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Selenium

Se • Atomic Number 34

Selenium

Selenium belongs to the oxygen group in the periodic table. Its properties are closely related to those of sulfur and tellurium. Like sulfur, selenium occurs in several allotropic forms.

Selenium is a rare element. It occasionally occurs in its native state together with elemental sulfur, but more commonly it is found in association with copper, mercury, lead, or silver in certain minerals.

It is an essential trace element for humans but becomes toxic at high concentrations.

The electrical conductivity of selenium increases when exposed to light, which is why its main application is in photovoltaics.

Selenium is obtained as a by-product during the refining of copper, lead, and other metals. The leading producer is China, with Jiangxi Copper being the world’s largest selenium producer.

  • History

    In 1817, Swedish chemist Jöns Jacob Berzelius, together with Johann Gottlieb Gahn, discovered a red substance derived from sulfide ores in the mines of Falun, Sweden. The following year, it was identified as an element similar to tellurium and was named selenium, after Selene, the Greek goddess of the Moon.

    Later, the different forms of selenium were studied — red amorphous selenium and gray metallic selenium.

    Selenium was first used in the glass industry for coloring and decolorizing glass. In 1873, Willoughby Smith discovered the photoconductivity of selenium.

    From the early 20th century, selenium rectifiers were developed for use in old radios, along with the first selenium-based solar cells. In 1938, Chester Carlson used selenium photoconductors to create the first modern photocopier. In 1957, selenium was recognized as an essential trace element for humans.

    Today, selenium plays an important role in photovoltaics and nanotechnology.

  • Applications and Uses

    The main applications of selenium are in photovoltaics and electronics. It is a key component of copper indium gallium selenide (CIGS) solar cells, an efficient thin-film photovoltaic technology.

    Selenium is also used in the glass industry for decolorizing as well as for producing red coloration in glass and ceramics.

    Selenium coatings protect metal surfaces from corrosion.

    In addition, selenium is used as an alloying element in copper and steel, improving machinability and reducing wear.

  • Occurrence, Mining and Extraction

    The largest selenium reserves are found in China, Russia, Canada, and Chile. There are no dedicated selenium mines; the element is obtained as a by-product during the refining of copper, lead, and other metals.

    China is the dominant producer, followed by Japan, Germany, and Russia as other major producing countries.

    The world’s largest selenium producer is Jiangxi Copper, located in Guixi, Jiangxi Province, China, with an annual output of several hundred tonnes. Tongling Nonferrous Metals Group is another key player in the global selenium market. In Japan, Mitsubishi Materials is the leading selenium producer, while Aurubis in Hamburg, Germany, is the largest selenium producer in Europe.

    The importance of recycling, particularly from old photocopiers and electronic waste, is increasing.

    Global selenium production amounts to approximately 3.500 tonnes per year.

  • Substitution

    The complete substitution of selenium in photovoltaics is unlikely, as copper indium gallium selenide (CIGS) solar cells offer high efficiency. Although CIGS cells can be replaced by perovskite, cadmium telluride, or kesterite solar cells, these alternatives often involve significant trade-offs in terms of efficiency or stability.

    Manganese and cobalt can partially replace selenium in decolorizing applications.

    The substitution of selenium–cadmium red (ruby glass) is possible with cerium sulfide, iron oxide–based pigments, or gold nanoparticles. However, selenium–cadmium red remains unmatched in terms of brilliance, heat resistance, and cost efficiency.

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Rutile

Rt • Mineral

Rutile

Rutile is a common mineral belonging to the class of oxides and hydroxides, with the chemical composition TiO₂, and is therefore chemically classified as titanium dioxide.

Rutile crystallizes in the tetragonal crystal system and typically forms short to elongated prismatic, vertically striated crystals. Crystal twinning is very common, often appearing as polysynthetic, lamellar, or cyclic twins, as well as quadruple and sextuple forms. It can also occur in granular to massive mineral aggregates. Most rutile crystals range in size from a few millimeters to several centimeters, although crystals up to 25 centimeters in length have been found. [3]

The color of the usually transparent to translucent crystals varies from reddish-brown to deep red, but may also appear golden-yellow, bluish, or violet. Iridescent tarnish colors can also occur. The crystal surfaces display a brilliant, diamond-like luster.

  • History

    Rutile was first described in 1803 by the German geologist Abraham Gottlob Werner, who named the mineral after its frequent reddish color, derived from the Latin word rutilus, meaning “red” or “reddish.”

    Until 1795, when its chemical composition was determined, rutile was mistakenly believed to belong to the tourmaline group.

     

  • Classification

    In the now outdated 8th edition (1982) of the Strunz Mineral Classification, rutile belonged to the mineral class of “Oxides and Hydroxides” and specifically to the division of oxides with the general formula “MO₂ and related compounds.” Within this system, it served as the namesake of the Rutile series with the system number IV/D.02, which also included cassiterite, plattnerite, and varlamoffite as members.

    In the most recent Lapis Mineral Directory (updated in 2018) by Stefan Weiß, which continues to follow the traditional Strunz classification for the sake of private and institutional collections, rutile received the system and mineral number IV/D.02-10. In the Lapis system, this corresponds to the division “Oxides with a metal-to-oxygen ratio of 1:2 (MO₂ and related compounds).”

    The 9th edition of the Strunz Mineral Classification, valid since 2001 and updated by the International Mineralogical Association (IMA) until 2009, also places rutile in the division “Oxides with a metal-to-oxygen ratio of 1:2 and related compounds.” However, this edition further subdivides minerals according to the size of the involved cations and the crystal structure. Based on its composition and crystal structure, rutile is assigned to the subgroup “With medium-sized cations; chains of edge-sharing octahedra.” Within this group, rutile again serves as the namesake of the Rutile group with the system number 4.DB.05, which includes the minerals argutite, cassiterite, plattnerite, pyrolusite, tripuhyite, tugarinovite, and varlamoffite.

    In the Dana classification system, rutile is likewise assigned to the class “Oxides and Hydroxides,” though it is first placed within the division of “Oxides.” Here, it is found together with ilmenorutile, struverite, pyrolusite, cassiterite, plattnerite, argutite, squawcreekite, and stishovite in the Rutile group (tetragonal: P4₂/mnm) with the system number 04.04.01, within the subdivision “Simple oxides with a cation charge of 4+ (AO₂).”

     

  • Crystal Structure

    The rutile structure is a common structural type for AB₂ compounds and, in contrast to the fluorite structure, is not based on a close-packed arrangement. The oxide anions are arranged in distorted and wavy “hexagonal” layers, with half of the octahedral interstices between them occupied by titanium cations. However, due to the tetragonal symmetry, these wavy layers do not form a true close packing.

    The crystal structure is therefore better described as a tetragonal rod packing of chains of edge-sharing [TiO₆] octahedra (according to Niggli notation: [TiO₄/₂O₂/₁]) running parallel to the crystallographic c-axis. These chains are further connected via shared corners to form a three-dimensional [TiO₆/₃] network, which simplifies to the overall chemical formula TiO₂.

    Each titanium cation is octahedrally coordinated by six oxygen atoms (coordination number 6), while each oxide anion is surrounded by three titanium atoms in a slightly distorted trigonal planar arrangement (coordination number 3).

    A number of other inorganic compounds also crystallize in the rutile structure, including the oxides NbO₂, TaO₂, MnO₂, and SnO₂, as well as the fluorides CrF₂, MnF₂, FeF₂, CoF₂, NiF₂, CuF₂, and ZnF₂.

  • Unique Properties

    Morphology

    Rutile commonly forms prismatic crystals with a thick-columnar to fine-needle-like habit, often dominated by the crystal forms {110} and {010}. The crystal faces are typically elongated and striated parallel to the prism axis. Among many other forms, ditetragonal prisms may also occur.

    In fine needle-like or fibrous inclusions, rutile is responsible for the optical phenomenon of asterism (the “star effect”) observed in gemstones such as sapphires and rubies. In microscopic inclusions, together with hematite and other minerals, rutile can accentuate “phantom crystals” often seen in quartz.

    Twinning is common in rutile and can occur according to two distinct laws. Twins, triplets, and polysynthetic multiples, often lamellar or cyclic, are most frequently formed on (101). The individuals meet at an angle of 65°35′, producing characteristic knee-shaped, visor-shaped, or V-shaped twin forms and even sixlings that form closed rings. Less common are heart-shaped twins on (301), where the vertical axes meet at an angle of 54°44′. Both twinning laws can occur simultaneously, forming lattice-like or net-like aggregates known as sagenite.

    Color

    Rutile can occur in various colors, but is most commonly found in reddish-brown to deep red and black. As inclusions in other minerals, such as quartz, rutile also shines in a rich golden yellow color and, in this form, is known as Venus hair and is often used in jewelry. Blue or violet hues, on the other hand, are rare.

    Chemical and Physical Properties

    Rutile is insoluble in acid and cannot be melted with a blowpipe. In its pure form, it is weakly paramagnetic with a specific magnetic susceptibility (mass susceptibility) of 7.7·10−7 emu/Oe·mg, but if it also contains iron, it becomes antiferromagnetic[4].
    Modifications and varieties.

    Rutile is the most important and only modification of titanium dioxide that is stable at high temperatures. The other two are anatase and brookite.

    Sagenite is the name given to a variety of rutile that exhibits flat, net-like to lattice-like intergrowths of needle-like fine rutile twins. It is also referred to as epitaxial (oriented) intergrowth.

    Nigrin is the name given to an iron-bearing, black rutile.

     

  • Formation and Occurrence

    Formation Conditions

    Rutile forms as a high-temperature and high-pressure mineral, occurring both magmatically and metamorphically. It is a common accessory mineral in many types of rocks and is also found as a placer mineral in river sediments. Accordingly, rutile is often associated with a wide range of other minerals, including the other TiO₂ polymorphs anatase and brookite, as well as adularia, albite, apatite, calcite, chlorite, ilmenite, pyrophyllite, titanite, and quartz. Rutile also forms epitaxial intergrowths with hematite.

    It occurs in eclogites and is the dominant titanium-bearing phase in garnet amphibolites.

    Localities

    As a common mineral species, rutile has been found in many locations worldwide, with around 5,900 occurrences documented as of 2019.

    Notable for their exceptional specimens are the Graves Mountain Mine in Lincoln County, Georgia (USA), where crystals up to 15 cm in size have been found; the Cavradi Gorge near Sedrun in the Swiss canton of Graubünden; and the municipality of Ibitiara in Bahia, Brazil, both known for their striking rutile–hematite epitaxial intergrowths. In Ibitiara and in Itabira (Minas Gerais, Brazil), rutile inclusions in smoky quartz are also common. Large knee- or visor-shaped crystal twins up to about 7 cm have been found near Golčův Jeníkov and Soběslav in the Czech Republic. Crystals up to 3 cm in diameter and 5 cm in length were discovered in the Paragachay deposit on Mount Kapudschuk in the Nakhichevan Autonomous Republic, Azerbaijan.

    In Germany, rutile has been identified in several regions, including the Black Forest (Baden-Württemberg), the Fichtelgebirge, Spessart, Bavarian Forest, and Upper Palatinate Forest (Bavaria), as well as in Hesse, Lower Saxony, the Siebengebirge (North Rhine-Westphalia), the Eifel (Rhineland-Palatinate), Saarland, the Ore Mountains (Saxony), Schleswig-Holstein, and Thuringia.

    In Austria, the mineral has been found in Burgenland, in alpine clefts in many regions of Carinthia, Salzburg, and Styria, in parts of Lower Austria and Tyrol, as well as in Upper Austria and Vorarlberg.

    In Switzerland, rutile occurs mainly in alpine clefts in the cantons of Graubünden, Ticino, and Valais.

    Rutile has also been identified in rock samples from the Mid-Atlantic Ridge and the Southwest Indian Ridge, as well as on the Moon, specifically in the Fra Mauro Highlands.

    Largest Producing Countries

    Worldwide, the mining reserves for the most important titanium minerals, ilmenite and rutile, are estimated at 692.58 million tons, with the largest regional concentrations found in China (28.9%), Australia (17.0%), and India (13.3%) (as of November 2014).

     

  • Applications and Uses

    Rutile, with a titanium content of about 60%, is the most important titanium mineral after ilmenite.

    In its TiO₂ modification, rutile is used as a white pigment due to its high refractive index. It is also used, either alone or mixed with cellulose, as a coating material for electrodes in arc welding, where it improves or even enables the welding process.

    Because of its semiconducting properties, rutile is employed in dye-sensitized solar cells (Grätzel cells). With a band gap of approximately 3.0 eV, it can absorb light with a wavelength shorter than about 400 nm.

    As a Gemstone

    Natural rutile is only occasionally cut and polished as a gemstone by collectors, as its crystals are typically too small. Synthetic rutile, however, has been produced since 1948 and marketed under the trade names Titania or Diamonite (not to be confused with Diamondite) as a diamond imitation. It even surpasses the brilliance of diamond, owing to its dispersion that is about six times higher.

    Rutile needles included within other minerals, particularly quartz, are also popular in jewelry. These inclusions not only produce a golden luster, but also give rise to various optical phenomena, such as asterism (a star-like light reflection) and chatoyancy (the cat’s-eye effect).

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Rhodium

Rh • Atomic Number 45

Rhodium

Rhodium is a silver-white precious metal that is extremely hard, durable, and resistant to acids. It belongs to the platinum group metals. Its electrical and thermal conductivity are higher than those of the other platinum metals. Rhodium is characterized by a high degree of light reflectivity and has a high melting point (1.964 degrees Celsius). In nature, rhodium occurs in its native form and is therefore recognized as a distinct mineral.

Rhodium is one of the rarest and most expensive metals in the world, more valuable than gold or platinum. Rhodium compounds are corrosive, highly toxic, and carcinogenic. Finely divided metallic rhodium, in the form of powder or dust, is easily flammable.

The precious metal is in high demand in industry, jewelry manufacturing, and high technology, with by far its most important application being in automotive exhaust catalysts.

Rhodium production is dominated by South Africa, where it is obtained as a by-product of platinum and palladium mining.

The largest source of rhodium is the Bushveld Complex. Sibanye-Stillwater, Anglo American Platinum, and Impala Platinum are the leading rhodium producers.

For the EU, the United States, Japan, and the United Kingdom, rhodium (platinum group metals) is classified as a critical raw material.

  • History

    Rhodium was discovered in 1803 by the English chemist William Hyde Wollaston, who isolated the metal from crude platinum ore. The name rhodium is derived from the Greek word rhodon, meaning “rose,” referring to the rose-red color of some of its salts.

    Because rhodium was extremely rare and difficult to obtain, it was initially used only for research purposes. The first practical application of the new metal appeared around 1820, when a rhodium–tin alloy was used for fountain pen nibs.

    Its high corrosion resistance and brilliant appearance made it a sought-after coating for luxury goods and jewelry in the 19th century.

    It was not until the 20th century that rhodium began to be used industrially, primarily in automotive catalytic converters.

  • Application

    Between 80 and 90 percent of all rhodium is used in the automotive industry for exhaust catalysts (three-way catalytic converters) to reduce emissions of harmful nitrogen oxides.

    Metallic rhodium has a high reflectivity and is therefore also used as a coating in high-quality mirrors. These coatings are both extremely hard and chemically stable.

    The metal is also used together with gold, platinum, and silver in the manufacture of jewelry and watches.

    Jewelers value rhodium plating for its brilliance and protective qualities. Silver treated with rhodium becomes brighter, more durable, and does not tarnish when exposed to air. Rhodium is also essential for producing both white and black gold.

    Although rhodium compounds are toxic and carcinogenic, the amount of rhodium used in certified jewelry poses no risk to human health.

    High demand from the automotive industry, combined with its rarity, makes rhodium one of the most expensive metals in the world.

  • Occurrence, Mining and Extraction

    Rhodium powder pressed melted small scaled e1638959887636

    Rhodium: processing – 1 g powder, 1 g pressed cylinder, 1 g argon arc remelted pellet.

    South Africa dominates the global rhodium market, accounting for 80 to 90 percent of world production. Rhodium is obtained as a by-product of platinum and palladium mining. The largest platinum deposit, the Bushveld Complex, is one of the most important sources of rhodium.

    The key industry players are Sibanye-Stillwater, Anglo American Platinum, and Impala Platinum, with Anglo American Platinum—part of the Anglo American Group—being the world leader.

    Outside South Africa, Norilsk Nickel in Russia is the largest rhodium producer.

    Global annual production is estimated at around 24 tonnes.

  • Substitution

    Rhodium is often replaced by other materials due to its high price and limited availability. Palladium serves as a substitute for rhodium, particularly in the jewelry industry and in catalytic converters.

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Rhenium

Re • Atomic Number 75

Rhenium

Rhenium is one of the densest metals in the Earth's crust and has one of the highest melting points (3,180 degrees Celsius). It does not occur freely in nature nor as a compound in any specific mineral. Instead, it is found in trace concentrations averaging about 0.001 ppm in various minerals, making it one of the rarest elements in the Earth's crust.

Rhenium is extremely resistant to corrosion and acids. Due to its strength at high temperatures, it is a key element in high-performance aerospace jet engines.

Its rarity and strategic importance to the aviation industry make it one of the most valuable metals in the world. In many industrialized countries, rhenium is listed as a critical raw material.

Chile is the world’s largest producer of rhenium, accounting for over 50 percent of global supply.

The Bingham Canyon copper mine, operated by Rio Tinto in the United States, is the largest single source of rhenium.

  • History

    Rhenium was predicted in 1869 by the Russian chemist Dmitri Ivanovich Mendeleev and discovered in 1925 by the German chemists Ida and Walter Noddack, together with Otto Carl Berg. The trio identified rhenium in platinum ores and columbite using X-ray spectroscopy. They named it after the Latin name for the Rhine River, in reference to their homeland.

    Due to its rarity and the difficulty of extraction, rhenium was long used exclusively in research laboratories.

    Industrial use began only in the 1950s, when it was incorporated into high-temperature alloys for aircraft turbines, catalysts for petroleum refining, as well as in medical X-ray tubes and electronics.

  • Application

    ChatGPT:

    The primary application of rhenium is in high-temperature superalloys used for turbine blades in jet engines and rocket motors. Superalloys based on nickel or tungsten are alloyed with three to six percent rhenium to increase strength and heat resistance, making aircraft engines more durable and efficient. Nearly three-quarters of the world’s rhenium production is used for this purpose.

    The second most important application of rhenium is in catalysts for the petroleum industry. Other uses include thermocouples for industrial furnaces, incandescent cathodes, X-ray technology, and medical applications.

  • Occurrence, Mining and Extraction

    There are no pure rhenium mines. The element is obtained as a by-product of copper and molybdenum mining.

    Production is concentrated in a few countries. Chile is the leading producer, accounting for more than half of global output. Major sources include the Chuquicamata and Escondida copper mines, operated by Codelco and BHP, respectively.

    The Chilean–Swiss company Molymet is one of the world’s largest rhenium processors.

    The United States also has notable rhenium production. The Bingham Canyon copper mine—also known as the Kennecott Copper Mine—operated by Rio Tinto, is the largest single source of rhenium. While it covers part of the U.S. demand, the country still relies on imports due to increasing demand for superalloys in the aerospace industry.

    Other major rhenium producers include Poland, with copper producer KGHM Polska Miedź, and China. Since 2020, Uzbekistan has also become an important rhenium producer through the Almalyk Mining and Metallurgical Combine.

    The United States and Germany are leaders in rhenium recycling.

    Global annual production amounts to approximately 60.000 kilograms.

  • Substitution

    Substitute materials for rhenium in platinum–rhenium catalysts are continuously being evaluated. Applications using iridium and tin have already achieved commercial success. Other metals being tested for catalytic use include gallium, germanium, indium, selenium, silicon, tungsten, and vanadium. The use of these and other metals in bimetallic catalysts could reduce the share of rhenium in the existing catalyst market.

    However, this may be offset by rhenium-containing catalysts that are being considered for use in several planned gas-to-liquid (GTL) projects.

    Materials that can replace rhenium in various end applications include cobalt and tungsten for coatings on copper X-ray targets; rhodium and rhodium–iridium for high-temperature thermocouples; tungsten and platinum–ruthenium for coatings on electrical contacts; and tungsten and tantalum for electron emitters.

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