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Ferroalloy refers to various
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
s of
iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
with a high proportion of one or more other elements such as
manganese Manganese is a chemical element; it has Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese was first isolated in the 1770s. It is a transition m ...
(Mn),
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
(Al), or
silicon Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...
(Si). They are used in the production of
steel Steel is an alloy of iron and carbon that demonstrates improved mechanical properties compared to the pure form of iron. Due to steel's high Young's modulus, elastic modulus, Yield (engineering), yield strength, Fracture, fracture strength a ...
s and alloys. The alloys impart distinctive qualities to steel and cast iron or serve important functions during production and are, therefore, closely associated with the iron and
steel industry Steel is an alloy of iron and carbon that demonstrates improved mechanical properties compared to the pure form of iron. Due to steel's high elastic modulus, yield strength, fracture strength and low raw material cost, steel is one of the ...
, the leading consumer of ferroalloys. The leading producers of ferroalloys in 2014 were
China China, officially the People's Republic of China (PRC), is a country in East Asia. With population of China, a population exceeding 1.4 billion, it is the list of countries by population (United Nations), second-most populous country after ...
,
South Africa South Africa, officially the Republic of South Africa (RSA), is the Southern Africa, southernmost country in Africa. Its Provinces of South Africa, nine provinces are bounded to the south by of coastline that stretches along the Atlantic O ...
,
India India, officially the Republic of India, is a country in South Asia. It is the List of countries and dependencies by area, seventh-largest country by area; the List of countries by population (United Nations), most populous country since ...
,
Russia Russia, or the Russian Federation, is a country spanning Eastern Europe and North Asia. It is the list of countries and dependencies by area, largest country in the world, and extends across Time in Russia, eleven time zones, sharing Borders ...
and
Kazakhstan Kazakhstan, officially the Republic of Kazakhstan, is a landlocked country primarily in Central Asia, with a European Kazakhstan, small portion in Eastern Europe. It borders Russia to the Kazakhstan–Russia border, north and west, China to th ...
, which accounted for 84% of the world production. World production of ferroalloys was estimated as 52.8 million tonnes in 2015.


Compounds

The main ferroalloys are: *FeAl – ferroaluminum *FeB – ferroboron – 12–20% of
boron Boron is a chemical element; it has symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three ...
, max. 3% of
silicon Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...
, max. 2%
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
, max. 1% of
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
*FeCe –
ferrocerium Ferrocerium (also known in Europe as Auermetall) is a synthetic pyrophoric alloy of mischmetal (cerium, lanthanum, neodymium, other trace lanthanides and some iron – about 95% lanthanides and 5% iron) hardened by blending in oxides ...
*FeCr –
ferrochromium Ferrochrome or ferrochromium (FeCr) is a type of ferroalloy, that is, an alloy of chromium and iron, generally containing 50 to 70% chromium by weight. Ferrochrome is produced by electric arc carbothermic reduction of chromite. Most of the glo ...
*FeMg – ferromagnesium *FeMn –
ferromanganese Ferromanganese is an alloy of iron and manganese, with other elements such as silicon, carbon, sulfur, nitrogen and phosphorus. The primary use of ferromanganese is as a type of processed manganese source to add to different types of steel, such ...
*FeMo – ferromolybdenum – min. 60% Mo, max. 1% Si, max. 0.5% Cu *FeNb –
ferroniobium Ferroniobium is an important iron-niobium alloy, with a niobium content of 60-70%. It is the main source for niobium alloying of HSLA steel and covers more than 80% of the worldwide niobium production. The niobium is mined from pyrochlore deposits ...
*FeNi – ferronickel (and nickel pig iron) *FeP – ferrophosphorus *FeSi –
ferrosilicon Ferrosilicon is an ferroalloy, alloy of iron and silicon. It has a typical silicon content of 15–90% by weight and a high proportion of iron silicides. Production and reactions Ferrosilicon is produced by reduction of silica or sand with coke ...
– 15–90% Si *FeSiMg – ferrosilicon magnesium (with Mg 4 to 25%), also called nodulizer *FeTa – ferrotantalum *FeTi – ferrotitanium – 10..30–65..75% Ti, max. 5–6.5% Al, max. 1–4% Si *FeU – ferrouranium *FeV – ferrovanadium *FeW – ferrotungsten


Production, by processes

upright=1.5, lang=en, Evolution of the global ferroalloys production, by processes. Ferroalloys are produced generally by two methods : in a
blast furnace A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals, generally pig iron, but also others such as lead or copper. ''Blast'' refers to the combustion air being supplied above atmospheric pressure. In a ...
or in an
electric arc furnace An electric arc furnace (EAF) is a Industrial furnace, furnace that heats material by means of an electric arc. Industrial arc furnaces range in size from small units of approximately one-tonne capacity (used in foundry, foundries for producin ...
. Blast furnace production continuously decreased during the 20th century, whereas the electric arc production is still increasing. Today, ferromanganese can be still efficiently produced in a blast furnace, but, even in this case, electric arc furnace are spreading. More commonly, ferroalloys are produced by
carbothermic reaction Carbothermic reactions involve the reduction of substances, often metal oxides (O2-), using carbon (C) as the reducing agent. The reduction is usually conducted in the electric arc furnace or reverberatory furnace, depending on the metal ore. The ...
s, involving reduction of oxides with carbon (as coke) in the presence of iron. Some ferroalloys are produced by the addition of elements into molten iron. It is also possible to produce some ferroalloys by
direct reduction read online, part I, pp. 240; 250-254; 257. (capacity 650,000 t/year).(fr) Adolf Ledebur (trans. Barbary de Langlade revised and annotated by F. Valton), ''Manuel théorique et pratique de la métallurgie du fer, Tome I et Tome II'', t. 2, Librairie ...
processes. For example, the Krupp-Renn Process is used in
Japan Japan is an island country in East Asia. Located in the Pacific Ocean off the northeast coast of the Asia, Asian mainland, it is bordered on the west by the Sea of Japan and extends from the Sea of Okhotsk in the north to the East China Sea ...
to produce ferronickel.


Production and consumption, by ferroalloys


Ferrochromium

The leading world chromite ore-producing countries in 2014 were South Africa (12 Mt), Kazakhstan (3.7 Mt), India (3.5 Mt), and Turkey (2.6 Mt). Most of the chromite ore production was smelted in electric-arc furnaces to produce ferrochromium for the metallurgical industry. The leading world ferrochromium-producing countries in 2014 were China (4.5 Mt), South Africa (3.6 Mt), Kazakhstan (1.2 Mt) and India (0.9 Mt). Most of the 11.7 Mt of ferrochromium produced worldwide was consumed in the manufacture of stainless steel which totalled 41.7 Mt in 2014.


Ferromanganese

Two manganese ferroalloys, ferromanganese and silicomanganese, are key ingredients for steelmaking. China is the leading world producer of manganese ferroalloys (2.7 Mt), with output much larger than the combined output of the next three biggest producers—Brazil (0.34 Mt), South Africa (0.61 Mt) and Ukraine (0.38 Mt).


Ferromolybdenum

Major producers of ferromolybdenum are Chile (16,918 t), China (40,000 t) and the United States (which, in 2008, accounted for 78% of world molybdenite ore production. Canada, Mexico and Peru accounted for the remainder. Molybdenite concentrates are roasted to form molybdic oxide, which can be converted into ferromolybdenum, molybdenum chemicals, or molybdenum metal. Although the United States was the second leading molybdenum-producing country in the world in 2008, it imported more than 70% of its ferromolybdenum requirements in 2008, mostly for the steel industry (83% of ferromolybdenum consumed).


Ferronickel

In 2014, about 33% of the world’s annual new
nickel Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...
was ferronickel, an extensive review article of which was published by Swartzendruber et al in 1991. Many of the
meteorites A meteorite is a rock that originated in outer space and has fallen to the surface of a planet or moon. When the original object enters the atmosphere, various factors such as friction, pressure, and chemical interactions with the atmospheri ...
that fall to Earth turn out to be ferronickel, and take the form of
kamacite Kamacite is an alloy of iron and nickel, which is found on Earth only in meteorites. According to the International Mineralogical Association (IMA) it is considered a proper nickel-rich variety of the mineral native iron. The proportion iron:ni ...
and/or
taenite Taenite is a mineral found naturally on Earth mostly in iron meteorites. It is an alloy of iron and nickel, with a chemical formula of and nickel proportions of 20% up to 65%. The name is derived from the Greek ταινία for "band, ribbo ...
. Ferronickel has a
face-centred cubic In crystallography, the cubic (or isometric) crystal system is a crystal system where the unit cell is in the shape of a cube. This is one of the most common and simplest shapes found in crystals and minerals. There are three main varieties o ...
crystal structure (via Ni). It can take the form of ferrite,
martensite Martensite is a very hard form of steel crystalline structure. It is named after German metallurgist Adolf Martens. By analogy the term can also refer to any crystal structure that is formed by diffusionless transformation. Properties Mar ...
, or
austenite Austenite, also known as gamma-phase iron (γ-Fe), is a metallic, non-magnetic allotrope of iron or a solid solution of iron with an alloying element. In plain-carbon steel, austenite exists above the critical eutectoid temperature of 1000 ...
. The binary Fe-Ni system has been investigated for analogic purposes to steel because the presence of nickel in high-alloy steels such as
austenitic stainless steel Austenitic stainless steel is one of the five families of stainless steel (along with ferritic, martensitic, duplex and precipitation hardened). Its primary crystalline structure is austenite (face-centered cubic). Such steels are not hardena ...
s and maraging steels is a key driver for the transition from body-centered cubic ferrite to face-centered cubic austenite. In the late 20th century, 60% of nickel production was based on the matte smelting of sulfide ores, this did not lend itself to ferronickel production. According to 2003 data, the share of laterites in primary nickel production was reported to be 42%. World annual production of ferronickel in 2014 was around 250,000 tonnes. The two largest producers were
BHP BHP Group Limited, founded as the Broken Hill Proprietary Company, is an Australian multinational mining and metals corporation. BHP was established in August 1885 and is headquartered in Melbourne, Victoria. As of 2024, BHP was the world� ...
and Société Le Nickel.
Laterite Laterite is a soil type rich in iron and aluminium and is commonly considered to have formed in hot and wet tropical areas. Nearly all laterites are of rusty-red coloration, because of high iron oxide content. They develop by intensive and prolo ...
ores are often used to supply the production process. The RKEF process is often used."Production of FeNi from high iron nickel ores" Svana, Erik and Ysteb, Roald (1983) Production of FeNi from high iron nickel ores. In: Proceedings of the Seminar on Problems and Prospects of Ferro-Alloy Industry in India, Oct. 24–26, 1983, NML, Jamshedpur. The energy consumption per tonne of product is high for laterite ores because of the low-grade feed, and hence produces a lot of waste slag and gaseous pollution. Generally, over 90% of the furnace output is in the form of
slag The general term slag may be a by-product or co-product of smelting (pyrometallurgical) ores and recycled metals depending on the type of material being produced. Slag is mainly a mixture of metal oxides and silicon dioxide. Broadly, it can be c ...
. The technique of refining molten ferronickel is a topic for specialists, and because of ore content variability the processes might even need to be tailored by source: for example the Larco process of Greek ores.Zevgolis, Emmanouil. (2004)
The evolution of the Greek ferronickel production process
International Laterite Nickel Symposium. 619–632.
"The main reason for adding nickel in ferrous alloys is to promote an austenitic microstructure. Nickel generally increases ductility, toughness and corrosion resistance." Nickel pig iron is distinguished from ferronickel by the former's low weight fraction (4–10%) of nickel and high carbon content (>3%). In contrast, ferronickel is a relatively pure binary alloy. In 2008, the major ferronickel-producing countries were Japan (301,000 t),
New Caledonia New Caledonia ( ; ) is a group of islands in the southwest Pacific Ocean, southwest of Vanuatu and east of Australia. Located from Metropolitan France, it forms a Overseas France#Sui generis collectivity, ''sui generis'' collectivity of t ...
(144,000 t) and Colombia (105,000 t). Together, these three countries accounted for about 51% of world production if China is excluded. Ukraine, Indonesia, Greece, and Macedonia, in descending order of gross weight output, all produced between 68,000 t and 90,000 t of ferronickel, accounting for an additional 31%, excluding China. China was excluded from statistics because its industry produced large tonnages of nickel pig iron in addition to a spectrum of conventional ferronickel grades, for an estimated combined output of 590,000 t gross weight. The nickel content of individual Chinese products varied from about 1.6% to as much as 80%, depending upon customer end use. In the United States, the steel industry accounted for virtually all the ferronickel consumed in 2008, with more than 98% used in stainless and heat-resistant steels; no ferronickel was produced in the US in 2008. The nickel pig iron is a low grade ferronickel made in China, which is very popular since the 2010s.


Ferrosilicon

Silicon ferroalloy consumption is driven by
cast iron Cast iron is a class of iron–carbon alloys with a carbon content of more than 2% and silicon content around 1–3%. Its usefulness derives from its relatively low melting temperature. The alloying elements determine the form in which its car ...
and steel production, where silicon alloys are used as deoxidizers. Some silicon metal was also used as an alloying agent with iron. On the basis of silicon content, net production of ferrosilicon and miscellaneous silicon alloys in the US was 148,000 t in 2008. China is the major supplier, which in 2008 produced more ferrosilicon (4.9 Mt) than the rest of the world combined. Other major manufacturers are Norway (0.21 Mt), Russia (0.85 Mt) and US (0.23 Mt).


Ferrotitanium

Titanium is used in steelmaking for deoxidation, grain-size control, and carbon and nitrogen control and stabilization. During steelmaking, titanium is usually introduced as ferrotitanium because of its relatively low melting temperature and high density. Steels with relatively high titanium content include interstitial-free, stainless and high-strength low-alloy steels. Ferrotitanium is usually produced by induction melting of titanium scrap with iron or steel; however, it also is produced directly from titanium mineral concentrates. The standard grades of ferrotitanium are 30% and 70% titanium. Ferrosilicon-titanium also is produced to allow the simultaneous addition of silicon and titanium. The leading ferrotitanium producing countries include Brazil, China, India, Japan, Russia, Ukraine, United Kingdom and the United States.


Ferrotantalum

Ferrotantalum is added to molten steel to create hardenable specialty steels. It is also used as welding material, spraying powder, and for powder metallurgy applications.


Ferrotungsten

Tungsten is an important alloying element in high-speed and other tool steels, and is used to a lesser extent in some stainless and structural steels. Tungsten is often added to steel melts as ferrotungsten, which can contain up to 80% tungsten. World ferrotungsten production is dominated by China, which in 2008 exported 4,835 t (gross weight) of the alloy. Ferrotungsten is relatively expensive, with the prices around $31–44 per kilogram of contained tungsten.


Ferrovanadium

In 2008, China, Russia (12,000 t) and South Africa (17,000 t) accounted for 98% of world vanadium mine production. In these three countries, vanadium was primarily recovered from titanium-bearing magnetite ore processed to produce pig iron. The process entails aluminothermic reduction of
vanadium(V) oxide Vanadium(V) oxide (''vanadia'') is the inorganic compound with the formula V2 O5. Commonly known as vanadium pentoxide, it is a dark yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of ...
, aluminium (as oxide getter), and scrap iron. This produces a slag containing 20% to 24% vanadium pentoxide, which can be further processed to ferrovanadium containing 40% to 50% vanadium. Of the 5,090 t of vanadium consumed in the United States in 2008, 84% came from ferrovanadium and nearly all of it (99%) went into steel manufacturing.


References

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