crucial for the industrial employment of this method. He was issued a patent later that year.[94][95]

 
World production of aluminium from 1885 to 1899.

The total amount of unalloyed aluminium produced using Deville's chemical method from 1856 to 1889 equaled 200 metric tons.[47] Production in 1890 alone was 175 metric tons. It grew to 715 metric tons in 1893 and to 4,034 metric tons in 1898.[70] The price fell to $2 per pound in 1889 and to $0.5 per pound in 1894.[96]

By the end of 1889, a consistently high purity of aluminium produced via electrolysis had been achieved.[97] In 1890, Webster's factory went obsolete after an electrolysis factory was opened in England.[67] Netto's main advantage, the high purity of the resulting aluminium, was outmatched by electrolytic aluminium and his company closed the following year.[97] Compagnie d'Alais et de la Camargue also decided to switch to electrolytic production, and their first plant using this method was opened in 1895.[73]

Modern production of the aluminium metal is based on the Bayer and Hall–Héroult processes. It was further improved in 1920 by a team led by Swedish chemist Carl Wilhelm Söderberg. Previously, anode electrodes had been made from pre-baked coal blocks, which quickly corrupted and required replacement; the team introduced continuous electrodes made from a coke and tar paste in a reduction chamber. This advance greatly increased the world output of aluminium.[98]

Mass usage edit

Give us aluminum in the right quantity, and we will be able to fight for another four years.

— Soviet leader Joseph Stalin to Harry Hopkins, personal representative of the U.S. President Franklin D. Roosevelt, in August 1941[99]
 
Nominal (in contemporary United States dollars, in blue) and real (in 1998 United States dollars, in red) prices of aluminium since 1900.

Prices for aluminium declined, and by the early 1890s, the metal had become widely used in jewelry, eyeglass frames, optical instruments, and many everyday items. Aluminium cookware began to be produced in the late 19th century and gradually supplanted copper and cast iron cookware 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 alloys 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.[100] Aviation used a new aluminium alloy, duralumin, invented in 1903.[101] Aluminium recycling began in the early 1900s and has been used extensively since[102] as aluminium is not impaired by recycling and thus can be recycled repeatedly.[103] At this point, only the metal that had not been used by end-consumers was recycled.[104] 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.[105][106] Overall production of aluminium peaked during the war: world production of aluminium in 1900 was 6,800 metric tons; in 1916, annual production exceeded 100,000 metric tons.[104] The war created a greater demand for aluminium, which the growing primary production was unable to fully satisfy, and recycling grew intensely as well.[102] The peak in production was followed by a decline, then a swift growth.[104]

 
The first aviation flight was performed by the Wright brothers in 1903. A strong light material was needed for the engine of the Wright Flyer; light aluminium alloyed with copper for strength was used.[107]

During the first half of the 20th century, the real price for aluminium fell continuously from $14,000 per metric ton in 1900 to $2,340 in 1948 (in 1998 United States dollars). There were some exceptions such as the sharp price rise during World War I.[104] Aluminium was plentiful, and in 1919 Germany began to replace its silver coins with aluminium ones; more and more denominations were switched to aluminium coins as hyperinflation progressed in the country.[108] By the mid-20th century, aluminium had become a part of everyday lives, becoming an essential component of housewares.[109] Aluminium freight cars first appeared in 1931. Their lower mass allowed them to carry more cargo.[106] During the 1930s, aluminium emerged as a civil engineering material used in both basic construction and building interiors.[110] Its use in military engineering for both airplanes and tank engines advanced.[111]

Aluminium obtained from recycling was considered inferior to primary aluminium because of poorer chemistry control as well as poor removal of dross and slags. Recycling grew overall but depended largely on the output of primary production: for instance, as electric energy prices declined in the United States in the late 1930s, more primary aluminium could be produced using the energy-expensive Hall–Héroult process. This rendered recycling less necessary, and thus aluminium recycling rates went down.[102] By 1940, mass recycling of post-consumer aluminium had begun.[104]

 
During World War II, the British collected aluminium utensils from households. The aluminium was made into aircraft.[112]

During World War II, production peaked again, exceeding 1,000,000 metric tons for the first time in 1941.[104] Aluminium was used heavily in aircraft production and was a strategic material of extreme importance; so much so that when Alcoa (successor of Hall's Pittsburgh Reduction Company and the aluminium production monopolist in the United States at the time) did not expand its production, the United States Secretary of the Interior proclaimed in 1941, "If America loses the war, it can thank the Aluminum Corporation of America".[113] In 1939, Germany was the world's leading producer of aluminium; the Germans thus saw aluminium as their edge in the war. Aluminium coins continued to be used but while they symbolized a decline on their introduction, by 1939, they had come to represent power.[114] (In 1941, they began to be withdrawn from circulation to save the metal for military needs.)[115] After the United Kingdom was attacked in 1940, it started an ambitious program of aluminium recycling; the newly appointed Minister of Aircraft Production appealed to the public to donate any household aluminium for airplane building.[112][k] The Soviet Union received 328,100 metric tons of aluminium from its co-combatants from 1941 to 1945;[120] this aluminium was used in aircraft and tank engines.[121] Without these shipments, the output of the Soviet aircraft industry would have fallen by over a half.[122]

After the wartime peak, world production fell for three late-war and post-war years but then regained its rapid growth.[104] In 1954, the world output equaled 2,810,000 metric tons;[104] this production surpassed that of copper,[l] historically second in production only to iron,[124][125] making it the most produced non-ferrous metal.

Aluminium Age edit

Nothing stops time. One epoch follows another, and sometimes we don't even notice it. The Stone Age... The Bronze Age... The Iron Age... [...] However one may assert that it is now that we stand on the threshold of the Aluminium Age.

— Russian aluminium producing company RUSAL in their book Aluminium: The Thirteenth Element in 2007[126]
 
Aluminium can.

Earth's first artificial satellite, launched in 1957, consisted of two joined aluminium hemispheres. All subsequent spacecraft have used aluminium to some extent.[98] The aluminium can was first manufactured in 1956 and employed as a container for drinks in 1958.[127] In the 1960s, aluminium was employed for the production of wires and cables.[128] Since the 1970s, high-speed trains have commonly used aluminium for its high strength-to-weight ratio. For the same reason, the aluminium content of cars is growing.[106]

By 1955, the world market[m] had been dominated by the Six Majors: Alcoa, Alcan (originated as a part of Alcoa), Reynolds, Kaiser, Pechiney (merger of Compagnie d'Alais et de la Camargue that bought Deville's smelter and Société électrométallurgique française that hired Héroult), and Alusuisse (successor of Héroult's Aluminium Industrie Aktien Gesellschaft); their combined share of the market equaled 86%.[129] 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.[130] The real price declined until the early 1970s;[131] in 1973, the real price equaled $2,130 per metric ton (in 1998 United States dollars).[104] The main drivers of the drop in price was the decline of extraction and processing costs, technological progress, and the increase in aluminium production,[131] which first exceeded 10,000,000 metric tons in 1971.[104]

 
Formwork at the Volokolamskaya metro station of the Moscow Metro.

In the late 1960s, governments became aware of waste from the industrial production; they enforced a series of regulations favoring recycling and waste disposal. Söderberg anodes, which save capital and labor to bake the anodes but are more harmful to the environment (because of a greater difficulty in collecting and disposing of the baking fumes),[132] fell into disfavor, and production began to shift back to the pre-baked anodes.[133] The aluminium industry began promoting the recycling of aluminium cans in an attempt to avoid restrictions on them.[102] This sparked recycling of aluminium previously used by end-consumers: for example, in the United States, levels of recycling of such aluminium increased 3.5 times from 1970 to 1980 and 7.5 times to 1990.[104] Production costs for primary aluminium grew in the 1970s and 1980s, and this also contributed to the rise of aluminium recycling.[102] Closer composition control and improved refining technology diminished the quality difference between primary and secondary aluminium.[102]

In the 1970s, the increased demand for aluminium made it an exchange commodity; it entered the London Metal Exchange, the world's oldest industrial metal exchange, in 1978.[98] Since then, aluminium has been traded for United States dollars and its price fluctuated along with the currency's exchange rate.[134] The need to exploit lower-grade poorer quality deposits and fast increasing input costs of energy, but also bauxite, as well as changes in exchange rates and greenhouse gas regulation, increased the net cost of aluminium;[131] the real price grew in the 1970s.[135]

 
World production of aluminium since 1900.

The increase of the real price, and changes of tariffs and taxes, began the redistribution of world producers' shares: 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%);[136] but their combined share only slightly exceeded 10% in 2012.[137] The production shift began in the 1970s with production moving from the United States, Japan, and Western Europe to Australia, Canada, the Middle East, Russia, and China, where it was cheaper due to lower electricity prices and favorable state regulation, such as low taxes or subsidies.[138] Production costs in the 1980s and 1990s declined because of advances in technology, lower energy and alumina prices, and high exchange rates of the United States dollar.[139]

In the 2000s, the BRIC countries' (Brazil, Russia, India and China) combined share grew from 32.6% to 56.5% in primary production and 21.4% to 47.8% in primary consumption.[140] China has accumulated an especially large share of world production, thanks to an abundance of resources, cheap energy, and governmental stimuli;[141] it also increased its share of consumption from 2% in 1972 to 40% in 2010.[142] The only other country with a two-digit percentage was the United States with 11%; no other country exceeded 5%.[143] In the United States, Western Europe and Japan, most aluminium was consumed in transportation, engineering, construction, and packaging.[143]

In the mid-2000s, increasing energy, alumina and carbon (used in anodes) prices caused an increase in production costs. This was amplified by a shift in currency exchange rates: not only a weakening of the United States dollar, but also a strengthening of the Chinese yuan. The latter became important as most Chinese aluminium was relatively cheap.[144]

World output continued growing: in 2018, it was a record 63,600,000 metric tons before falling slightly in 2019.[104] Aluminium is produced in greater quantities than all other non-ferrous metals combined.[145] Its real price (in 1998 United States dollars) in 2019 was $1,400 per metric ton ($2,190 per ton in contemporary dollars).[104]

See also edit

Notes edit

  1. ^ Deville had established that heating a mixture of sodium chloride, clay, and charcoal yields numerous aluminium 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. According to Duboin, this hints at the possibility that boric acid, potash, and clay under the reducing influence of coal may have produced aluminium in Rome.[4]
  2. ^ A similar story is attributed to Pliny, which mentions instead a light bright metal extracted from clay—a description that matches that of aluminium. Both Petronius and Pliny, however, mentioned glass[6] (and Dio did not mention the material at all).[7] A possible source of the error is French general Louis Gaspard Gustave Adolphe Yvelin de Béville, who was openly cited by Deville in 1864. De Béville searched in the Roman sources for possible ancient mentions of the new metal and discovered among others the story in Satiricon. De Béville might have misinterpreted Petronius's expression aurum pro luto habere (literally "to have gold as dirt"), assuming that lutum stands for "clay" (a possible translation), whereas the word throughout the book actually means something valueless in general. German chemist Gerhard Eggert concluded that this story was erroneous.[6] After evaluating other possible explanations, he announced the original story was also probably made up; however, he did not evaluate Duboin's suggestion.[6]
  3. ^ Alumina was plentiful and could be reduced by coke in the presence of copper, giving aluminium–copper alloys. Existing works by Chinese alchemists show that alloys with a small aluminium content could be produced in China. The Chinese did not have the technology to produce pure aluminium and the temperatures needed (around 2000 °C) were unachievable. A number of high-aluminium artifacts were found in China supposedly relating to the times of the first Jin dynasty, but it was later shown the technology needed to make them was not available at the time and thus the artifacts were not authentic.[8]
  4. ^ The terms "earth of alum" and "alumina" refer to the same substance. German-speaking authors mentioned in this section used "earth of alum" (Alaun-Erde), while French authors used "alumina" (alumine).
  5. ^ Ørsted's description of the isolation of the new element, as recorded by the Royal Danish Academy of Sciences and Letters,[26] does not include a name for the metal, neither the name "aluminium" nor a suggestion of his own; in comparison, Wöhler put the word "aluminium" into the title of his article.[33]
  6. ^ Note the difference between cost and price. Cost is the amount of money (and, sometimes, other resources, such as time) that was spent in making a product whereas price is the amount of money (or, sometimes, other goods or services) the product is sold for. Manufacturer's price equals cost plus manufacturer's profit.
  7. ^ Although very similar and now commonly seen as one, Hall and Héroult processes had some small initial differences. For instance, Héroult used coal anodes while Hall used copper.[79]
  8. ^ The Cowles brothers did not wish to change their production method because they feared that mass production of aluminium would immediately reduce the metal's price. The president of the company considered purchasing Hall's patent (which was still not granted at the time) to ensure that competitors would not make use of it.[86]
  9. ^ Hall was able to prove his originality thanks to his keeping record on experiments. Hall documented the isolation of aluminium in February 1886, and his family members provided evidence for that. In contrast, the earliest date to which Héroult's invention could be traced back was the date of granting of the French patent in April.[80]
  10. ^ Because the principle of internal heating was missing from Hall's patent, the Cowles brothers believed Hall had stolen it from them and sued his company in 1891. This lawsuit was resolved only in 1903; the Pittsburgh Reduction Company had to pay a large indemnity.[88][89]
  11. ^ This campaign was not effective as a means to achieve the declared goal, collecting of aluminium for production of airplanes: the collected metal was not of high quality,[116] required manual working (such as removal of wooden handles of pans),[117] and aluminium was available as unused kitchenware in stores and as scrap;[116] already existing scrap in particular could be easily converted into the required grade purity of aluminium and could not be sold elsewhere.[118] However, the campaign boosted the morale of the British civilian public who engaged in the wartime effort.[116][119]
  12. ^ Compare annual statistics of aluminium[104] and copper[123] production by USGS.
  13. ^ Note that not all economies in the world were market economies; for example, the Soviet Union had a planned economy.

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  132. ^ Bockris, John (2013). Comprehensive Treatise of Electrochemistry: Electrochemical Processing. Springer Science & Business Media. p. 303. ISBN 9781468437850.
  133. ^ United States Environmental Protection Agency (1973). The Cost of Clean Air. United States Government Printing Office. pp. IE-87.
  134. ^ Nappi 2013, pp. 12–13.
  135. ^ Nappi 2013, pp. 9–10.
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  137. ^ Nappi 2013, p. 3.
  138. ^ Nappi 2013, p. 10.
  139. ^ Nappi 2013, pp. 14–15.
  140. ^ Nappi 2013, p. 17.
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Bibliography edit

  • Chisholm, Hugh, ed. (1911). "Aluminium" . Encyclopædia Britannica. Vol. 01 (11th ed.). Cambridge University Press. pp. 767–773.
  • Drozdov, Andrey (2007). (PDF). RUSAL Library. ISBN 978-5-91523-002-5. Archived from the original (PDF) on 2016-04-16. Retrieved 2019-06-09.
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  • Nappi, Carmine (2013). The global aluminium industry 40 years from 1972 (PDF) (Report). International Aluminium Institute.
  • Richards, Joseph William (1896). Aluminium: Its history, occurrence, properties, metallurgy and applications, including its alloys (3 ed.). Henry Carey Baird & Co.
  • Skrabec, Quentin R. (2017). Aluminum in America: A History. McFarland. ISBN 978-1-4766-2564-5.

history, aluminium, aluminium, aluminum, metal, very, rare, native, form, process, refine, from, ores, complex, most, human, history, unknown, however, compound, alum, been, known, since, century, used, extensively, ancients, dyeing, during, middle, ages, dyei. Aluminium or aluminum metal is very rare in native form and the process to refine it from ores is complex so for most of human history it was unknown However the compound alum has been known since the 5th century BCE and was used extensively by the ancients for dyeing During the Middle Ages its use for dyeing made it a commodity of international commerce Renaissance scientists believed that alum was a salt of a new earth during the Age of Enlightenment it was established that this earth alumina was an oxide of a new metal Discovery of this metal was announced in 1825 by Danish physicist Hans Christian Orsted whose work was extended by German chemist Friedrich Wohler Extrusion billets of aluminium in Yugoslavia 1968 Aluminium was difficult to refine and thus uncommon in actual use Soon after its discovery the price of aluminium exceeded that of gold It was reduced only after the initiation of the first industrial production by French chemist Henri Etienne Sainte Claire Deville in 1856 Aluminium became much more available to the public with the Hall Heroult process developed independently by French engineer Paul Heroult and American engineer Charles Martin Hall in 1886 and the Bayer process developed by Austrian chemist Carl Joseph Bayer in 1889 These processes have been used for aluminium production up to the present The introduction of these methods for the mass production of aluminium led to extensive use of the light corrosion resistant metal in industry and everyday life Aluminium began to be used in engineering and construction In World Wars I and II aluminium was a crucial strategic resource for aviation World production of the metal grew from 6 800 metric tons in 1900 to 2 810 000 metric tons in 1954 when aluminium became the most produced non ferrous metal surpassing copper In the second half of the 20th century aluminium gained usage in transportation and packaging Aluminium production became a source of concern due to its effect on the environment and aluminium recycling gained ground The metal became an exchange commodity in the 1970s Production began to shift from developed countries to developing ones by 2010 China had accumulated an especially large share in both production and consumption of aluminium World production continued to rise reaching 58 500 000 metric tons in 2015 Aluminium production exceeds those of all other non ferrous metals combined Contents 1 Early history 2 Establishing the nature of alum 3 Isolation of metal 4 Early industrial production 5 Electrolytic production and commercialization 6 Mass usage 7 Aluminium Age 8 See also 9 Notes 10 References 11 BibliographyEarly history editToday 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 Giovanni da Castro to his godfather Pope Pius II in 1461 after discovering a rich source of alum at Tolfa near Rome 1 nbsp Crystals of alum the naturally occurring form of which was known back to the ancients The history of aluminium was shaped by the usage of its compound alum The first written record of alum was in the 5th century BCE by Greek historian Herodotus 2 The ancients used it as a dyeing mordant in medicine in chemical milling and as a fire resistant coating for wood to protect fortresses from enemy arson 3 Aluminium metal was unknown Roman writer Petronius mentioned in his novel Satyricon that an unusual glass had been presented to the emperor after it was thrown on the pavement it did not break but only deformed It was returned to its former shape using a hammer After learning from the inventor that nobody else knew how to produce this material the emperor had the inventor executed so that it did not diminish the price of gold 4 Variations of this story were mentioned briefly in Natural History by Roman historian Pliny the Elder who noted the story had been current through frequent repetition rather than authentic 5 and Roman History by Roman historian Cassius Dio 4 Some sources suggest this glass could be aluminium a b It is possible aluminium containing alloys were produced in China during the reign of the first Jin dynasty 266 420 c After the Crusades alum was a commodity of international commerce 9 it was indispensable in the European fabric industry 10 Small alum mines were worked in Catholic Europe but most alum came from the Middle East 11 Alum continued to be traded through the Mediterranean Sea until the mid 15th century when the Ottomans greatly increased export taxes In a few years alum was discovered in great abundance in Italy Pope Pius II forbade all imports from the east using the profits from the alum trade to start a war with the Ottomans 1 This newly found alum long played an important role in European pharmacy but the high prices set by the papal government eventually made other states start their own production large scale alum mining came to other regions of Europe in the 16th century 12 Establishing the nature of alum editI think it not too venturesome to predict that a day will come when the metallic nature of the base of alum will be incontestably proven French chemist Theodore Baron d Henouville in 1760 at the Paris Academy of Sciences 13 nbsp Antoine Lavoisier established that alumina was an oxide of an unknown metal At the start of the Renaissance the nature of alum remained unknown Around 1530 Swiss physician Paracelsus recognized alum as separate from vitriole sulfates and suggested it was a salt of an earth 14 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 15 for the undiscovered earth that formed alum he proposed the name alumina 14 German chemist Georg Ernst Stahl stated that the unknown base of alum was akin to lime or chalk in 1702 this mistaken view was shared by many scientists for half a century 16 In 1722 German chemist Friedrich Hoffmann suggested that the base of alum was a distinct earth 16 In 1728 French chemist Etienne Geoffroy Saint Hilaire claimed alum was formed by an unknown earth and sulfuric acid 16 he mistakenly believed burning that earth yielded silica 17 Geoffroy s mistake was corrected only in 1785 by German chemist and pharmacist Johann Christian Wiegleb He determined that earth of alum could not be synthesized from silica and alkalis contrary to contemporary belief 18 French chemist Jean Gello proved the earth in clay and the earth resulting from the reaction of an alkali on alum were identical in 1739 19 German chemist Johann Heinrich Pott showed the precipitate obtained from pouring an alkali into a solution of alum was different from lime and chalk in 1746 20 German chemist Andreas Sigismund Marggraf synthesized the earth of alum by boiling clay in sulfuric acid and adding potash in 1754 16 He realized that adding soda potash or an alkali to a solution of the new earth in sulfuric acid yielded alum 21 He described the earth as alkaline as he had discovered it dissolved in acids when dried Marggraf also described salts of this earth chloride nitrate and acetate 19 In 1758 French chemist Pierre Macquer wrote that alumina d resembled a metallic earth 13 In 1760 French chemist Theodore Baron d Henouville expressed his confidence that alumina was a metallic earth 13 In 1767 Swedish chemist Torbern Bergman synthesized alum by boiling alunite in sulfuric acid and adding potash to the solution He also synthesized alum as a reaction product between sulfates of potassium and earth of alum demonstrating that alum was a double salt 14 Swedish German pharmaceutical chemist Carl Wilhelm Scheele demonstrated that both alum and silica originated from clay and alum did not contain silicon in 1776 22 Writing in 1782 French chemist Antoine Lavoisier considered alumina an oxide of a metal with an affinity for oxygen so strong that no known reducing agents could overcome it 23 Swedish chemist Jons Jacob Berzelius suggested 24 the formula AlO3 for alumina in 1815 25 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 25 Isolation of metal editThis amalgam quickly separates in air and by distillation in an inert atmosphere gives a lump of metal which in color and luster somewhat resembles tin Danish physicist Hans Christian Orsted in 1825 describing isolation of aluminium at the Royal Danish Academy of Sciences and Letters 26 nbsp Hans Christian Orsted discoverer of aluminium metal In 1760 Baron de Henouville unsuccessfully attempted to reduce alumina to its metal He claimed he had tried every method of reduction known at the time though his methods were unpublished It is probable he mixed alum with carbon or some organic substance with salt or soda for flux and heated it in a charcoal fire 13 Austrian chemists Anton Leopold Ruprecht and Matteo Tondi repeated Baron s experiments in 1790 significantly increasing the temperatures They found small metallic particles they believed were the sought after metal but later experiments by other chemists showed these were iron phosphide from impurities in the 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 27 Lavoisier in 1794 28 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 28 American chemist Robert Hare melted alumina with an oxyhydrogen blowpipe in 1802 also obtaining the enamel but still found no metal 27 In 1807 British chemist Humphry Davy successfully electrolyzed alumina with alkaline batteries but the resulting alloy contained potassium and sodium and Davy had no means to separate the desired metal from these He then heated alumina with potassium forming potassium oxide but was unable to produce the sought after metal 27 In 1808 Davy set up a different experiment on electrolysis of alumina establishing that alumina decomposed in the electric arc but formed metal alloyed with iron he was unable to separate the two 29 Finally he tried yet another electrolysis experiment seeking to collect the metal on iron but was again unable to separate the coveted metal from it 27 Davy suggested the metal be named alumium in 1808 30 and aluminum in 1812 thus producing the modern name 29 Other scientists used the spelling aluminium the former spelling regained usage in the United States in the following decades 31 American chemist Benjamin Silliman repeated Hare s experiment in 1813 and obtained small granules of the sought after metal which almost immediately burned 27 In 1824 Danish physicist Hans Christian Orsted attempted to produce the metal He reacted anhydrous aluminium chloride with potassium amalgam yielding a lump of metal that looked similar to tin 26 32 33 He presented his results and demonstrated a sample of the new metal in 1825 In 1826 he wrote aluminium has a metallic luster and somewhat grayish color and breaks down water very slowly this suggests he had obtained an aluminium potassium alloy rather than pure aluminium 34 Orsted placed little importance on his discovery 35 He did not notify either Davy or Berzelius both of whom he knew and published his work in a Danish magazine unknown to the European public 35 As a result he is often not credited as the discoverer of the element 36 some earlier sources claimed Orsted had not isolated aluminium 37 nbsp Friedrich Wohler pioneer researcher of the properties of aluminium Berzelius tried isolating the metal in 1825 by carefully washing the potassium analog of the base salt in cryolite in a crucible Prior to the experiment he had correctly identified the formula of this salt 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 38 German chemist Friedrich Wohler visited Orsted in 1827 and received explicit permission to continue the aluminium research which Orsted did not have time for 35 Wohler repeated Orsted s experiments but did not identify any aluminium Wohler later wrote to Berzelius what Oersted assumed to be a lump of aluminium was certainly nothing but aluminium containing potassium 39 He conducted a similar experiment mixing anhydrous aluminium chloride with potassium and produced a powder of aluminium 33 After hearing about this Orsted suggested that his own aluminium might have contained potassium 35 Wohler continued his research and in 1845 was able to produce small pieces of the metal and described some of its physical properties Wohler s description of the properties indicates that he had obtained impure aluminium 40 Other scientists also failed to reproduce Orsted s experiment 40 and Wohler was credited as the discoverer for many years 41 While Orsted was not concerned with the priority of the discovery 35 e some Danes tried to demonstrate he had obtained aluminium 35 In 1921 the reason for the inconsistency between Orsted s and Wohler s experiments was discovered by Danish chemist Johan Fogh who demonstrated that Orsted s experiment was successful thanks to use of a large amount of excess aluminium chloride and an amalgam with low potassium content 40 In 1936 scientists from American aluminium producing company Alcoa successfully recreated that experiment 42 However many later sources still credit Wohler with the discovery of aluminium as well as its successful isolation in a relatively pure form 43 Early industrial production editMy first thought was I had laid my hands on this intermediate metal which would find its place in man s uses and needs when we would find the way of taking it out of the chemists laboratory and putting it in the industry Preface of Aluminium its properties manufacture and applications book written by French chemist Henri Etienne Sainte Claire Deville in 1859 44 nbsp Henri Etienne Sainte Claire Deville was the first to establish a method to manufacture aluminium Since Wohler s method could not yield large amounts of aluminium the metal remained uncommon its cost f had exceeded that of gold before a new method was devised In 1852 aluminium was sold at US 34 per ounce 45 In comparison the price of gold at the time was 19 per ounce 46 French chemist Henri Etienne Sainte Claire Deville announced an industrial method of aluminium production in 1854 at the Paris Academy of Sciences 47 Aluminium chloride could be reduced by sodium a metal more convenient and less expensive than potassium used by Wohler 48 Deville was able to produce an ingot of the metal 49 Napoleon III of France promised Deville an unlimited subsidy for aluminium research in total Deville used 36 000 French francs 20 times the annual income of an ordinary family 50 Napoleon s interest in aluminium lay in its potential military use he wished weapons helmets armor and other equipment for the French army could be made of the new light shiny metal 50 While the metal was still not displayed to the public Napoleon is reputed to have held a banquet where the most honored guests were given aluminium utensils while others made do with gold 51 Twelve small ingots of aluminium were later exhibited for the first time to the public at the Exposition Universelle of 1855 50 The metal was presented as the silver from clay aluminium is very similar to silver visually and this name was soon widely used 50 It attracted widespread attention it was suggested aluminium be used in arts music medicine cooking and tableware 52 The metal was noticed by the avant garde writers of the time Charles Dickens Nikolay Chernyshevsky and Jules Verne who envisioned its use in the future 53 However not all attention was favorable Newspapers wrote The Parisian expo put an end to the fairy tale of the silver from clay saying that much of what had been said about the metal was exaggerated if not untrue and that the amount of the presented metal about a kilogram contrasted with what had been expected and was not a lot for a discovery that was said to turn the world upside down 50 Overall the fair led to the eventual commercialization of the metal 53 That year aluminium was put to the market at a price of 300 F per kilogram 54 At the next fair in Paris in 1867 visitors were presented with aluminium wire and foil as well a new alloy aluminium bronze notable for its low cost of production high resistance to corrosion and desirable mechanical properties 55 nbsp 20 French francs aluminium coin from 1857 featuring a portrait of Napoleon III of France patron of research of aluminium production Manufacturers did not wish to divert resources from producing well known and marketable metals such as iron and bronze to experiment with a new one moreover produced aluminium was still not of great purity and differed in properties by sample This led to an initial general reluctance to produce the new metal 50 Deville and partners established the world s first industrial production of aluminium at a smelter in Rouen in 1856 47 Deville s smelter moved that year to La Glaciere and then Nanterre and in 1857 to Salindres For the factory in Nanterre an output of 2 kilograms of aluminium per day was recorded 56 with a purity of 98 57 Originally production started with synthesis of pure alumina which was obtained from calcination of ammonium alum In 1858 Deville was introduced to bauxite and soon developed into what became known as the Deville process employing the mineral as a source for alumina production 58 In 1860 Deville sold his aluminium interests to Henri Merle a founder of Compagnie d Alais et de la Camargue this company dominated the aluminium market in France decades later 59 nbsp The 2 85 kilogram 6 3 lb capstone of the Washington Monument Washington D C was made from aluminium in 1884 At the time it was the largest piece of aluminium ever cast 60 Some chemists including Deville sought to use cryolite as the source ore but with little success 61 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 the closure of the plant in three years 57 British ironmaster Isaac Lowthian Bell produced aluminium from 1860 to 1874 During the opening of his factory he waved to the crowd with a unique and costly aluminium top hat 62 No statistics about this production can be recovered but it cannot be very high 63 Deville s output grew to 1 metric ton per year in 1860 1 7 metric tons in 1867 and 1 8 metric tons in 1872 63 At the time demand for aluminium was low for example sales of Deville s aluminium by his British agents equaled 15 kilograms in 1872 57 Aluminium at the time was often compared with silver like silver it was found to be suitable for making jewelry and objets d art 55 Price for aluminium steadily declined to 240 F in 1859 200 F in 1862 120 F in 1867 64 Other production sites began to appear in the 1880s British engineer James Fern Webster launched the industrial production of aluminium by reduction with sodium in 1882 his aluminium was much purer than Deville s it contained 0 8 impurities whereas Deville s typically contained 2 65 World production of aluminium in 1884 equaled 3 6 metric tons 66 In 1884 American architect William Frishmuth combined production of sodium alumina and aluminium into a single technological process this contrasted with the previous need to collect sodium which combusts in water and sometimes air 67 his aluminium production cost was about 16 per pound compare to silver s cost of 19 per pound or the French price an equivalent of 12 per pound 68 In 1885 Aluminium und Magnesiumfabrik started production in Hemelingen 69 Its production figures strongly exceeded those of the factory in Salindres but the factory stopped production in 1888 70 In 1886 American engineer Hamilton Castner devised a method of cheaper production of sodium which decreased the cost of aluminium production to 8 per pound but he did not have enough capital to construct a large factory like Deville s 71 In 1887 he constructed a factory in Oldbury Webster constructed a plant nearby and bought Castner s sodium to use it in his own production of aluminium 65 In 1889 German metallurgist Curt Netto launched a method of reduction of cryolite with sodium that produced aluminium containing 0 5 1 0 of impurities 72 Electrolytic production and commercialization editI m going for that metal Purportedly American student Charles Martin Hall in 1880 after hearing from his chemistry professor that an industrial production of aluminium would be a great good for humanity and a source of wealth for the discoverer 66 nbsp Cover of the patent granted to Charles Martin Hall for his process of reducing aluminium by electrolysis Hall applied for the patent two months after Heroult as a result it took him almost three years to prove the originality of his method and the patent was only granted in 1889 73 Aluminium was first produced independently using electrolysis in 1854 by the German chemist Robert Wilhelm Bunsen and Deville Their methods did not become the basis for industrial production of aluminium because electrical supplies were inefficient at the time This changed only with Belgian engineer Zenobe Theophile Gramme s invention of the dynamo in 1870 which made creation of large amounts of electricity possible The invention of the three phase current by Russian engineer Mikhail Dolivo Dobrovolsky in 1889 made transmission of this electricity over long distances achievable 74 Soon after his discovery Bunsen moved on to other areas of interest while Deville s work was noticed by Napoleon III this was the reason Deville s Napoleon funded research on aluminium production had been started Deville quickly realized electrolytic production was impractical at the time and moved on to chemical methods presenting results later that year 66 75 Electrolytic mass production remained difficult because electrolytic baths could not withstand prolonged contact with molten salts succumbing to corrosion The first attempt to overcome this for aluminium production was made by American engineer Charles Bradley in 1883 Bradley heated aluminium salts internally the highest temperature was inside the bath and the lowest was on its walls where salts would solidify and protect the bath Bradley then sold his patent claim to brothers Alfred and Eugene Cowles who used it at a smelter in Lockport and later in Stoke upon Trent but the method was modified to yield alloys rather than pure aluminium 76 Bradley applied for a patent in 1883 due to his broad wordings it was rejected as composed of prior art After a necessary two year break he re applied This process lasted for six years as the patent office questioned whether Bradley s ideas were original 77 When Bradley was granted a patent electrolytic aluminium production had already been in place for several years 78 The first large scale production method was independently developed by French engineer Paul Heroult and American engineer Charles Martin Hall in 1886 it is now known as the Hall Heroult process Electrolysis of pure alumina is impractical given its very high melting point both Heroult and Hall realized it could be greatly lowered by the presence of molten cryolite g Heroult was granted a patent in France in April 80 and subsequently in several other European countries 81 he also applied for a U S patent in May 80 After securing a patent Heroult could not find interest in his invention When asking professionals for advice he was told there was no demand for aluminium but some for aluminium bronze The factory in Salindres did not wish to improve its process In 1888 Heroult and his companions founded Aluminium Industrie Aktiengesellschaft and started industrial production of aluminium bronze in Neuhausen am Rheinfall Then Societe electrometallurgique francaise was founded in Paris They convinced Heroult to return to France purchased his patents and appointed him as the director of a smelter in Isere which produced aluminium bronze on a large scale at first and pure aluminium in a few months 82 83 nbsp Statue of Anteros Greek god of requited love on Piccadilly Circus in London This statue was erected in 1893 and is considered the first major work in aluminium 84 At the same time Hall produced aluminium by the same process in his home at Oberlin 85 He applied for a patent in July and the patent office notified Hall of an interference with Heroult s application The Cowles brothers offered legal support By then Hall had failed to develop a commercial process for his first investors and he turned to experimenting at Cowles smelter in Lockport He experimented for a year without much success but gained the attention of investors h Hall co founded the Pittsburgh Reduction Company in 1888 and initiated production of aluminium 87 Hall s patent was granted in 1889 73 i In 1889 Hall s production began to use the principle of internal heating j By September 1889 Hall s production grew to 385 pounds 175 kilograms at a cost of 0 65 per pound 90 By 1890 Hall s company still lacked capital and did not pay dividends Hall had to sell some of his shares to attract investments 91 During that year a new factory in Patricroft was constructed 92 The smelter in Lockport was unable to withstand the competition and shut down by 1892 93 The Hall Heroult process converts alumina into the metal Austrian chemist Carl Josef Bayer discovered a way of purifying bauxite to yield alumina in 1888 at a textile factory in Saint Petersburg and was issued a patent later that year 94 this is 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 of pure aluminium hydroxide which decomposed to alumina on heating In 1892 while working at a chemical plant in Yelabuga he discovered the aluminium contents of bauxite dissolved in the alkaline leftover from isolation of alumina solids this was crucial for the industrial employment of this method He was issued a patent later that year 94 95 nbsp World production of aluminium from 1885 to 1899 The total amount of unalloyed aluminium produced using Deville s chemical method from 1856 to 1889 equaled 200 metric tons 47 Production in 1890 alone was 175 metric tons It grew to 715 metric tons in 1893 and to 4 034 metric tons in 1898 70 The price fell to 2 per pound in 1889 and to 0 5 per pound in 1894 96 By the end of 1889 a consistently high purity of aluminium produced via electrolysis had been achieved 97 In 1890 Webster s factory went obsolete after an electrolysis factory was opened in England 67 Netto s main advantage the high purity of the resulting aluminium was outmatched by electrolytic aluminium and his company closed the following year 97 Compagnie d Alais et de la Camargue also decided to switch to electrolytic production and their first plant using this method was opened in 1895 73 Modern production of the aluminium metal is based on the Bayer and Hall Heroult processes It was further improved in 1920 by a team led by Swedish chemist Carl Wilhelm Soderberg Previously anode electrodes had been made from pre baked coal blocks which quickly corrupted and required replacement the team introduced continuous electrodes made from a coke and tar paste in a reduction chamber This advance greatly increased the world output of aluminium 98 Mass usage editGive us aluminum in the right quantity and we will be able to fight for another four years Soviet leader Joseph Stalin to Harry Hopkins personal representative of the U S President Franklin D Roosevelt in August 1941 99 nbsp Nominal in contemporary United States dollars in blue and real in 1998 United States dollars in red prices of aluminium since 1900 Prices for aluminium declined and by the early 1890s the metal had become widely used in jewelry eyeglass frames optical instruments and many everyday items Aluminium cookware began to be produced in the late 19th century and gradually supplanted copper and cast iron cookware 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 alloys 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 100 Aviation used a new aluminium alloy duralumin invented in 1903 101 Aluminium recycling began in the early 1900s and has been used extensively since 102 as aluminium is not impaired by recycling and thus can be recycled repeatedly 103 At this point only the metal that had not been used by end consumers was recycled 104 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 105 106 Overall production of aluminium peaked during the war world production of aluminium in 1900 was 6 800 metric tons in 1916 annual production exceeded 100 000 metric tons 104 The war created a greater demand for aluminium which the growing primary production was unable to fully satisfy and recycling grew intensely as well 102 The peak in production was followed by a decline then a swift growth 104 nbsp The first aviation flight was performed by the Wright brothers in 1903 A strong light material was needed for the engine of the Wright Flyer light aluminium alloyed with copper for strength was used 107 During the first half of the 20th century the real price for aluminium fell continuously from 14 000 per metric ton in 1900 to 2 340 in 1948 in 1998 United States dollars There were some exceptions such as the sharp price rise during World War I 104 Aluminium was plentiful and in 1919 Germany began to replace its silver coins with aluminium ones more and more denominations were switched to aluminium coins as hyperinflation progressed in the country 108 By the mid 20th century aluminium had become a part of everyday lives becoming an essential component of housewares 109 Aluminium freight cars first appeared in 1931 Their lower mass allowed them to carry more cargo 106 During the 1930s aluminium emerged as a civil engineering material used in both basic construction and building interiors 110 Its use in military engineering for both airplanes and tank engines advanced 111 Aluminium obtained from recycling was considered inferior to primary aluminium because of poorer chemistry control as well as poor removal of dross and slags Recycling grew overall but depended largely on the output of primary production for instance as electric energy prices declined in the United States in the late 1930s more primary aluminium could be produced using the energy expensive Hall Heroult process This rendered recycling less necessary and thus aluminium recycling rates went down 102 By 1940 mass recycling of post consumer aluminium had begun 104 nbsp During World War II the British collected aluminium utensils from households The aluminium was made into aircraft 112 During World War II production peaked again exceeding 1 000 000 metric tons for the first time in 1941 104 Aluminium was used heavily in aircraft production and was a strategic material of extreme importance so much so that when Alcoa successor of Hall s Pittsburgh Reduction Company and the aluminium production monopolist in the United States at the time did not expand its production the United States Secretary of the Interior proclaimed in 1941 If America loses the war it can thank the Aluminum Corporation of America 113 In 1939 Germany was the world s leading producer of aluminium the Germans thus saw aluminium as their edge in the war Aluminium coins continued to be used but while they symbolized a decline on their introduction by 1939 they had come to represent power 114 In 1941 they began to be withdrawn from circulation to save the metal for military needs 115 After the United Kingdom was attacked in 1940 it started an ambitious program of aluminium recycling the newly appointed Minister of Aircraft Production appealed to the public to donate any household aluminium for airplane building 112 k The Soviet Union received 328 100 metric tons of aluminium from its co combatants from 1941 to 1945 120 this aluminium was used in aircraft and tank engines 121 Without these shipments the output of the Soviet aircraft industry would have fallen by over a half 122 After the wartime peak world production fell for three late war and post war years but then regained its rapid growth 104 In 1954 the world output equaled 2 810 000 metric tons 104 this production surpassed that of copper l historically second in production only to iron 124 125 making it the most produced non ferrous metal Aluminium Age editNothing stops time One epoch follows another and sometimes we don t even notice it The Stone Age The Bronze Age The Iron Age However one may assert that it is now that we stand on the threshold of the Aluminium Age Russian aluminium producing company RUSAL in their book Aluminium The Thirteenth Element in 2007 126 nbsp Aluminium can Earth s first artificial satellite launched in 1957 consisted of two joined aluminium hemispheres All subsequent spacecraft have used aluminium to some extent 98 The aluminium can was first manufactured in 1956 and employed as a container for drinks in 1958 127 In the 1960s aluminium was employed for the production of wires and cables 128 Since the 1970s high speed trains have commonly used aluminium for its high strength to weight ratio For the same reason the aluminium content of cars is growing 106 By 1955 the world market m had been dominated by the Six Majors Alcoa Alcan originated as a part of Alcoa Reynolds Kaiser Pechiney merger of Compagnie d Alais et de la Camargue that bought Deville s smelter and Societe electrometallurgique francaise that hired Heroult and Alusuisse successor of Heroult s Aluminium Industrie Aktien Gesellschaft their combined share of the market equaled 86 129 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 130 The real price declined until the early 1970s 131 in 1973 the real price equaled 2 130 per metric ton in 1998 United States dollars 104 The main drivers of the drop in price was the decline of extraction and processing costs technological progress and the increase in aluminium production 131 which first exceeded 10 000 000 metric tons in 1971 104 nbsp Formwork at the Volokolamskaya metro station of the Moscow Metro In the late 1960s governments became aware of waste from the industrial production they enforced a series of regulations favoring recycling and waste disposal Soderberg anodes which save capital and labor to bake the anodes but are more harmful to the environment because of a greater difficulty in collecting and disposing of the baking fumes 132 fell into disfavor and production began to shift back to the pre baked anodes 133 The aluminium industry began promoting the recycling of aluminium cans in an attempt to avoid restrictions on them 102 This sparked recycling of aluminium previously used by end consumers for example in the United States levels of recycling of such aluminium increased 3 5 times from 1970 to 1980 and 7 5 times to 1990 104 Production costs for primary aluminium grew in the 1970s and 1980s and this also contributed to the rise of aluminium recycling 102 Closer composition control and improved refining technology diminished the quality difference between primary and secondary aluminium 102 In the 1970s the increased demand for aluminium made it an exchange commodity it entered the London Metal Exchange the world s oldest industrial metal exchange in 1978 98 Since then aluminium has been traded for United States dollars and its price fluctuated along with the currency s exchange rate 134 The need to exploit lower grade poorer quality deposits and fast increasing input costs of energy but also bauxite as well as changes in exchange rates and greenhouse gas regulation increased the net cost of aluminium 131 the real price grew in the 1970s 135 nbsp World production of aluminium since 1900 The increase of the real price and changes of tariffs and taxes began the redistribution of world producers shares 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 60 136 but their combined share only slightly exceeded 10 in 2012 137 The production shift began in the 1970s with production moving from the United States Japan and Western Europe to Australia Canada the Middle East Russia and China where it was cheaper due to lower electricity prices and favorable state regulation such as low taxes or subsidies 138 Production costs in the 1980s and 1990s declined because of advances in technology lower energy and alumina prices and high exchange rates of the United States dollar 139 In the 2000s the BRIC countries Brazil Russia India and China combined share grew from 32 6 to 56 5 in primary production and 21 4 to 47 8 in primary consumption 140 China has accumulated an especially large share of world production thanks to an abundance of resources cheap energy and governmental stimuli 141 it also increased its share of consumption from 2 in 1972 to 40 in 2010 142 The only other country with a two digit percentage was the United States with 11 no other country exceeded 5 143 In the United States Western Europe and Japan most aluminium was consumed in transportation engineering construction and packaging 143 In the mid 2000s increasing energy alumina and carbon used in anodes prices caused an increase in production costs This was amplified by a shift in currency exchange rates not only a weakening of the United States dollar but also a strengthening of the Chinese yuan The latter became important as most Chinese aluminium was relatively cheap 144 World output continued growing in 2018 it was a record 63 600 000 metric tons before falling slightly in 2019 104 Aluminium is produced in greater quantities than all other non ferrous metals combined 145 Its real price in 1998 United States dollars in 2019 was 1 400 per metric ton 2 190 per ton in contemporary dollars 104 See also edit nbsp Chemistry portalList of countries by primary aluminium productionNotes edit Deville had established that heating a mixture of sodium chloride clay and charcoal yields numerous aluminium globules This was published in the Proceedings of the Academy of Sciences but eventually forgotten 4 French chemist Andre 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 According to Duboin this hints at the possibility that boric acid potash and clay under the reducing influence of coal may have produced aluminium in Rome 4 A similar story is attributed to Pliny which mentions instead a light bright metal extracted from clay a description that matches that of aluminium Both Petronius and Pliny however mentioned glass 6 and Dio did not mention the material at all 7 A possible source of the error is French general Louis Gaspard Gustave Adolphe Yvelin de Beville who was openly cited by Deville in 1864 De Beville searched in the Roman sources for possible ancient mentions of the new metal and discovered among others the story in Satiricon De Beville might have misinterpreted Petronius s expression aurum pro luto habere literally to have gold as dirt assuming that lutum stands for clay a possible translation whereas the word throughout the book actually means something valueless in general German chemist Gerhard Eggert concluded that this story was erroneous 6 After evaluating other possible explanations he announced the original story was also probably made up however he did not evaluate Duboin s suggestion 6 Alumina was plentiful and could be reduced by coke in the presence of copper giving aluminium copper alloys Existing works by Chinese alchemists show that alloys with a small aluminium content could be produced in China The Chinese did not have the technology to produce pure aluminium and the temperatures needed around 2000 C were unachievable A number of high aluminium artifacts were found in China supposedly relating to the times of the first Jin dynasty but it was later shown the technology needed to make them was not available at the time and thus the artifacts were not authentic 8 The terms earth of alum and alumina refer to the same substance German speaking authors mentioned in this section used earth of alum Alaun Erde while French authors used alumina alumine Orsted s description of the isolation of the new element as recorded by the Royal Danish Academy of Sciences and Letters 26 does not include a name for the metal neither the name aluminium nor a suggestion of his own in comparison Wohler put the word aluminium into the title of his article 33 Note the difference between cost and price Cost is the amount of money and sometimes other resources such as time that was spent in making a product whereas price is the amount of money or sometimes other goods or services the product is sold for Manufacturer s price equals cost plus manufacturer s profit Although very similar and now commonly seen as one Hall and Heroult processes had some small initial differences For instance Heroult used coal anodes while Hall used copper 79 The Cowles brothers did not wish to change their production method because they feared that mass production of aluminium would immediately reduce the metal s price The president of the company considered purchasing Hall s patent which was still not granted at the time to ensure that competitors would not make use of it 86 Hall was able to prove his originality thanks to his keeping record on experiments Hall documented the isolation of aluminium in February 1886 and his family members provided evidence for that In contrast the earliest date to which Heroult s invention could be traced back was the date of granting of the French patent in April 80 Because the principle of internal heating was missing from Hall s patent the Cowles brothers believed Hall had stolen it from them and sued his company in 1891 This lawsuit was resolved only in 1903 the Pittsburgh Reduction Company had to pay a large indemnity 88 89 This campaign was not effective as a means to achieve the declared goal collecting of aluminium for production of airplanes the collected metal was not of high quality 116 required manual working such as removal of wooden handles of pans 117 and aluminium was available as unused kitchenware in stores and as scrap 116 already existing scrap in particular could be easily converted into the required grade purity of aluminium and could not be sold elsewhere 118 However the campaign boosted the morale of the British civilian public who engaged in the wartime effort 116 119 Compare annual statistics of aluminium 104 and copper 123 production by USGS Note that not all economies in the world were market economies for example the Soviet Union had a planned economy References edit a b Setton Kenneth Meyer 1976 Pius II the Crusade and the Venetian war against the Turks The Papacy and the Levant 1204 1571 The fifteenth century American Philosophical Society pp 231 270 ISBN 978 0 87169 127 9 Drozdov 2007 p 12 Drozdov 2007 pp 12 14 a b c d Duboin A 1902 Les Romains ont ils connu l aluminium Did the Romans know about aluminum La Revue Scientifique in French 18 24 751 753 Archived from the original on 2018 11 16 Retrieved 2018 11 16 Pliny sNatural History Translated by Rackham H Jones W H S Eichholz D E Harvard University Press William Heinemann 1949 1954 Archived from the original on January 1 2017 a b c Eggert Gerhard 1995 Ancient aluminum Flexible glass Looking for the real heart of a legend PDF Skeptical Inquirer 19 3 37 40 Foster Herbert Baldwin ed 1954 Dio s Roman History PDF Translated by Cary Earnest 7 ed William Heinemann Limited Harvard University Press p 173 Archived PDF from the original on 2016 06 20 Retrieved 2018 12 04 Butler Anthony R Glidewell Christopher Pritchard Sharee E 1986 Aluminium Objects from a Jin Dynasty Tomb Can They Be Authentic Interdisciplinary Science Reviews 11 1 88 94 Bibcode 1986ISRv 11 88B doi 10 1179 isr 1986 11 1 88 Drozdov 2007 p 16 Clapham John Harold Power Eileen Edna 1941 The Cambridge Economic History of Europe From the Decline of the Roman Empire CUP Archive p 207 ISBN 978 0 521 08710 0 Balston John Noel 1998 Appendix I In Defence of Alum The Whatmans and Wove Paper Its Invention and Development in the West Research Into the Origins of Wove Paper and of Genuine Loom Woven Wirecloth Vol 3 John Balston p 198 ISBN 978 0 9519505 3 1 Drozdov 2007 pp 17 18 a b c d Richards 1896 p 3 a b c Drozdov 2007 p 25 Weeks Mary Elvira 1968 Discovery of the elements Vol 1 7 ed Journal of Chemical Education p 187 ISBN 9780608300177 a b c d Richards 1896 p 2 Drozdov 2007 p 26 Wiegleb Johann Christian 1790 Geschichte des wachsthums und der erfindungen in der chemie in der neuern zeit History of growth and inventions in chemistry in the modern time Nicolai Christoph Friedrich p 357 a b Drozdov 2007 p 27 Pott Johann Heinrich 1746 Chymische Untersuchungen welche furnehmlich von der Lithogeognosia oder Erkantniss und Bearbeitung der gemeinen einfacheren Steine und Erden ingleichen von Feuer und Licht handeln Chemical investigations which primarily concern lithogeognosia or knowledge and processing of common simple rocks and earths as well as fire and light in German Vol 1 Voss 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15 Nappi 2013 p 17 Nappi 2013 p 20 Nappi 2013 p 22 a b Nappi 2013 p 23 Nappi 2013 p 15 United Nations Environment Programme 2006 Report card Aluminium Class of 2006 Industry Report Cards on Environment and Social Responsibility UNEP Earthprint p 69 ISBN 978 92 807 2713 5 Bibliography editChisholm Hugh ed 1911 Aluminium Encyclopaedia Britannica Vol 01 11th ed Cambridge University Press pp 767 773 Drozdov Andrey 2007 Aluminium The Thirteenth Element PDF RUSAL Library ISBN 978 5 91523 002 5 Archived from the original PDF on 2016 04 16 Retrieved 2019 06 09 McNeil Ian 2002 An Encyclopedia of the History of Technology Routledge ISBN 978 1 134 98165 6 Nappi Carmine 2013 The global aluminium industry 40 years from 1972 PDF Report International Aluminium Institute Richards Joseph William 1896 Aluminium Its history occurrence properties metallurgy and applications including its alloys 3 ed Henry Carey Baird amp Co Skrabec Quentin R 2017 Aluminum in America A History McFarland ISBN 978 1 4766 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