Aluminium

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Aluminium or aluminum (Symbol Al) (see the spelling section below) is a silvery and ductile member of the poor metal group of chemical elements. Its atomic number is 13. Aluminium is found primarily as the ore bauxite and is remarkable for its resistance to oxidation (due to the phenomenon of passivation), its strength, and its light weight. Aluminium is used in many industries to make millions of different products and is very important to the world economy. Structural components made from aluminium are vital to the aerospace industry and very important in other areas of transportation and building in which light weight, durability, and strength are needed.

Properties

A piece of aluminium metal about 15 centimetres long.

Aluminium is a soft and lightweight metal with a dull silvery appearance, due to a thin layer of oxidation that forms quickly when it is exposed to air. Aluminium is about one-third as dense as steel or copper; is malleable, ductile, and easily machined and cast; and has excellent corrosion resistance and durability due to the protective oxide layer. It is also nonmagnetic and nonsparking and is the second most malleable metal (after gold) and the sixth most ductile.

Applications

Whether measured in terms of quantity or value, the use of aluminium exceeds that of any other metal except iron, and it is important in virtually all segments of the world economy.

Pure aluminium has a low tensile strength, but readily forms alloys with many elements such as copper, zinc, magnesium, manganese and silicon. When combined with thermo-mechanical processing these aluminium alloys display a marked improvement in mechanical properties. Aluminium alloys form vital components of aircraft and rockets as a result of their high strength to weight ratio.

When aluminium is evaporated in a vacuum it forms a coating that reflects both visible light and radiant heat. These coatings form a thin layer of protective aluminium oxide that does not deteriorate as silver coatings do. In particular, nearly all modern mirrors are made using a thin reflective coating of aluminium on the back surface of a sheet of float glass. Telescope mirrors are also coated with a thin layer of aluminium, but are front coated to avoid internal reflections even though this makes the surface more susceptible to damage.

Some of the many uses for aluminium are in:

  • Transportation (automobiles, airplanes, trucks, railroad cars, marine vessels, etc.)
  • Packaging (cans, foil, etc.)
  • Water treatment
  • Construction (windows, doors, siding, building wire, etc.
  • Consumer durable goods (appliances, cooking utensils, etc.)
  • Electrical transmission lines (aluminium conductors are half the weight of copper for equal conductivity and lower in price[1])
  • Machinery.
  • Although non-magnetic itself, aluminium is used in MKM steel and Alnico magnets.
  • Super purity aluminium (SPA, 99.980% to 99.999% Al) is used in electronics and CDs.
  • Powdered aluminium is commonly used for silvering in paint. Aluminium flakes may also be included in undercoat paints, particularly wood primer — on drying, the flakes overlap to produce a water resistant barrier.
  • Anodized aluminium is more stable to further oxidation, and is used in various fields of construction.
  • Most modern computer CPU heat sinks are made of aluminium due to its ease of manufacture and good heat conductivity. Copper heat sinks are smaller although more expensive and harder to manufacture.

Aluminium oxide, alumina, is found naturally as corundum (rubies and sapphires), emery, and is used in glass making. Synthetic ruby and sapphire are used in lasers for the production of coherent light.

Aluminium oxidizes very energetically and as a result has found use in solid rocket fuels, thermite, and other pyrotechnic compositions.

Engineering use

Improper use of aluminium can result in problems, particularly in contrast to iron or steel, which appear "better behaved" to the intuitive designer, mechanic, or technician. The reduction by two thirds of the weight of an aluminium part compared to a similarly sized iron or steel part seems enormously attractive, but it should be noted that it is accompanied by a reduction by two thirds in the stiffness of the part. Therefore, although direct replacement of an iron or steel part with a duplicate made from aluminium may still give acceptable strength to withstand peak loads, the increased flexibility will cause three times more deflection in the part.

Where failure is not an issue but excessive flex is undesirable due to requirements for precision of location or efficiency of transmission of power, simple replacement of steel tubing with similarly sized aluminium tubing will result in a degree of flex which is undesirable; for instance, the increased flex under operating loads caused by replacing steel bicycle frame tubing with aluminium tubing of identical dimensions will cause misalignment of the power-train as well as absorbing the operating force. To increase the rigidity by increasing the thickness of the walls of the tubing increases the weight proportionately, so that the advantages of lighter weight are lost as the rigidity is restored.

Aluminium can best be used by redesigning the part to suit its characteristics; for instance making a bicycle of aluminium tubing which has an oversize diameter rather than thicker walls. In this way, rigidity can be restored or even enhanced without increasing weight. The limit to this process is the increase in susceptibility to what is termed "crippling" failure, where the deviation of the force from any direction other than directly along the axis of the tubing causes folding of the walls of the tubing. For instance, a common aluminium soft drink can should be able to support an enormous weight directly along its axis; in practice, however, the walls of the can buckle, crumple, and/or fold up under even a mild force, due to minute deviations from the precise axial direction, making possible the common pastime of flattening an empty can by slamming it against one's forehead.

The latest models of the Corvette automobile, among others, are a good example of redesigning parts to make best use of aluminium's advantages. The aluminium chassis members and suspension parts of these cars have large overall dimensions for stiffness but are lightened by reducing cross-sectional area and removing unneeded metal; as a result, they are not only equally or more durable and stiff as the usual steel parts, but they possess an airy gracefulness which most people find attractive. Similarly, aluminium bicycle frames can be optimally designed so as to provide rigidity where required, yet have flexibility in terms of absorbing the shock of bumps from the road and not transmitting them to the rider.

The strength and durability of aluminium varies widely, not only as a result of the components of the specific alloy, but also as a result of the particular manufacturing process; for this reason, it has from time to time gained a bad reputation. For instance, a high frequency of failure in many early aluminium bicycle frames in the 1970s resulted in just such a poor reputation; with a moment's reflection, however, the widespread use of aluminium components in the aerospace and automotive high performance industries, where huge stresses are undergone with vanishingly small failure rates, proves that properly built aluminium bicycle components should not be unusually unreliable, and this has subsequently proved to be the case.

Similarly, use of aluminium in automotive applications, particularly in engine parts which must survive in difficult conditions, has benefited from development over time. An Audi engineer commented about the V12 engine, producing over 500 horsepower (370 kW), of an Auto Union race car of the 1930s which was recently restored by the Audi factory, that the aluminium alloy of which the engine was constructed would today be used only for lawn furniture and the like. Even the aluminium cylinder heads and crankcase of the Corvair, built as recently as the 1960s, earned a reputation for failure and stripping of threads in holes, even as large as spark plug holes, which is not seen in current aluminium cylinder heads.

Often, aluminium's sensitivity to heat must also be considered. Even a relatively routine procedure such as welding is complicated by the fact that aluminium will melt long before it gets even dully red hot; therefore, unlike steel or iron, where the experienced welder can know from its hue how close the metal is to the melting point, welding aluminium requires a degree of expertise incorporating an almost intuitive sense of the metal's temperature, or else the part suddenly and without warning melts into a puddle. Aluminium also will accumulate internal stresses and strains under conditions of overheating; while not immediately obvious, the tendency of the metal to "creep" under sustained stresses results in delayed distortions, for instance the commonly observed warping or cracking of aluminium automobile cylinder heads after an engine is overheated, sometimes as long as years later, or the tendency of welded aluminium bicycle frames to gradually twist out of alignment from the stresses accumulated during the welding process. For this reason, many uses of aluminium in the aerospace industry avoid heat altogether by joining parts using adhesives; this was also used for some of the early aluminium bicycle frames in the 1970s, with unfortunate results when the aluminium tubing corroded slightly, loosening the bond of the adhesive and leading to failure of the frame. Stresses from overheating aluminium can be relieved by heat-treating the parts in an oven and gradually cooling, in effect annealing the stresses; this can also result, however, in the part becoming distorted as a result of these stresses, so that such heat-treating of welded bicycle frames, for instance, results in a significant fraction becoming misaligned. If the misalignment is not too severe, once cooled they can be bent back into alignment with no negative consequences; of course, if the frame is properly designed for rigidity (see above), this will require enormous force.

Household wiring

Because of its high conductivity and relatively low price compared to copper at the time, aluminium was introduced for household electrical wiring to a large degree in the United States in the 1960s. Unfortunately, many of the wiring fixtures at the time were not designed to accept aluminium wire. More specifically:

  • The greater coefficient of thermal expansion of aluminium, causes the wire to expand and contract relative to the dissimilar metal screw connection, eventually loosening the connection.
  • Pure aluminium has a tendency to "creep" under steady sustained pressure (to a greater degree as the temperature rises), again producing a degree of looseness in an initially tight connection.
  • Galvanic corrosion from the dissimilar metals increases the electrical resistance of the connection.

In combination, these properties caused connections between electrical fixtures and aluminium wiring to overheat which resulted in several fires. As a result, aluminium household wiring has become unpopular, and in many jurisdictions is not permitted in very small sizes in new construction. However, aluminium wiring can be safely used with fixtures whose connections are designed to avoid loosening and overheating. Older fixtures of this type are marked "Al/Cu", and newer ones are marked "CO/ALR". Otherwise, aluminium wiring can be terminated by crimping it to a short "pigtail" of copper wire, which can be treated as any other copper wire. A properly done crimp, requiring high pressure produced by the proper tool, is tight enough not only to eliminate any thermal expansion of the aluminium, but also to exclude any atmospheric oxygen and thus prevent corrosion between dissimilar metals. New alloys are used for aluminium building wire today in combination with aluminium terminations. Connections made with these standard industry products are as safe and reliable as copper connections.

History

The oldest suspected (although unprovable) reference to aluminium is in Pliny the Elder's Naturalis Historia:

One day a goldsmith in Rome was allowed to show the Emperor Tiberius a dinner plate of a new metal. The plate was very light, and almost as bright as silver. The goldsmith told the Emperor that he had produced the metal from ordinary clay. He also assured the Emperor that only he, himself, and the gods knew how to produce this metal from clay. The Emperor became very interested, and, as a financial expert, he was also worried. He feared that all his treasures of gold and silver would fall in value if people started producing this bright metal from clay. Therefore, instead of giving the goldsmith the recognition the latter had anticipated, he ordered him to be beheaded. Notes - Source

The ancient Greeks and Romans used salts of this metal as dyeing mordants and as astringents for dressing wounds, and alum is still used as a styptic. Further Joseph Needham suggested finds in 1974 showed the ancient Chinese used aluminium (see the link for "Notes" above). In 1761 Guyton de Morveau suggested calling the base alum 'alumine'. In 1808, Humphry Davy identified the existence of a metal base of alum, which he named (see Spelling below for more information on the name).

Friedrich Wöhler is generally credited with isolating aluminium (Latin alumen, alum) in 1827 by mixing anhydrous aluminium chloride with potassium. However, the metal had been produced for the first time two years earlier in an impure form by the Danish physicist and chemist Hans Christian Ørsted. Therefore almanacs and chemistry sites often list Oersted as the discoverer of aluminium.Source Still it would further be P. Berthier who discovered aluminium in bauxite ore and successfully extracted it. The Frenchman Henri Saint-Claire Deville improved Wöhler's method in 1846 and described his improvements in a book in 1859, chief among these being the substitution of sodium for the considerably more expensive potassium.

The American Charles Martin Hall of Oberlin, OH applied for a patent (400655) in 1886 for an electrolytic process to extract aluminium using the same technique that was independently being developed by the Frenchman Paul Héroult in Europe. The invention of the Hall-Héroult process in 1886 made extracting aluminium from minerals cheaper, and is now the principal method in common use throughout the world. Upon approval of his patent in 1889, Hall, with the financial backing of Alfred E. Hunt of Pittsburgh, PA, started the Pittsburgh Reduction Company, renamed to Aluminum Company of America in 1907, later shortened to Alcoa.

The statue known as Eros in Piccadilly Circus London, was made in 1893 and is one of the first statues to be cast in aluminium.

Aluminium was selected as the material to be used for the apex of the Washington Monument, at a time when one ounce cost twice the daily wages of a common worker in the project. Source

Germany became the world leader in aluminium production soon after Adolf Hitler seized power. By 1942, however, new hydroelectric power projects such as the Grand Coulee Dam gave the United States something Nazi Germany could not hope to compete with, namely the capability of producing enough aluminium to manufacture sixty thousand warplanes in four years. [2]

Natural occurrence

Although Al is an abundant element in Earth's crust (believed to be 7.5% to 8.1%), it is very rare in its free form and was once considered a precious metal more valuable than gold. Napoleon III of France had a set of aluminium plates reserved for his finest guests. Others had to make do with gold ones. Aluminium has been produced in commercial quantities for just over 100 years.

Aluminium was, when it was first discovered, extremely difficult to separate from its ore. Aluminium is among the most difficult metals on earth to refine, despite the fact that it is one of the planet's most common. The reason is that aluminium is oxidized very rapidly and that its oxide is an extremely stable compound that, unlike rust on iron, does not flake off. The very reason for which aluminium is used in many applications is why it is so hard to produce.

Recovery of this metal from scrap (via recycling) has become an important component of the aluminium industry. Recycling involves simply melting the metal, which is far less expensive than creating it from ore. Refining aluminium requires enormous amounts of electricity; recycling it requires only 5% of the energy to produce it. A common practice since the early 1900s, aluminium recycling is not new. It was, however, a low-profile activity until the late 1960s when the exploding popularity of aluminium beverage cans finally placed recycling into the public consciousness. Other sources for recycled aluminium include automobile parts, windows and doors, appliances, containers and other products.

Aluminium is a reactive metal and it is hard to extract it from its ore, aluminium oxide (Al2O3). Direct reduction, with carbon for example, is not economically viable since aluminium oxide has a melting point of about 2000°C. Therefore, it is extracted by electrolysis — the aluminium oxide is dissolved in molten cryolite and then reduced to the pure metal. By this process, the actual operational temperature of the reduction cells is around 950 to 980°C. Cryolite was originally found as a mineral on Greenland, but has been replaced by a synthetic cryolite. Cryolite is a mixture of aluminium, sodium, and calcium fluorides: (Na3AlF6). The aluminium oxide (a white powder) is obtained by refining bauxite, which is red since it contains 30 to 40% iron oxide. This is done using the so-called Bayer process. Previously, the Deville process was the predominant refining technology.

The electolytic process replaced the Wöhler process, which involved the reduction of anhydrous aluminium chloride with potassium. Both of the electrodes used in the electrolysis of aluminium oxide are carbon. Once the ore is in the molten state, its ions are free to move around. The reaction at the negative cathode is

Al3+ + 3e- → Al

Here the aluminium ion is being reduced (electrons are added). The aluminium metal then sinks to the bottom and is tapped off.

At the positive electrode (anode) oxygen gas is formed:

2O2- → O2 + 4e-

This carbon anode is then oxidized by the oxygen. The anodes in a reduction must therefore be replaced regularly, since they are consumed in the process:

O2 + C → CO2

Contrary to the anodes, the cathodes are not consumed during the operation, since there is no oxygen present at the cathode. The carbon cathode is protected by the liquid aluminium inside the cells. Cathodes do erode, mainly due to electrochemical processes. After 5 to 10 years, depending on the current used in the electrolysis, a cell has to be reconstructed completely, because the cathodes are completely worn.

Aluminium electrolysis with the Hall-Héroult process consumes a lot of energy, but alternative processes were always found to be less viable economically and/or ecologically. The world-wide average specific energy consumption is approximately 15±0.5 kilowatt-hours per kilogram of aluminium produced (52 to 56 MJ/kg). The most modern smelters reach approximately 12.8 kW·h/kg (46.1 MJ/kg). Reduction line current for older technologies are typically 100 to 200 kA. State-of-the-art smelters operate with about 350 kA. Trials have been reported with 500 kA cells.

Electric power represents about 20 to 40% of the cost of producing aluminium, depending on the location of the aluminium smelter. Smelters tend to be located where electric power is plentiful and inexpensive, such as South Africa, the South Island of New Zealand, Australia, China, Middle-East, Russia, Iceland and Quebec in Canada.

China is currently (2004) the top world producer of aluminium. Suriname depends on aluminium exports for 70% of its export earnings.[3]

Isotopes

Aluminium has nine isotopes, whose mass numbers range from 23 to 30. Only Al-27 (stable isotope) and Al-26 (radioactive isotope, t1/2 = 7.2 × 105 y) occur naturally, however Al-27 has a natural abundance of 100%. Al-26 is produced from argon in the atmosphere by spallation caused by cosmic-ray protons. Aluminium isotopes have found practical application in dating marine sediments, manganese nodules, glacial ice, quartz in rock exposures, and meteorites. The ratio of Al-26 to beryllium-10 has been used to study the role of transport, deposition, sediment storage, burial times, and erosion on 105 to 106 year time scales.

Cosmogenic Al-26 was first applied in studies of the Moon and meteorites. Meteorite fragments, after departure from their parent bodies, are exposed to intense cosmic-ray bombardment during their travel through space, causing substantial Al-26 production. After falling to Earth, atmospheric shielding protects the meteorite fragments from further Al-26 production, and its decay can then be used to determine the meteorite's terrestrial age. Meteorite research has also shown that Al-26 was relatively abundant at the time of formation of our planetary system. Possibly, the energy released by the decay of Al-26 was responsible for the remelting and differentiation of some asteroids after their formation 4.6 billion years ago.

Clusters

In the journal Science of 14 January 2005 it was reported that clusters of 13 aluminium atoms (Al13) had been made to behave like an iodine atom; and, 14 aluminium atoms (Al14) behaved like an alkaline earth atom. The researchers also bound 12 iodine atoms to an Al13 cluster to form a new class of polyiodide. This discovery is reported to give rise to the possibility of a new characterisation of the periodic table: "cluster elements". The research teams were led by Shiv N. Khanna (Virginia Commonwealth University) and A. Welford Castleman Jr (Penn State University). [4]

Precautions

Aluminium is one of the few abundant elements that appears to have no beneficial function in living cells, but a few percent of people are allergic to it — they experience contact dermatitis from any form of it: an itchy rash from using styptic or antiperspirant products, digestive disorders and inability to absorb nutrients from eating food cooked in aluminium pans, and vomiting and other symptoms of poisoning from ingesting such products as Rolaids , Amphojel, and Maalox (antacids). In other persons, aluminium is not considered as toxic as heavy metals, but there is evidence of some toxicity if it is consumed in excessive amounts, although the use of aluminium cookware, popular because of its corrosion resistance and good heat conduction, has not been shown to lead to aluminium toxicity in general. Excessive consumption of antacids containing aluminium compounds and excessive use of aluminium-containing antiperspirants are more likely causes of toxicity. It has been suggested that aluminium may be linked to Alzheimer's disease, although that research has recently been refuted; aluminium accumulation may be a consequence of the Alzheimer's damage, not the cause. In any event, if there is any toxicity of aluminium it must be via a very specific mechanism, since total human exposure to the element in the form of naturally occurring clay in soil and dust is enormously large over a lifetime.

Care must be taken to prevent aluminium from coming into contact with certain chemicals that can cause it to corrode quickly. For example, just a small amount of mercury applied to the surface of a piece of aluminium can break up the normal aluminium oxide barrier usually present. Within a few hours, even a heavy structural beam can be significantly weakened. For this reason, mercury thermometers are not allowed on many airliners, as aluminium is a common structural component in aircraft.

Spelling

In the English-speaking world, the spellings (and associated pronunciations) aluminium and aluminum are both in common use in both scientific and nonscientific contexts. In most English-speaking nations, the spelling aluminium predominates, and the spelling aluminum is largely unknown. However, in the United States and Canada, the converse is true: the spelling aluminium is largely unknown, and the spelling aluminum predominates.

The International Union of Pure and Applied Chemistry (IUPAC) adopted aluminium as the standard international name for the element in 1990, but three years later recognized aluminum as an acceptable variant. Hence their periodic table includes both, but places aluminium first [5]. IUPAC officially prefers the use of aluminium in its internal publications, although several IUPAC publications use the spelling aluminum.[6] Nevertheless the "ium" spelling has the advantage that the non-English-speaking world prefers the -ium spelling: aluminium is the name used in French and German, and identical or similar forms are used in many other languages. As the non-English speaking world has more people, the forms used in languages other than English are one of the reasons IUPAC chose to officially prefer aluminium over aluminum.

Nomenclature history

In 1808, Humphry Davy originally proposed the name alumium while trying to isolate the new metal electrolytically from the mineral alumina. In 1812 he changed the name to aluminum to match its Latin root. The same year, an anonymous contributor to the Quarterly Review, a British political-literary journal, objected to aluminum, and proposed the name aluminium.

Aluminium, for so we shall take the liberty of writing the word, in preference to aluminum, which has a less classical sound. (Q. Review VIII. 72, 1812. Cited in OED.)

This had the advantage of conforming to the -ium suffix precedent set by other newly discovered elements of the period: potassium, sodium, magnesium, calcium, and strontium (all of which Davy had isolated himself). Nevertheless, -um spellings for elements were not unknown at the time: platinum, which had been known to Europeans since the 16th century, molybdenum, which was discovered in 1778, lanthanum, which was discovered in 1839, and tantalum, which was discovered in 1802, all have spellings ending in -um. For the thirty years following its discovery, both the -um and -ium endings were used interchangeably in the scientific literature.

Curiously, the United States adopted the -ium for most of the 19th century with aluminium appearing in Webster's Dictionary of 1828. However Charles Martin Hall selected the -um spelling in an advertising handbill for his new efficient electrolytic method for the production of aluminium, four years after he had patented the process in 1888. Hall's domination of production of the metal ensured that the spelling aluminum became the standard in North America, even though the Webster Unabridged Dictionary of 1913 continued to use the -ium version.

In 1926, the American Chemical Society officially decided to use aluminum in its publications, and American dictionaries typically label the spelling aluminium as a British variant.

Chemistry

Oxidation state 1

  • AlH is produced when aluminium is heated at 1500 °C in an atmosphere of hydrogen.
  • Al2O is made by heating the normal oxide, Al2O3, with silicon at 1800 °C in a vacuum.
  • Al2S can be made by heating Al2S3 with aluminium shavings at 1300 °C in a vacuum. It quickly disproportionates to the starting materials. The selenide is made in a parallel manner.
  • AlF, AlCl and AlBr exist in the gaseous phase when the tri-halide is heated with aluminium.

Oxidation state 2

  • Aluminium suboxide, AlO can be shown to be present when aluminium powder burns in oxygen.

Oxidation state 3

  • Fajans rules show that the simple trivalent cation Al3+ is not expected to be found in anhydrous salts or binary compounds such as Al2O3. The hydroxide is a weak base and aluminium salts of weak bases, such as carbonate, can't be prepared. The salts of strong acids, such as nitrate, are stable and soluble in water, forming hydrates with at least six molecules of water of crystallization.
  • Aluminium hydride, (AlH3)n, can be produced from trimethylaluminium and an excess of hydrogen. It burns explosively in air. It can also be prepared by the action of aluminium chloride on lithium hydride in ether solution, but cannot be isolated free from the solvent.
  • Aluminium carbide, Al4C3 is made by heating a mixture of the elements above 1000 °C. The pale yellow crystals have a complex lattice structure, and react with water or dilute acids to give methane. The acetylide, Al2(C2)3, is made by passing acetylene over heated aluminium.
  • Aluminium nitride, AlN, can be made from the elements at 800 °C. It is hydrolysed by water to form ammonia and aluminium hydroxide.
  • Aluminium phosphide, AlP, is made similarly, and hydrolyses to give phosphine.
  • Aluminium oxide, Al2O3, occurs naturally as corundum, and can be made by burning aluminium in oxygen or by heating the hydroxide, nitrate or sulfate. As a gemstone, its hardness is only exceeded by diamond, boron nitride and carborundum. It is almost insoluble in water.
  • Aluminium hydroxide may be prepared as a gelatinous precipitate by adding ammonia to an aqueous solution of an aluminium salt. It is amphoteric, being both a very weak acid, and forming aluminates with alkalis. It exists in various crystalline forms.
  • Aluminium sulfide, Al2S3, may be prepared by passing hydrogen sulfide over aluminium powder. It is polymorphic.
  • Aluminium fluoride, AlF3, is made by treating the hydroxide with HF, or can be made from the elements. It consists of a giant molecule which sublimes without melting at 1291 °C. It is very inert. The other trihalides are dimeric, having a bridge-like structure.
  • Organo-metallic compounds of empirical formula AlR3 exist and, if not also giant molecules, are at least dimers or trimers. They have some uses in organic synthesis, for instance trimethylaluminium.
  • Alumino-hydrides of the most electropositive elements are known, the most useful being lithium aluminium hydride, Li[AlH4]. It decomposes into lithium hydride, aluminium and hydrogen when heated, and is hydrolysed by water. It has many uses in organic chemistry. The aluminohalides have a similar structure.

Aluminium in fiction

See also

References

External links

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Patents

  • US400664Process of reducing aluminum from its floride salts by electrolysis – C. M. Hall

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