Самарий: свойства, применение и история открытия

Samarium is a chemical element; it has symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually has the oxidation state +3. Compounds of samarium(II) are also known, most notably the monoxide SmO, monochalcogenides SmS, SmSe and SmTe, as well as samarium(II) iodide. Discovered in 1879 by French chemist Paul Émile Lecoq de Boisbaudran, samarium was named after the mineral samarskite from which it was isolated. The mineral itself was named after a Russian mine official, Colonel Vassili Samarsky Bykhovets, who thus became the first person to have a chemical element named after him, albeit indirectly. Samarium occurs in concentration up to 2.8% in several minerals including cerite, gadolinite, samarskite, monazite and bastnäsite, the last two being the most common commercial sources of the element. These minerals are mostly found in China, the United States, Brazil, India, Sri Lanka and Australia; China is by far the world leader in samarium mining and production. The main commercial use of samarium is in samarium–cobalt magnets, which have permanent magnetization second only to neodymium magnets; however, samarium compounds can withstand significantly higher temperatures, above 700 °C (1292 °F), without losing their permanent magnetic properties. The radioisotope samarium 153 is the active component of the drug samarium (153Sm) lexidronam (Quadramet), which kills cancer cells in lung cancer, prostate cancer, breast cancer and osteosarcoma. Another isotope, samarium 149, is a strong neutron absorber and so is added to control rods of nuclear reactors. It also forms as a decay product during the reactor operation and is one of the important factors considered in the reactor design and operation. Other uses of samarium include catalysis of chemical reactions, radioactive dating and X ray lasers. Samarium(II) iodide, in particular, is a common reducing agent in chemical synthesis. Samarium has no biological role; some samarium salts are slightly toxic. In ambient conditions, samarium has a rhombohedral structure (α form). Upon heating to 731 °C (1348 °F), its crystal symmetry changes to hexagonal close packed (hcp),; it has actual transition temperature depending on metal purity. Further heating to 922 °C (1692 °F) transforms the metal into a body centered cubic (bcc) phase. Heating to 300 °C (572 °F) plus compression to 40 kbar results in a double hexagonally close packed structure (dhcp). Higher pressure of the order of hundreds or thousands of kilobars induces a series of phase transformations, in particular with a tetragonal phase appearing at about 900 kbar. Samarium and its sesquioxide are paramagnetic at room temperature. Their corresponding effective magnetic moments, below 2 bohr magnetons, are the third lowest among lanthanides (and their oxides) after lanthanum and lutetium. The metal transforms to an antiferromagnetic state upon cooling to 14.8 K. Individual samarium atoms can be isolated by encapsulating them into fullerene molecules. They can also be intercalated into the interstices of the bulk C60 to form a solid solution of nominal composition Sm3C60, which is superconductive at a temperature of 8 K. Samarium doping of iron based superconductors – a class of high temperature superconductor – increases their transition to normal conductivity temperature up to 56 K, the highest value achieved so far in this series.

Formula color symmetry space group No Pearson symbol a (pm) b (pm) c (pm) Z density, g/cm3 Sm silvery trigonal I4/mmm 139 tI2 240.2 240.2 423.1 2 20.46 SmO golden cubic Fmm 225 cF8 494.3 494.3 494.3 4 9.15 Sm2O3 trigonal Pm1 164 hP5 377.8 377.8 594 1 7.89 Sm2O3 monoclinic Ia 206 cI80 1093 1093 1093 16 7.1 SmH2 cubic Fmm 225 cF12 537.73 537.73 537.73 4 6.51 SmH3 hexagonal Pc1 165 hP24 377.1 377.1 667.2 6 Sm2B5 gray monoclinic P21/c 14 mP28 717.9 718 720.5 4 6.49 SmB2 hexagonal P6/mmm 191 hP3 331 331 401.9 1 7.49 SmB4 tetragonal P4/mbm 127 tP20 717.9 717.9 406.7 4 6.14 SmB6 cubic Pmm 221 cP7 413.4 413.4 413.4 1 5.06 SmB66 cubic Fmc 226 cF1936 2348.7 2348.7 2348.7 24 2.66 Sm2C3 cubic I4/mmm 139 tI6 377 377 633.1 2 6.44 SmF2 purple Fmm 225 cF12 587.1 587.1 587.1 4 6.18 SmF3 white Pnma 62 oP12 756.28 450.77 901.09 4 4.79 SmCl3 yellow Pnma 62 oP12 797.7 475.4 950.6 4 5.72 SmBr3 yellow Cmcm 63 oS16 404 1265 908 2 5.58 SmI2 green monoclinic P21/c 14 mP12 SmI3 orange R 63 hR24 749 749 2080 6 5.24 SmN cubic Fmm 225 cF8 357 357 357 4 8.48 SmP cubic Fmm 225 cF8 576 576 576 4 6.3 SmAs cubic Fmm 225 cF8 591.5 591.5 591.5 4 7.23

The most stable oxide of samarium is the sesquioxide Sm2O3. Like many samarium compounds, it exists in several crystalline phases. The trigonal form is obtained by slow cooling from the melt. The melting point of Sm2O3 is high (2345 °C), so it is usually melted not by direct heating, but with induction heating, through a radio frequency coil. Sm2O3 crystals of monoclinic symmetry can be grown by the flame fusion method (Verneuil process) from Sm2O3 powder, that yields cylindrical boules up to several centimeters long and about one centimeter in diameter. The boules are transparent when pure and defect free and are orange otherwise. Heating the metastable trigonal Sm2O3 to 1900 °C (3452 °F) converts it to the more stable monoclinic phase.

Samarium forms a trivalent sulfide, selenide and telluride. Divalent chalcogenides SmS, SmSe and SmTe with a cubic rock salt crystal structure are known. These chalcogenides convert from a semiconducting to metallic state at room temperature upon application of pressure. Whereas the transition is continuous and occurs at about 20–30 kbar in SmSe and SmTe, it is abrupt in SmS and requires only 6.5 kbar. This effect results in a spectacular color change in SmS from black to golden yellow when its crystals of films are scratched or polished. The transition does not change the lattice symmetry, but there is a sharp decrease (~15%) in the crystal volume. It exhibits hysteresis, i. e., when the pressure is released, SmS returns to the semiconducting state at a much lower pressure of about 0.4 kbar.

Sintering powders of samarium oxide and boron, in a vacuum, yields a powder containing several samarium boride phases; the ratio between these phases can be controlled through the mixing proportion. It belongs to a class of Kondo insulators; at temperatures above 50 K, its properties are typical of a Kondo metal, with metallic electrical conductivity characterized by strong electron scattering, whereas at lower temperatures, it behaves as a non magnetic insulator with a narrow band gap of about 4–14 meV. The cooling induced metal insulator transition in SmB6 is accompanied by a sharp increase in the thermal conductivity, peaking at about 15 K. The reason for this increase is that electrons themselves do not contribute to the thermal conductivity at low temperatures, which is dominated by phonons, but the decrease in electron concentration reduces the rate of electron phonon scattering.

Samarium carbides are prepared by melting a graphite metal mixture in an inert atmosphere. After the synthesis, they are unstable in air and need to be studied under an inert atmosphere.

Samarium forms a cyclopentadienide |Sm(C5H5)3 and its chloroderivatives |Sm(C5H5)2Cl and |Sm(C5H5)Cl2. They are prepared by reacting samarium trichloride with |NaC5H5 in tetrahydrofuran. Contrary to cyclopentadienides of most other lanthanides, in |Sm(C5H5)3 some |C5H5 rings bridge each other by forming ring vertexes η1 or edges η2 toward another neighboring samarium, thus creating polymeric chains. The (|C5H5)− ion in samarium cyclopentadienides can be replaced by the indenide (|C9H7)− or cyclooctatetraenide (|C8H8)2− ring, resulting in |Sm(C9H7)3 or |KSm(\h(8)\sC8H8)2. The latter compound has a structure similar to uranocene. There is also a cyclopentadienide of divalent samarium, |Sm(C5H5)2 a solid that sublimates at about 85 °C (185 °F). Contrary to ferrocene, the |C5H5 rings in |Sm(C5H5)2 are not parallel but are tilted by 40°. A metathesis reaction in tetrahydrofuran or ether gives alkyls and aryls of samarium: but some sources state that it is radioactive, with a lower bound for its half life given as 2 years. Some observationally stable samarium isotopes are predicted to decay to isotopes of neodymium. The long lived isotopes 146Sm, 147Sm, and 148Sm undergo alpha decay to neodymium isotopes. Lighter unstable isotopes of samarium mainly decay by electron capture to promethium, while heavier ones beta decay to europium. The known isotopes range from 129Sm to 168Sm. The half lives of 151Sm and 145Sm are 90 years and 340 days, respectively. All remaining radioisotopes have half lives that are less than 2 days, and most these have half life less than 48 seconds. Samarium also has twelve known nuclear isomers, the most stable of which are 141mSm (half life 22.6 minutes), 143m1Sm (t1/2 = 66 seconds), and 139mSm (t1/2 = 10.7 seconds). Natural samarium has a radioactivity of 127 Bq/g, mostly due to 147Sm, which alpha decays to 143Nd with a half life of 1.06 years and is used in samarium–neodymium dating. 146Sm is an extinct radionuclide, with the half life of 1.03×108 years. There have been searches of samarium 146 as a primordial nuclide, because its half life is long enough such that minute quantities of the element should persist today. It can be used in radiometric dating. Samarium 149 is an observationally stable isotope of samarium (predicted to decay, but no decays have ever been observed, giving it a half life at least several orders of magnitude longer than the age of the universe), and a product of the decay chain from the fission product 149Nd (yield 1.0888%). 149Sm is a decay product and neutron absorber in nuclear reactors, with a neutron poison effect that is second in importance for reactor design and operation only to 135Xe. Its neutron cross section is 41000 barns for thermal neutrons. Because samarium 149 is not radioactive and is not removed by decay, it presents problems somewhat different from those encountered with xenon 135. The equilibrium concentration (and thus the poisoning effect) builds to an equilibrium value during reactor operations in about 500 hours (about three weeks), and since samarium 149 is stable, its concentration remains essentially constant during reactor operation. Samarium 153 is a beta emitter with a half life of 46.3 hours. It is used to kill cancer cells in lung cancer, prostate cancer, breast cancer, and osteosarcoma. For this purpose, samarium 153 is chelated with ethylene diamine tetramethylene phosphonate (EDTMP) and injected intravenously. The chelation prevents accumulation of radioactive samarium in the body that would result in excessive irradiation and generation of new cancer cells.

Detection of samarium and related elements was announced by several scientists in the second half of the 19th century; however, most sources give priority to French chemist Paul Émile Lecoq de Boisbaudran. Boisbaudran isolated samarium oxide and/or hydroxide in Paris in 1879 from the mineral samarskite |((Y,Ce,U,Fe)3(Nb,Ta,Ti)5O16) and identified a new element in it via sharp optical absorption lines. Swiss chemist Marc Delafontaine announced a new element decipium (from decipiens meaning "deceptive, misleading") in 1878, but later in 1880–1881 demonstrated that it was a mix of several elements, one being identical to Boisbaudran's samarium. Though samarskite was first found in the Ural Mountains in Russia, by the late 1870s it had been found in other places, making it available to many researchers. In particular, it was found that the samarium isolated by Boisbaudran was also impure and had a comparable amount of europium. The pure element was produced only in 1901 by Eugène Anatole Demarçay. Boisbaudran named his element samarium after the mineral samarskite, which in turn honored Vassili Samarsky Bykhovets (1803–1870). Samarsky Bykhovets, as the Chief of Staff of the Russian Corps of Mining Engineers, had granted access for two German mineralogists, the brothers Gustav and Heinrich Rose, to study the mineral samples from the Urals. Samarium was thus the first chemical element to be named after a person. Before the advent of ion exchange separation technology in the 1950s, pure samarium had no commercial uses. However, a by product of fractional crystallization purification of neodymium was a mix of samarium and gadolinium that got the name "Lindsay Mix" after the company that made it, and was used for nuclear control rods in some early nuclear reactors. Nowadays, a similar commodity product has the name "samarium europium gadolinium" (SEG) concentrate. It is prepared by solvent extraction from the mixed lanthanides isolated from bastnäsite (or monazite). Since heavier lanthanides have more affinity for the solvent used, they are easily extracted from the bulk using relatively small proportions of solvent. Not all rare earth producers who process bastnäsite do so on a large enough scale to continue by separating the components of SEG, which typically makes up only 12% of the original ore. Such producers therefore make SEG with a view to marketing it to the specialized processors. In this manner, the valuable europium in the ore is rescued for use in making phosphor. Samarium purification follows the removal of the europium. , being in oversupply, samarium oxide is cheaper on a commercial scale than its relative abundance in the ore might suggest. Distribution of samarium in soils strongly depends on its chemical state and is very inhomogeneous: in sandy soils, samarium concentration is about 200 times higher at the surface of soil particles than in the water trapped between them, and this ratio can exceed 1,000 in clays. Samarium is usually sold as oxide, which at the price of about US$30/kg is one of the cheapest lanthanide oxides. Whereas mischmetal – a mixture of rare earth metals containing about 1% of samarium – has long been used, relatively pure samarium has been isolated only recently, through ion exchange processes, solvent extraction techniques, and electrochemical deposition. The metal is often prepared by electrolysis of a molten mixture of samarium(III) chloride with sodium chloride or calcium chloride. Samarium can also be obtained by reducing its oxide with lanthanum. The product is then distilled to separate samarium (boiling point 1794 °C) and lanthanum (b. p. 3464 °C). Samarium 151 is produced in nuclear fission of uranium with a yield of about 0.4% of all fissions. It is also made by neutron capture by samarium 149, which is added to the control rods of nuclear reactors. Therefore, Sm is present in spent nuclear fuel and radioactive waste. Samarium(II) iodide is a very common reducing and coupling agent in organic synthesis, for example in desulfonylation reactions; annulation; Danishefsky, Kuwajima, Mukaiyama and Holton Taxol total syntheses; strychnine total synthesis; Barbier reaction and other reductions with samarium(II) iodide. In its usual oxidized form, samarium is added to ceramics and glasses where it increases absorption of infrared light. As a (minor) part of mischmetal, samarium is found in the "flint" ignition devices of many lighters and torches.

Samarium doped calcium fluoride crystals were used as an active medium in one of the first solid state lasers designed and built by Peter Sorokin (co inventor of the dye laser) and Mirek Stevenson at IBM research labs in early 1961. This samarium laser gave pulses of red light at 708.5 nm. It had to be cooled by liquid helium and so did not find practical applications. Another samarium based laser became the first saturated X ray laser operating at wavelengths shorter than 10 nanometers. It gave 50 picosecond pulses at 7.3 and 6.8 nm suitable for uses in holography, high resolution microscopy of biological specimens, deflectometry, interferometry, and radiography of dense plasmas related to confinement fusion and astrophysics. Saturated operation meant that the maximum possible power was extracted from the lasing medium, resulting in the high peak energy of 0.3 mJ. The active medium was samarium plasma produced by irradiating samarium coated glass with a pulsed infrared Nd glass laser (wavelength ~1.05 μm).

In 2007 it was shown that nanocrystalline BaFCl:Sm as prepared by co precipitation can serve as a very efficient X ray storage phosphor. The co precipitation leads to nanocrystallites of the order of 100–200 nm in size and their sensitivity as X ray storage phosphors is increased a remarkable ~500,000 times because of the specific arrangements and density of defect centers in comparison with microcrystalline samples prepared by sintering at high temperature. The mechanism is based on reduction of Sm to Sm by trapping electrons that are created upon exposure to ionizing radiation in the BaFCl host. The D–F f–f luminescence lines can be very efficiently excited via the parity allowed 4f→4f5d transition at ~417 nm. The latter wavelength is ideal for efficient excitation by blue violet laser diodes as the transition is electric dipole allowed and thus relatively intense (400 L/(mol⋅cm)). The phosphor has potential applications in personal dosimetry, dosimetry and imaging in radiotherapy, and medical imaging.

The change in electrical resistivity in samarium monochalcogenides can be used in a pressure sensor or in a memory device triggered between a low resistance and high resistance state by external pressure, and such devices are being developed commercially. Samarium monosulfide also generates electric voltage upon moderate heating to about 150 °C (302 °F) that can be applied in thermoelectric power converters. Analysis of relative concentrations of samarium and neodymium isotopes Sm, Nd, and Nd allows determination of the age and origin of rocks and meteorites in samarium–neodymium dating. Both elements are lanthanides and are very similar physically and chemically. Thus, Sm–Nd dating is either insensitive to partitioning of the marker elements during various geologic processes, or such partitioning can well be understood and modeled from the ionic radii of said elements. The Sm ion is a potential activator for use in warm white light emitting diodes. It offers high luminous efficacy due to narrow emission bands; but the generally low quantum efficiency and too little absorption in the UV A to blue spectral region hinders commercial application. Samarium is used for ionosphere testing. A rocket spreads samarium monoxide as a red vapor at high altitude, and researchers test how the atmosphere disperses it and how it impacts radio transmissions. Samarium hexaboride, |SmB6, has recently been shown to be a topological insulator with potential uses in quantum computing.

Samarium salts stimulate metabolism, but it is unclear whether this is from samarium or other lanthanides present with it. The total amount of samarium in adults is about 50 μg, mostly in liver and kidneys and with ~8 μg/L being dissolved in blood. Samarium is not absorbed by plants to a measurable concentration and so is normally not part of human diet. However, a few plants and vegetables may contain up to 1 part per million of samarium. Insoluble salts of samarium are non toxic and the soluble ones are only slightly toxic. When ingested, only 0.05% of samarium salts are absorbed into the bloodstream and the remainder are excreted. From the blood, 45% goes to the liver and 45% is deposited on the surface of the bones where it remains for 10 years; the remaining 10% is excreted.