Iron is a lustrous, ductile, malleable, silver-gray metal found in Group 8 of the periodic table. It is known to exist in four distinct crystalline forms (see allotropy). The most common is the α-form, which is stable below about 770°C;, and has a body-centered cubic crystalline structure; it is often called ferrite. Iron is attracted by a magnet and is itself easily magnetized (see magnetism). It is a good conductor of heat and electricity. It displaces hydrogen from hydrochloric or dilute sulfuric acid, but becomes passive (loses its normal chemical activity) when treated with cold nitric acid.
Iron forms such compounds as oxides, hydroxides, halides, acetates, carbonates, sulfides, nitrates, sulfates, and a number of complex ions. It is chemically active and forms two major series of chemical compounds, the bivalent iron (II), or ferrous, compounds and the trivalent iron (III), or ferric, compounds. Ferrous sulfate heptahydrate, FeSO4·7H2O, sometimes called green vitriol, is a compound formed by the reaction of dilute sulfuric acid (formerly called oil of vitriol) with metallic iron; it is used in the manufacture of ink, in dyeing, and as a disinfectant. Ferric chloride hexahydrate, FeCl3·6H2O, is a yellow-brown crystalline compound used as a mordant in dyeing and as an etching compound. Ferric oxide, Fe2O3, is a reddish-brown powder used as a paint pigment and in abrasive rouges. Prussian blue, KFe2(CN)6, is a pigment containing the ferrocyanide complex ion. Iron rusts readily in moist air, forming a complex mixture of compounds that is mostly a ferrous-ferric oxide with the composition Fe3O4.
Iron is an abundant element in the universe; it is found in many stars, including the sun. Iron is the fourth most abundant element in the earth's crust, of which it constitutes about 5% by weight, and is believed to be the major component of the earth's core. Iron is found distributed in the soil in low concentrations and is found dissolved in groundwaters and the ocean to a limited extent. It is rarely found uncombined in nature except in meteorites, but iron ores and minerals are abundant and widely distributed.
The principal ores of iron are hematite (ferric oxide, Fe2O3) and limonite (ferric oxide trihydrate, Fe2O3·3H2O). Other ores include siderite (ferrous carbonate, FeCO3), taconite (an iron silicate), and magnetite (ferrous-ferric oxide, Fe3O4), which often occurs as a white sand. Iron pyrite (iron disulfide, FeS2) is a crystalline gold-colored mineral known as fool's gold. Chromite is a chromium ore that contains iron. Lodestone is a form of magnetite that exhibits natural magnetic properties.
Iron is produced in the United States chiefly from oxide ores. For many years rich hematite ores were produced by open-pit mining in the Mesabi Range near Lake Superior. However, these ores have been largely depleted, and iron is now produced from low-grade ores that are treated to improve their quality; this process is called beneficiation. Iron ores are refined in the blast furnace. The product of the blast furnace is called pig iron and contains about 4% carbon and small amounts of manganese, silicon, phosphorus, and sulfur. About 95% of this iron is processed further to make steel, often by the open-hearth process or the Bessemer process, but more recently in the United States and other countries by the basic oxygen process or by an electric arc furnace. The balance is cast in sand molds into blocks called pigs. It is further processed in iron foundries (see casting).Cast Iron
Cast iron is made when pig iron is remelted in small cupola furnaces (similar to the blast furnace in design and operation) and poured into molds to make castings. It usually contains 2% to 6% carbon. Scrap iron or steel is often added to vary the composition. Cast iron is used extensively to make machine parts, engine cylinder blocks, stoves, pipes, steam radiators, and many other products. Gray cast iron, or gray iron, is produced when the iron in the mold is cooled slowly. Part of the carbon separates out in plates in the form of graphite but remains physically mixed in the iron. Gray iron is brittle but soft and easily machined. White cast iron, or white iron, which is harder and more brittle, is made by cooling the molten iron rapidly. The carbon remains distributed throughout the iron as cementite (iron carbide, Fe3C). A malleable cast iron can be made by annealing white iron castings in a special furnace. Some of the carbon separates from the cementite; it is much more finely divided than in gray iron. A ductile iron may be prepared by adding magnesium to the molten pig iron; when the iron is cast the carbon forms tiny spherical nodules around the magnesium. Ductile iron is strong, shock resistant, and easily machined.Wrought Iron
Wrought iron is commercially purified iron. In the Aston process, pig iron is refined in a Bessemer converter and then poured into molten iron silicate slag. The resulting semisolid mass is passed between rollers that squeeze out most of the slag. The wrought iron has a fibrous structure with threads of slag running through it; it is tough, malleable, ductile, corrosion resistant, and melts only at high temperatures. It is used to make rivets, bolts, pipes, chains, and anchors, and is also used for ornamental ironwork.
See W. H. Dennis, Metallurgy of the Ferrous Metals (1963) and Foundations of Iron and Steel Metallurgy (1967).
Iron is notable for being the final elements produced by stellar nucleosynthesis, and are therefore the heaviest elements which do not require a red giant or supernova for formation. Iron and nickel are therefore the most abundant metals in metallic meteorites and in the dense-metal cores of planets such as Earth. Iron and iron alloys are also the most common source of ferromagnetic materials in everyday use.
Iron is the sixth most abundant element in the universe, formed as the final act of nucleosynthesis by carbon burning in massive stars. While it makes up about 5% of the Earth's crust, the earth's core is believed to consist largely of an iron-nickel alloy constituting 35% of the mass of the Earth as a whole. Iron is consequently the most abundant element on Earth, but only the fourth most abundant element in the Earth's crust. Most of the iron in the crust is found combined with oxygen as iron oxide minerals such as hematite and magnetite. About 1 in 20 meteorites consist of the unique iron-nickel minerals taenite (35-80% iron) and kamacite (90-95% iron). Although rare, meteorites are the major form of natural metallic iron on the earth's surface.
The reason for Mars' red colour is thought to be an iron-oxide-rich soil.
Iron is a metal extracted mainly from the iron ore hematite. It oxidises readily in air and water to form and is rarely found as a free element. In order to obtain elemental iron, oxygen and other impurities must be removed by chemical reduction. The properties of iron can be modified by alloying it with various other metals and some non-metals, notably carbon and silicon to form steels.
Nuclei of iron atoms have some of the highest binding energies per nucleon, surpassed only by the nickel isotope 62Ni. The universally most abundant of the highly stable nuclides is, however, 56Fe. This is formed by nuclear fusion in stars. Although a further tiny energy gain could be extracted by synthesizing 62Ni, conditions in stars are unsuitable for this process to be favoured, and iron abundance on Earth greatly favors iron over nickel, and also presumably in supernova element production.
Iron (as Fe2+, ferrous ion) is a necessary trace element used by almost all living organisms. The only exceptions are several organisms that live in iron-poor environments and have evolved to use different elements in their metabolic processes, such as manganese instead of iron for catalysis, or hemocyanin instead of hemoglobin. Iron-containing enzymes, usually containing heme prosthetic groups, participate in catalysis of oxidation reactions in biology, and in transport of a number of soluble gases. See hemoglobin, cytochrome, and catalase.
As molten iron cools down it crystallises at 1538°C into its delta allotrope, which has a body-centred cubic (BCC) crystal structure. As it cools further its crystal structure changes to face-centred cubic (FCC) at 1394°C, when it is known as gamma-iron, or austenite. At 912°C the crystal structure again becomes BCC as alpha-iron is formed, and at 770°C (the Curie point, Tc) the iron becomes magnetic. As the iron passes through the Curie temperature there is no change in crystalline structure, but there is a change in 'domain structure', where each domain contains iron atoms with a particular electronic spin. In unmagnetised iron, all the electronic spins of the atoms within one domain are in the same direction; however, in neighbouring domains they point in various directions and thus cancel out. In magnetised iron, the electronic spins of all the domains are all aligned, so that the magnetic effects of neighbouring domains reinforce each other. Although each domain contains billions of atoms, they are very small, about one thousandth of a centimetre across.
Iron is of most importance when mixed with certain other metals and with carbon to form steels. There are many types of steels, all with different properties; and an understanding of the properties of the allotropes of iron is key to the manufacture of good quality steels.
Alpha iron, also known as ferrite, is the most stable form of iron at normal temperatures. It is a fairly soft metal that can dissolve only a small concentration of carbon (no more than 0.021% by mass at 910 °C).
Above 912°C and up to 1401°C alpha iron undergoes a phase transition from body-centred cubic to the face-centred cubic configuration of gamma iron, also called austenite. This is similarly soft and metallic but can dissolve considerably more carbon (as much as 2.04% by mass at 1146°C). This form of iron is used in the type of stainless steel used for making cutlery, and hospital and food-service equipment.
The main disadvantage of iron and steel is that pure iron, and most of its alloys, suffer badly from rust if not protected in some way. Painting, galvanization, passivation, plastic coating and bluing are some techniques used to protect iron from rust by excluding water and oxygen or by sacrificial protection.
The first iron used by mankind during prehistory came from meteors. The smelting of iron in bloomeries probably began in Anatolia, India or the Caucasus in the second millennium BC or the later part of the preceding one. Cast iron was first produced in China about 550 BC, but not in Europe until the medieval period. During the medieval period, means were found in Europe of producing wrought iron from cast iron (in this context known as pig iron) using finery forges. For all these processes, charcoal was required as fuel.
Steel (with a smaller carbon content than pig iron but more than wrought iron) was first produced in antiquity. New methods of producing it by carburizing bars of iron in the cementation process were devised in the 17th century AD. In the Industrial Revolution, new methods of producing bar iron without charcoal were devised and these were later applied to produce steel. In the late 1850s, Henry Bessemer invented a new steelmaking process, involving blowing air through molten pig iron, to produce mild steel. This and other 19th century and later processes have led to wrought iron no longer being produced.
The production of iron or steel is a process unless the desired final product is cast iron. The first stage is to produce pig iron in a blast furnace. The second is to make wrought iron or steel from pig iron by a further process.
Ninety percent of all mining of metallic ores is for the extraction of iron. Industrially, iron is produced starting from iron ores, principally haematite (nominally Fe2O3) and magnetite (Fe3O4) by a carbothermic reaction (reduction with carbon) in a blast furnace at temperatures of about 2000 °C. In a blast furnace, iron ore, carbon in the form of coke, and a flux such as limestone (which is used to remove impurities in the ore which would otherwise clog the furnace with solid material) are fed into the top of the furnace, while a blast of heated air is forced into the furnace at the bottom.
The flux is present to melt impurities in the ore, principally silicon dioxide sand and other silicates. Common fluxes include limestone (principally calcium carbonate) and dolomite (calcium-magnesium carbonate). Other fluxes may be used depending on the impurities that need to be removed from the ore. In the heat of the furnace the limestone flux decomposes to calcium oxide (quicklime):
Then calcium oxide combines with silicon dioxide to form a slag.
The slag melts in the heat of the furnace. In the bottom of the furnace, the molten slag floats on top of the denser molten iron, and apertures in the side of the furnace are opened to run off the iron and the slag separately. The iron once cooled, is called pig iron, while the slag can be used as a material in road construction or to improve mineral-poor soils for agriculture.
In 2005, approximately 1,544 Mt (million metric tons) of iron ore were produced worldwide. China was the top producer of iron ore with at least one-fourth world share followed by Brazil, Australia and India, reports the British Geological Survey.
Alternatively pig iron may be made into steel (with up to about 2% carbon) or wrought iron (commercially pure iron). Various processes have been used for this, including finery forges, puddling furnaces, Bessemer converters, open hearth furnaces, basic oxygen furnaces, and electric arc furnaces. In all cases, the objective is to oxidise some or all of the carbon, together with other impurities. On the other hand, other metals may be added to make alloy steels.
The hardness of the steel depends upon its carbon content. The higher the proportion of carbon, the greater the hardness and the lesser the ductility. The properties of the steel can also be changed by tempering it. To harden the steel, it is heated to red hot and then cooled by quenching it in the water. It becomes harder and more brittle. This steel is then heated to a required temperature and allowed to cool. The steel thus formed is less brittle.
Much of the past work on measuring the isotopic composition of Fe has centered on determining 60Fe variations due to processes accompanying nucleosynthesis (i.e., meteorite studies) and ore formation. In the last decade however, advances in mass spectrometry technology have allowed the detection and quantification of minute, naturally occurring variations in the ratios of the stable isotopes of iron. Much of this work has been driven by the Earth and planetary science communities, although applications to biological and industrial systems are beginning to emerge.
The isotope 56Fe is of particular interest to nuclear scientists. A common misconception is that this isotope represents the most stable nucleus possible, and that it thus would be impossible to perform fission or fusion on 56Fe and still liberate energy. This is not true, as both 62Ni and 58Fe are more stable, being the most stable nuclei. However, since 56Fe is much more easily produced from lighter nuclei in nuclear reactions, it is the endpoint of fusion chains inside extremely massive stars and is therefore common in the universe, relative to other metals.
In phases of the meteorites Semarkona and Chervony Kut a correlation between the concentration of 60Ni, the daughter product of 60Fe, and the abundance of the stable iron isotopes could be found which is evidence for the existence of 60Fe at the time of formation of the solar system. Possibly the energy released by the decay of 60Fe contributed, together with the energy released by decay of the radionuclide 26Al, to the remelting and differentiation of asteroids after their formation 4.6 billion years ago. The abundance of 60Ni present in extraterrestrial material may also provide further insight into the origin of the solar system and its early history. Of the stable isotopes, only 57Fe has a nuclear spin (−1/2).
Iron is essential to nearly all known organisms. In cells, iron is generally stored in the centre of metalloproteins, because "free" iron -- which binds non-specifically to many cellular components -- can catalyse production of toxic free radicals. Iron deficiency can lead to iron deficiency anemia.
In animals, plants, and fungi, iron is often incorporated into the heme complex. Heme is an essential component of cytochrome proteins, which mediate redox reactions, and of oxygen carrier proteins such as hemoglobin, myoglobin, and leghemoglobin. Inorganic iron also contributes to redox reactions in the iron-sulfur clusters of many enzymes, such as nitrogenase (involved in the synthesis of ammonia from nitrogen and hydrogen) and hydrogenase. Non-heme iron proteins include the enzymes methane monooxygenase (oxidizes methane to methanol), ribonucleotide reductase (reduces ribose to deoxyribose; DNA biosynthesis), hemerythrins (oxygen transport and fixation in marine invertebrates) and purple acid phosphatase (hydrolysis of phosphate esters).
Iron distribution is heavily regulated in mammals, partly because iron has a high potential for biological toxicity. Iron distribution is also regulated because many bacteria require iron, so restricting its availability to bacteria (generally by sequestering it inside cells) can help to prevent or limit infections. This is probably the reason for the relatively low amounts of iron in mammalian milk. A major component of this regulation is the protein transferrin, which binds iron absorbed from the duodenum and carries it in the blood to cells.
Iron provided by dietary supplements is often found as iron (II) fumarate, although iron sulfate is cheaper and is absorbed equally well. Elemental iron, despite being absorbed to a much smaller extent (stomach acid is sufficient to convert some of it to ferrous iron), is often added to foods such as breakfast cereals or "enriched" wheat flour (where it is listed as "reduced iron" in the list of ingredients). Iron is most available to the body when chelated to amino acids - iron in this form is ten to fifteen times more bioavailable than any other, and is also available for use as a common iron supplement. Often the amino acid chosen for this purpose is the cheapest and most common amino acid, glycine, leading to "iron glycinate" supplements. The RDA for iron varies considerably based on age, gender, and source of dietary iron (heme-based iron has higher bioavailability). Infants may require iron supplements if they are not breast-fed. Blood donors and pregnant women are at special risk of low iron levels and are often advised to supplement their iron intake.
Iron uptake is tightly regulated by the human body, which has no regulated physiological means of excreting iron. Only small amounts of iron are lost daily due to mucosal and skin epithelial cell sloughing, so control of iron levels is mostly by regulating uptake. However, large amounts of ingested iron can cause excessive levels of iron in the blood because high iron levels can damage the cells of the gastrointestinal tract, preventing them from regulating iron absorption. High blood concentrations of iron damage cells in the heart, liver and elsewhere, which can cause serious problems, including long-term organ damage and even death.
Humans experience iron toxicity above 20 milligrams of iron for every kilogram of mass, and 60 milligrams per kilogram is a lethal dose. Over-consumption of iron, often the result of children eating large quantities of ferrous sulfate tablets intended for adult consumption, is one of the most common toxicological causes of death in children under six. The DRI lists the Tolerable Upper Intake Level (UL) for adults as 45 mg/day. For children under fourteen years old the UL is 40 mg/day.
Regulation of iron uptake is impaired in some people as a result of a genetic defect that maps to the HLA-H gene region on chromosome 6. In these people, excessive iron intake can result in iron overload disorders, such as hemochromatosis. Many people have a genetic susceptibility to iron overload without realizing it or being aware of a family history of the problem. For this reason, it is advised that people not take iron supplements unless they suffer from iron deficiency and have consulted a doctor. Hemochromatosis is estimated to cause disease in between 0.3 and 0.8% of Caucasians.