Yttrium


Yttrium is a chemical element with the symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a "rare-earth element". Yttrium is almost always found in combination with lanthanide elements in rare-earth minerals, and is never found in nature as a free element. 89Y is the only stable isotope, and the only isotope found in the Earth's crust.
The most important uses of yttrium are LEDs and phosphors, particularly the red phosphors in television set cathode ray tube displays. Yttrium is also used in the production of electrodes, electrolytes, electronic filters, lasers, superconductors, various medical applications, and tracing various materials to enhance their properties.
Yttrium has no known biological role. Exposure to yttrium compounds can cause lung disease in humans.
The name is historical and comes from the village of Ytterby, in Sweden where, in 1787, the famous chemist Arrhenius found a new mineral and named it ytterbite.

Characteristics

Properties

Yttrium is a soft, silver-metallic, lustrous and highly crystalline transition metal in group 3. As expected by periodic trends, it is less electronegative than its predecessor in the group, scandium, and less electronegative than the next member of period 5, zirconium; additionally, it is more electronegative to its successor in its group, lanthanum, surpassing in electronegativity to the later lanthanides due to the lanthanide contraction. Yttrium is the first d-block element in the fifth period.
The pure element is relatively stable in air in bulk form, due to passivation of a protective oxide film that forms on the surface. This film can reach a thickness of 10 µm when yttrium is heated to 750 °C in water vapor. When finely divided, however, yttrium is very unstable in air; shavings or turnings of the metal can ignite in air at temperatures exceeding 400 °C. Yttrium nitride is formed when the metal is heated to 1000 °C in nitrogen.

Similarity to the lanthanides

The similarities of yttrium to the lanthanides are so strong that the element has historically been grouped with them as a rare-earth element, and is always found in nature together with them in rare-earth minerals. Chemically, yttrium resembles those elements more closely than its neighbor in the periodic table, scandium, and if physical properties were plotted against atomic number, it would have an apparent number of 64.5 to 67.5, placing it between the lanthanides gadolinium and erbium.
It often also falls in the same range for reaction order, resembling terbium and dysprosium in its chemical reactivity. Yttrium is so close in size to the so-called 'yttrium group' of heavy lanthanide ions that in solution, it behaves as if it were one of them. Even though the lanthanides are one row farther down the periodic table than yttrium, the similarity in atomic radius may be attributed to the lanthanide contraction.
One of the few notable differences between the chemistry of yttrium and that of the lanthanides is that yttrium is almost exclusively trivalent, whereas about half the lanthanides can have valences other than three; nevertheless, only for four of the fifteen lanthanides are these other valences important in aqueous solution.

Compounds and reactions

As a trivalent transition metal, yttrium forms various inorganic compounds, generally in the oxidation state of +3, by giving up all three of its valence electrons. A good example is yttrium oxide, also known as yttria, a six-coordinate white solid.
Yttrium forms a water-insoluble fluoride, hydroxide, and oxalate, but its bromide, chloride, iodide, nitrate and sulfate are all soluble in water. The Y3+ ion is colorless in solution because of the absence of electrons in the d and f electron shells.
Water readily reacts with yttrium and its compounds to form. Concentrated nitric and hydrofluoric acids do not rapidly attack yttrium, but other strong acids do.
With halogens, yttrium forms trihalides such as yttrium fluoride, yttrium chloride, and yttrium bromide at temperatures above roughly 200 °C. Similarly, carbon, phosphorus, selenium, silicon and sulfur all form binary compounds with yttrium at elevated temperatures.
Organoyttrium chemistry is the study of compounds containing carbon–yttrium bonds. A few of these are known to have yttrium in the oxidation state 0. Some trimerization reactions were generated with organoyttrium compounds as catalysts. These syntheses use as a starting material, obtained from and concentrated hydrochloric acid and ammonium chloride.
Hapticity is a term to describe the coordination of a group of contiguous atoms of a ligand bound to the central atom; it is indicated by the Greek character eta, η. Yttrium complexes were the first examples of complexes where carboranyl ligands were bound to a d0-metal center through a η7-hapticity. Vaporization of the graphite intercalation compounds graphite–Y or graphite– leads to the formation of endohedral fullerenes such as Y@C82. Electron spin resonance studies indicated the formation of Y3+ and 3− ion pairs. The carbides Y3C, Y2C, and YC2 can be hydrolyzed to form hydrocarbons.

Isotopes and nucleosynthesis

Yttrium in the Solar System was created through stellar nucleosynthesis, mostly by the s-process, but also by the r-process. The r-process consists of rapid neutron capture by lighter elements during supernova explosions. The s-process is a slow neutron capture of lighter elements inside pulsating red giant stars.
is an example of the type of red giant star in which most of the yttrium in the solar system was created
Yttrium isotopes are among the most common products of the nuclear fission of uranium in nuclear explosions and nuclear reactors. In the context of nuclear waste management, the most important isotopes of yttrium are 91Y and 90Y, with half-lives of 58.51 days and 64 hours, respectively. Though 90Y has a short half-life, it exists in secular equilibrium with its long-lived parent isotope, strontium-90 with a half-life of 29 years.
All group 3 elements have an odd atomic number, and therefore few stable isotopes. Scandium has one stable isotope, and yttrium itself has only one stable isotope, 89Y, which is also the only isotope that occurs naturally. However, the lanthanide rare earths contain elements of even atomic number and many stable isotopes. Yttrium-89 is thought to be more abundant than it otherwise would be, due in part to the s-process, which allows enough time for isotopes created by other processes to decay by electron emission. Such a slow process tends to favor isotopes with atomic mass numbers around 90, 138 and 208, which have unusually stable atomic nuclei with 50, 82, and 126 neutrons, respectively. 89Y has a mass number close to 90 and has 50 neutrons in its nucleus.
At least 32 synthetic isotopes of yttrium have been observed, and these range in atomic mass number from 76 to 108. The least stable of these is 106Y with a half-life of >150 ns and the most stable is 88Y with a half-life of 106.626 days. Apart from the isotopes 91Y, 87Y, and 90Y, with half-lives of 58.51 days, 79.8 hours, and 64 hours, respectively, all the other isotopes have half-lives of less than a day and most of less than an hour.
Yttrium isotopes with mass numbers at or below 88 decay primarily by positron emission to form strontium isotopes. Yttrium isotopes with mass numbers at or above 90 decay primarily by electron emission to form zirconium isotopes. Isotopes with mass numbers at or above 97 are also known to have minor decay paths of β− delayed neutron emission.
Yttrium has at least 20 metastable isomers ranging in mass number from 78 to 102. Multiple excitation states have been observed for 80Y and 97Y. While most of yttrium's isomers are expected to be less stable than their ground state, 78mY, 84mY, 85mY, 96mY, 98m1Y, 100mY, and 102mY have longer half-lives than their ground states, as these isomers decay by beta decay rather than isomeric transition.

History

In 1787, army lieutenant and part-time chemist Carl Axel Arrhenius found a heavy black rock in an old quarry near the Swedish village of Ytterby. Thinking that it was an unknown mineral containing the newly discovered element tungsten, he named it ytterbite and sent samples to various chemists for analysis.
discovered yttrium oxide
Johan Gadolin at the University of Åbo identified a new oxide in Arrhenius' sample in 1789, and published his completed analysis in 1794. Anders Gustaf Ekeberg confirmed the identification in 1797 and named the new oxide yttria. In the decades after Antoine Lavoisier developed the first modern definition of chemical elements, it was believed that earths could be reduced to their elements, meaning that the discovery of a new earth was equivalent to the discovery of the element within, which in this case would have been yttrium.
Friedrich Wöhler is credited with first isolating the metal in 1828 by reacting a volatile chloride that he believed to be yttrium chloride with potassium.
In 1843, Carl Gustaf Mosander found that samples of yttria contained three oxides: white yttrium oxide, yellow terbium oxide and rose-colored erbium oxide. A fourth oxide, ytterbium oxide, was isolated in 1878 by Jean Charles Galissard de Marignac. New elements were later isolated from each of those oxides, and each element was named, in some fashion, after Ytterby, the village near the quarry where they were found. In the following decades, seven other new metals were discovered in "Gadolin's yttria". Since yttria was found to be a mineral and not an oxide, Martin Heinrich Klaproth renamed it gadolinite in honor of Gadolin.
Until the early 1920s, the chemical symbol Yt was used for the element, after which Y came into common use.
In 1987, yttrium barium copper oxide was found to achieve high-temperature superconductivity. It was only the second material known to exhibit this property, and it was the first known material to achieve superconductivity above the boiling point of nitrogen.

Occurrence

Abundance

Yttrium is found in most rare-earth minerals, it is found in some uranium ores, but is never found in the Earth's crust as a free element. About 31 ppm of the Earth's crust is yttrium, making it the 28th most abundant element, 400 times more common than silver. Yttrium is found in soil in concentrations between 10 and 150 ppm and in sea water at 9 ppt. Lunar rock samples collected during the American Apollo Project have a relatively high content of yttrium.
Yttrium has no known biological role, though it is found in most, if not all, organisms and tends to concentrate in the liver, kidney, spleen, lungs, and bones of humans. Normally, as little as 0.5 milligrams is found in the entire human body; human breast milk contains 4 ppm. Yttrium can be found in edible plants in concentrations between 20 ppm and 100 ppm, with cabbage having the largest amount. With as much as 700 ppm, the seeds of woody plants have the highest known concentrations.
there are reports of the discovery of very large reserves of rare-earth elements on a tiny Japanese island. Minami-Torishima Island, also known as Marcus Island, is described as having "tremendous potential" for rare-earth elements and yttrium, according to a study published in Scientific Reports.
"This REY-rich mud has great potential as a rare-earth metal resource because of the enormous amount available and its advantageous mineralogical features," the study reads. The study shows that more than 16 million tons of rare-earth elements could be "exploited in the near future."
Including yttrium, which is used in products like camera lenses and mobile phone screens, the rare-earth elements found are: Europium, Terbium and Dysprosium.

Production

Since yttrium is chemically so similar to the lanthanides, it occurs in the same ores and is extracted by the same refinement processes. A slight distinction is recognized between the light and the heavy rare-earth elements, but the distinction is not perfect. Yttrium is concentrated in the HREE group because of its ion size, though it has a lower atomic mass.
Rare-earth elements come mainly from four sources:
One method for obtaining pure yttrium from the mixed oxide ores is to dissolve the oxide in sulfuric acid and fractionate it by ion exchange chromatography. With the addition of oxalic acid, the yttrium oxalate precipitates. The oxalate is converted into the oxide by heating under oxygen. By reacting the resulting yttrium oxide with hydrogen fluoride, yttrium fluoride is obtained. When quaternary ammonium salts are used as extractants, most yttrium will remain in the aqueous phase. When the counter-ion is nitrate, the light lanthanides are removed, and when the counter-ion is thiocyanate, the heavy lanthanides are removed. In this way, yttrium salts of 99.999% purity are obtained. In the usual situation, where yttrium is in a mixture that is two-thirds heavy-lanthanide, yttrium should be removed as soon as possible to facilitate the separation of the remaining elements.
Annual world production of yttrium oxide had reached 600 tonnes by 2001; by 2014 it had increased to 7,000 tons. Global reserves of yttrium oxide were estimated in 2014 to be more than 500,000 tons. The leading countries for these reserves included Australia, Brazil, China, India, and the United States. Only a few tonnes of yttrium metal are produced each year by reducing yttrium fluoride to a metal sponge with calcium magnesium alloy. The temperature of an arc furnace of greater than 1,600 °C is sufficient to melt the yttrium.

Applications

Consumer

The red component of color television cathode ray tubes is typically emitted from a yttria or yttrium oxide sulfide host lattice doped with europium cation phosphors. The red color itself is emitted from the europium while the yttrium collects energy from the electron gun and passes it to the phosphor. Yttrium compounds can serve as host lattices for doping with different lanthanide cations. Tb3+ can be used as a doping agent to produce green luminescence. As such yttrium compounds such as yttrium aluminium garnet are useful for phosphors and are an important component of white LEDs.
Yttria is used as a sintering additive in the production of porous silicon nitride.
Yttrium compounds are used as a catalyst for ethylene polymerization. As a metal, yttrium is used on the electrodes of some high-performance spark plugs. Yttrium is used in gas mantles for propane lanterns as a replacement for thorium, which is radioactive.
Currently under development is yttrium-stabilized zirconia as a solid electrolyte and as an oxygen sensor in automobile exhaust systems.

Garnets

Yttrium is used in the production of a large variety of synthetic garnets, and yttria is used to make yttrium iron garnets, which are very effective microwave filters which were recently shown to have magnetic interactions more complex and longer-ranged than understood over the previous four decades. Yttrium, iron, aluminium, and gadolinium garnets 5O12 and Y3 have important magnetic properties. YIG is also very efficient as an acoustic energy transmitter and transducer. Yttrium aluminium garnet has a hardness of 8.5 and is also used as a gemstone in jewelry. Cerium-doped yttrium aluminium garnet crystals are used as phosphors to make white LEDs.
YAG, yttria, yttrium lithium fluoride, and yttrium orthovanadate are used in combination with dopants such as neodymium, erbium, ytterbium in near-infrared lasers. YAG lasers can operate at high power and are used for drilling and cutting metal. The single crystals of doped YAG are normally produced by the Czochralski process.

Material enhancer

Small amounts of yttrium have been used to reduce the grain sizes of chromium, molybdenum, titanium, and zirconium. Yttrium is used to increase the strength of aluminium and magnesium alloys. The addition of yttrium to alloys generally improves workability, adds resistance to high-temperature recrystallization, and significantly enhances resistance to high-temperature oxidation.
Yttrium can be used to deoxidize vanadium and other non-ferrous metals. Yttria stabilizes the cubic form of zirconia in jewelry.
Yttrium has been studied as a nodulizer in ductile cast iron, forming the graphite into compact nodules instead of flakes to increase ductility and fatigue resistance. Having a high melting point, yttrium oxide is used in some ceramic and glass to impart shock resistance and low thermal expansion properties. Those same properties make such glass useful in camera lenses.

Medical

The radioactive isotope yttrium-90 is used in drugs such as Yttrium Y 90-DOTA-tyr3-octreotide and Yttrium Y 90 ibritumomab tiuxetan for the treatment of various cancers, including lymphoma, leukemia, liver, ovarian, colorectal, pancreatic and bone cancers. It works by adhering to monoclonal antibodies, which in turn bind to cancer cells and kill them via intense β-radiation from the yttrium-90.
A technique called radioembolization is used to treat hepatocellular carcinoma and liver metastasis. Radioembolization is a low toxicity, targeted liver cancer therapy that uses millions of tiny beads made of glass or resin containing radioactive yttrium-90. The radioactive microspheres are delivered directly to the blood vessels feeding specific liver tumors/segments or lobes. It is minimally invasive and patients can usually be discharged after a few hours. This procedure may not eliminate all tumors throughout the entire liver, but works on one segment or one lobe at a time and may require multiple procedures.
Also see Radioembolization in the case of combined cirrhosis and Hepatocellular carcinoma.
Needles made of yttrium-90, which can cut more precisely than scalpels, have been used to sever pain-transmitting nerves in the spinal cord, and yttrium-90 is also used to carry out radionuclide synovectomy in the treatment of inflamed joints, especially knees, in sufferers of conditions such as rheumatoid arthritis.
A neodymium-doped yttrium-aluminium-garnet laser has been used in an experimental, robot-assisted radical prostatectomy in canines in an attempt to reduce collateral nerve and tissue damage, and erbium-doped lasers are coming into use for cosmetic skin resurfacing.

Superconductors

Yttrium is a key ingredient in the yttrium barium copper oxide superconductor developed at the University of Alabama and the University of Houston in 1987. This superconductor is notable because the operating superconductivity temperature is above liquid nitrogen's boiling point. Since liquid nitrogen is less expensive than the liquid helium required for metallic superconductors, the operating costs for applications would be less.
The actual superconducting material is often written as YBa2Cu3O7–d, where d must be less than 0.7 for superconductivity. The reason for this is still not clear, but it is known that the vacancies occur only in certain places in the crystal, the copper oxide planes, and chains, giving rise to a peculiar oxidation state of the copper atoms, which somehow leads to the superconducting behavior.
The theory of low temperature superconductivity has been well understood since the BCS theory of 1957. It is based on a peculiarity of the interaction between two electrons in a crystal lattice. However, the BCS theory does not explain high temperature superconductivity, and its precise mechanism is still a mystery. What is known is that the composition of the copper-oxide materials must be precisely controlled for superconductivity to occur.
This superconductor is a black and green, multi-crystal, multi-phase mineral. Researchers are studying a class of materials known as perovskites that are alternative combinations of these elements, hoping to develop a practical high-temperature superconductor.

Lithium batteries

Yttrium is used in small quantities in cathodes of some Lithium iron phosphate battery, and then called commonly LiFeYPO4 chemistry, or LYP. Similar to LFP, LYP batteries offer high energy density, good safety and long life. But LYP, offer higher cathode stability, and prolong life of battery, by protecting physical structure of the cathode, especially at higher temperatures and higher charging / discharge current. LYP batteries do find use in stationary applications, electric vehicles, as well other applications, similar to LFP batteries, but often at improved safety and cycle life time. LYP cells have essentially same nominal voltage as LFP, of 3.25V, and very similar charging and discharge characteristic.
Major manufacturer of LFP batteries is Shenzhen Smart Lion Power Battery Limited, with brands Winston and Thunder Sky.

Other applications

In 2009, Professor Mas Subramanian and associates at Oregon State University discovered that yttrium can be combined with indium and manganese to form an intensely blue, non-toxic, inert, fade-resistant pigment, YInMn blue, the first new blue pigment discovered in 200 years.

Precautions

Yttrium currently has no biological role, and it can be highly toxic to humans and other animals.
Water-soluble compounds of yttrium are considered mildly toxic, while its insoluble compounds are non-toxic. In experiments on animals, yttrium and its compounds caused lung and liver damage, though toxicity varies with different yttrium compounds. In rats, inhalation of yttrium citrate caused pulmonary edema and dyspnea, while inhalation of yttrium chloride caused liver edema, pleural effusions, and pulmonary hyperemia.
Exposure to yttrium compounds in humans may cause lung disease. Workers exposed to airborne yttrium europium vanadate dust experienced mild eye, skin, and upper respiratory tract irritation—though this may be caused by the vanadium content rather than the yttrium. Acute exposure to yttrium compounds can cause shortness of breath, coughing, chest pain, and cyanosis. The Occupational Safety and Health Administration limits exposure to yttrium in the workplace to 1 mg/m3 over an 8-hour workday. The National Institute for Occupational Safety and Health recommended exposure limit is 1 mg/m3 over an 8-hour workday. At levels of 500 mg/m3, yttrium is immediately dangerous to life and health. Yttrium dust is flammable.