Americium is a synthetic chemical element; it has Chemical symbol Am and atomic number 95. It is radioactive and a transuranic member of the actinide series in the periodic table, located under the lanthanide element europium and was thus named after the Americas by analogy.
Americium was first produced in 1944 by the group of Glenn T. Seaborg from Berkeley, California, at the Metallurgical Laboratory of the University of Chicago, as part of the Manhattan Project. Although it is the third element in the transuranic series, it was discovered fourth, after the heavier curium. The discovery was kept secret and only released to the public in November 1945. Most americium is produced by uranium or plutonium being bombarded with in – one tonne of spent nuclear fuel contains about 100 grams of americium. It is widely used in commercial ionization chamber , as well as in and industrial gauges. Several unusual applications, such as nuclear battery or fuel for space ships with nuclear propulsion, have been proposed for the isotope 242mAm, but they are as yet hindered by the scarcity and high price of this nuclear isomer.
Americium is a relatively soft radioactive metal with a silvery appearance. Its most common isotopes are 241Am and 243Am. In chemical compounds, americium usually assumes the oxidation state +3, especially in solutions. Several other oxidation states are known, ranging from +2 to +7, and can be identified by their characteristic optical absorption spectra. The crystal lattices of solid americium and its compounds contain small intrinsic radiogenic defects, due to metamictization induced by self-irradiation with alpha particles, which accumulates with time; this can cause a drift of some material properties over time, more noticeable in older samples.
The new element was isolated from its in a complex, multi-step process. First plutonium-239 nitrate (239PuNO3) solution was coated on a platinum foil of about 0.5 cm2 area, the solution was evaporated and the residue was converted into plutonium dioxide (PuO2) by calcining. After cyclotron irradiation, the coating was dissolved with nitric acid, and then precipitated as the hydroxide using concentrated aqueous ammonia solution. The residue was dissolved in perchloric acid. Further separation was carried out by ion exchange, yielding a certain isotope of curium. The separation of curium and americium was so painstaking that those elements were initially called by the Berkeley group as (from Greek for all demons or hell) and (from Latin for madness).
Initial experiments yielded four americium isotopes: 241Am, 242Am, 239Am and 238Am. Americium-241 was directly obtained from plutonium upon absorption of two neutrons. It decays by emission of a α-particle to 237Np; the half-life of this decay was first determined as years but then corrected to 432.2 years.
The second isotope 242Am was produced upon neutron bombardment of the already-created 241Am. Upon rapid β-decay, 242Am converts into the isotope of curium 242Cm (which had been discovered previously). The half-life of this decay was initially determined at 17 hours, which was close to the presently accepted value of 16.02 h.
The discovery of americium and curium in 1944 was closely related to the Manhattan Project; the results were confidential and declassified only in 1945. Seaborg leaked the synthesis of the elements 95 and 96 on the U.S. radio show for children Quiz Kids five days before the official presentation at an American Chemical Society meeting on 11 November 1945, when one of the listeners asked whether any new transuranium element besides plutonium and neptunium had been discovered during the war. After the discovery of americium isotopes 241Am and 242Am, their production and compounds were patented listing only Seaborg as the inventor.Seaborg, Glenn T. "Element", Filing date: 23 August 1946, Issue date: 10 November 1964 The initial americium samples weighed a few micrograms; they were barely visible and were identified by their radioactivity. The first substantial amounts of metallic americium weighing 40–200 micrograms were not prepared until 1951 by reduction of americium(III) fluoride with barium metal in high vacuum at 1100 °C.
Existing americium is concentrated in the areas used for the atmospheric nuclear weapons tests conducted between 1945 and 1980, as well as at the sites of nuclear incidents, such as the Chernobyl disaster. For example, the analysis of the debris at the testing site of the first U.S. hydrogen bomb, Ivy Mike, (1 November 1952, Enewetak Atoll), revealed high concentrations of various actinides including americium; but due to military secrecy, this result was not published until later, in 1956. Trinitite, the glassy residue left on the desert floor near Alamogordo, New Mexico, after the plutonium-based Trinity test nuclear testing on 16 July 1945, contains traces of americium-241. Elevated levels of americium were also detected at the crash site of a US Boeing B-52 bomber aircraft, which carried four hydrogen bombs, in 1968 in Greenland.
In other regions, the average radioactivity of surface soil due to residual americium is only about 0.01 picocuries per gram (0.37 mBq/g). Atmospheric americium compounds are poorly soluble in common solvents and mostly adhere to soil particles. Soil analysis revealed about 1,900 times higher concentration of americium inside sandy soil particles than in the water present in the soil pores; an even higher ratio was measured in loam soils. Human Health Fact Sheet on Americium , Los Alamos National Laboratory, Retrieved 28 November 2010
Americium is produced mostly artificially in small quantities, for research purposes. A tonne of spent nuclear fuel contains about 100 grams of various americium isotopes, mostly 241Am and 243Am.Hoffmann, Klaus Kann man Gold machen? Gauner, Gaukler und Gelehrte. Aus der Geschichte der chemischen Elemente (Can you make gold? Crooks, clowns, and scholars. From the history of the chemical elements), Urania-Verlag, Leipzig, Jena, Berlin 1979, no ISBN, p. 233 Their prolonged radioactivity is undesirable for the disposal, and therefore americium, together with other long-lived actinides, must be neutralized. The associated procedure may involve several steps, where americium is first separated and then converted by neutron bombardment in special reactors to short-lived nuclides. This procedure is well known as nuclear transmutation, but it is still being developed for americium.Baetslé, L. Application of Partitioning/Transmutation of Radioactive Materials in Radioactive Waste Management , Nuclear Research Centre of Belgium Sck/Cen, Mol, Belgium, September 2001, Retrieved 28 November 2010Fioni, Gabriele; Cribier, Michel and Marie, Frédéric Can the minor actinide, americium-241, be transmuted by thermal neutrons? , Department of Astrophysics, CEA/Saclay, Retrieved 28 November 2010 The transuranic elements from americium to fermium occurred naturally in the natural nuclear fission reactor at Oklo, but no longer do so.
Americium is also one of the elements that have theoretically been detected in Przybylski's Star.
Americium is not synthesized directly from uranium – the most common reactor material – but from the plutonium isotope 239Pu. The latter needs to be produced first, according to the following nuclear process:
The capture of two neutrons by 239Pu (a so-called (n,γ) reaction), followed by a β-decay, results in 241Am:
The plutonium present in spent nuclear fuel contains about 12% of 241Pu. Because it to 241Am, 241Pu can be extracted and may be used to generate further 241Am. However, this process is rather slow: half of the original amount of 241Pu decays to 241Am after about 15 years, and the 241Am amount reaches a maximum after 70 years. BREDL Southern Anti-Plutonium Campaign, Blue Ridge Environmental Defense League, Retrieved 28 November 2010
The obtained 241Am can be used for generating heavier americium isotopes by further neutron capture inside a nuclear reactor. In a light water reactor (LWR), 79% of 241Am converts to 242Am and 10% to its nuclear isomer 242mAm:The "metastable" state is marked by the letter m. article/200410/000020041004A0333355.php Abstract
Metallic americium is obtained by Redox from its compounds. Americium(III) fluoride was first used for this purpose. The reaction was conducted using elemental barium as reducing agent in a water- and oxygen-free environment inside an apparatus made of tantalum and tungsten. Gmelin Handbook of Inorganic Chemistry, System No. 71, transuranics, Part B 1, pp. 57–67.Penneman, p. 3
An alternative is the reduction of americium dioxide by metallic lanthanum or thorium:
At ambient conditions, americium is present in its most stable α form which has a hexagonal crystal symmetry, and a space group P63/mmc with cell parameters a = 346.8 picometer and c = 1124 pm, and four atoms per unit cell. The crystal consists of a double-hexagonal close packing with the layer sequence ABAC and so is isotypic with α-lanthanum and several actinides such as α-curium. The crystal structure of americium changes with pressure and temperature. When compressed at room temperature to 5 GPa, α-Am transforms to the β modification, which has a face-centered cubic ( fcc) symmetry, space group Fmm and lattice constant a = 489 pm. This fcc structure is equivalent to the closest packing with the sequence ABC. Upon further compression to 23 GPa, americium transforms to an orthorhombic γ-Am structure similar to that of α-uranium. There are no further transitions observed up to 52 GPa, except for an appearance of a monoclinic phase at pressures between 10 and 15 GPa. There is no consistency on the status of this phase in the literature, which also sometimes lists the α, β and γ phases as I, II and III. The β-γ transition is accompanied by a 6% decrease in the crystal volume; although theory also predicts a significant volume change for the α-β transition, it is not observed experimentally. The pressure of the α-β transition decreases with increasing temperature, and when α-americium is heated at ambient pressure, at 770 °C it changes into an fcc phase which is different from β-Am, and at 1075 °C it converts to a body-centered cubic structure. The pressure-temperature phase diagram of americium is thus rather similar to those of lanthanum, praseodymium and neodymium.
As with many other actinides, self-damage of the crystal structure due to alpha-particle irradiation is intrinsic to americium. It is especially noticeable at low temperatures, where the mobility of the produced structure defects is relatively low, by broadening of X-ray diffraction peaks. This effect makes somewhat uncertain the temperature of americium and some of its properties, such as electrical resistivity. So for americium-241, the resistivity at 4.2 K increases with time from about 2 μOhm·cm to 10 μOhm·cm after 40 hours, and saturates at about 16 μOhm·cm after 140 hours. This effect is less pronounced at room temperature, due to annihilation of radiation defects; also heating to room temperature the sample which was kept for hours at low temperatures restores its resistivity. In fresh samples, the resistivity gradually increases with temperature from about 2 μOhm·cm at liquid helium to 69 μOhm·cm at room temperature; this behavior is similar to that of neptunium, uranium, thorium and protactinium, but is different from plutonium and curium which show a rapid rise up to 60 K followed by saturation. The room temperature value for americium is lower than that of neptunium, plutonium and curium, but higher than for uranium, thorium and protactinium.
Americium is paramagnetic in a wide temperature range, from that of liquid helium, to room temperature and above. This behavior is markedly different from that of its neighbor curium which exhibits antiferromagnetic transition at 52 K. The thermal expansion coefficient of americium is slightly anisotropic and amounts to along the shorter a axis and for the longer c hexagonal axis. The enthalpy of dissolution of americium metal in hydrochloric acid at standard conditions is , from which the standard enthalpy change of formation (Δf H°) of aqueous Am3+ ion is . The standard potential Am3+/Am0 is .
Americium compounds with oxidation state +4 and higher are strong oxidizing agents, comparable in strength to the permanganate ion () in acidic solutions.Wiberg, p. 1956 Whereas the Am4+ ions are unstable in solutions and readily convert to Am3+, compounds such as americium dioxide (AmO2) and americium(IV) fluoride (AmF4) are stable in the solid state.
The pentavalent oxidation state of americium was first observed in 1951. In acidic aqueous solution the ion is unstable with respect to disproportionation.Greenwood, p. 1275 The reaction
is typical. The chemistry of Am(V) and Am(VI) is comparable to the chemistry of uranium in those oxidation states. In particular, compounds like and are comparable to and the ion is comparable to the uranyl ion, . Such compounds can be prepared by oxidation of Am(III) in dilute nitric acid with ammonium persulfate. Other oxidising agents that have been used include silver(I) oxide, ozone and sodium persulfate.
The oxalate of americium(III), vacuum dried at room temperature, has the chemical formula Am2(C2O4)3·7H2O. Upon heating in vacuum, it loses water at 240 °C and starts decomposing into AmO2 at 300 °C, the decomposition completes at about 470 °C. The initial oxalate dissolves in nitric acid with the maximum solubility of 0.25 g/L.Penneman, p. 5
Reduction of Am(III) compounds with sodium amalgam yields Am(II) salts – the black halides AmCl2, AmBr2 and AmI2. They are very sensitive to oxygen and oxidize in water, releasing hydrogen and converting back to the Am(III) state. Specific lattice constants are:
Americium(III) fluoride (AmF3) is poorly soluble and precipitates upon reaction of Am3+ and fluoride ions in weak acidic solutions:
The tetravalent americium(IV) fluoride (AmF4) is obtained by reacting solid americium(III) fluoride with molecular fluorine:Greenwood, p. 1271
Another known form of solid tetravalent americium fluoride is KAmF5.Penneman, p. 6 Tetravalent americium has also been observed in the aqueous phase. For this purpose, black Am(OH)4 was dissolved in 15-M NH4F with the americium concentration of 0.01 M. The resulting reddish solution had a characteristic optical absorption spectrum which is similar to that of AmF4 but differed from other oxidation states of americium. Heating the Am(IV) solution to 90 °C did not result in its disproportionation or reduction, however a slow reduction was observed to Am(III) and assigned to self-irradiation of americium by alpha particles.
Most americium(III) halides form hexagonal crystals with slight variation of the color and exact structure between the halogens. So, chloride (AmCl3) is reddish and has a structure isotypic to uranium(III) chloride (space group P63/m) and the melting point of 715 °C. The fluoride is isotypic to LaF3 (space group P63/mmc) and the iodide to BiI3 (space group R). The bromide is an exception with the orthorhombic PuBr3-type structure and space group Cmcm. Crystals of americium(III) chloride hexahydrate (AmCl3·6H2O) can be prepared by dissolving americium dioxide in hydrochloric acid and evaporating the liquid. Those crystals are hygroscopic and have yellow-reddish color and a monoclinic crystal structure.
Oxyhalides of americium in the form AmVIO2X2, AmVO2X, AmIVOX2 and AmIIIOX can be obtained by reacting the corresponding americium halide with oxygen or Sb2O3, and AmOCl can also be produced by vapor phase hydrolysis:
Formation of the complexes of the type Am(n-C3H7-BTP)3, where BTP stands for 2,6-di(1,2,4-triazin-3-yl)pyridine, in solutions containing n-C3H7-BTP and Am3+ ions has been confirmed by EXAFS. Some of these BTP-type complexes selectively interact with americium and therefore are useful in its selective separation from lanthanides and another actinides.
There are proposals of very compact 10-kW high-flux reactors using as little as 20 grams of 242mAm. Such low-power reactors would be relatively safe to use as for Nuclear medicine in hospitals.
Americium-241 decays to 237Np emitting alpha particles of 5 different energies, mostly at 5.486 MeV (85.2%) and 5.443 MeV (12.8%). Because many of the resulting states are metastable, they also emit with the discrete energies between 26.3 and 158.5 keV.
Americium-242 is a short-lived isotope with a half-life of 16.02 h. It mostly (82.7%) converts by β-decay to 242Cm, but also by electron capture to 242Pu (17.3%). Both 242Cm and 242Pu transform via nearly the same decay chain through 238Pu down to 234U.
Nearly all (99.541%) of 242m1Am decays by internal conversion to 242Am and the remaining 0.459% by α-decay to 238Np. The latter subsequently decays to 238Pu and then to 234U.
Americium-243 transforms by α-emission into 239Np, which converts by β-decay to 239Pu, and the 239Pu changes into 235U by emitting an α-particle.
The amount of americium in a typical new smoke detector is 1 microcurie (37 kBq) or 0.29 microgram. This amount declines slowly as the americium decays into neptunium-237, a different transuranic element with a much longer half-life (about 2.14 million years). With its half-life of 432.2 years, the americium in a smoke detector includes about 3% neptunium after 19 years, and about 5% after 32 years. The radiation passes through an ionization chamber, an air-filled space between two , and permits a small, constant Electric current between the electrodes. Any smoke that enters the chamber absorbs the alpha particles, which reduces the ionization and affects this current, triggering the alarm. Compared to the alternative optical smoke detector, the ionization smoke detector is cheaper and can detect particles which are too small to produce significant light scattering; however, it is more prone to false alarms.Residential Smoke Alarm Performance, Thomas Cleary. Building and Fire Research Laboratory, National Institute of Standards and Technology; UL Smoke and Fire Dynamics Seminar. November 2007Bukowski, R. W. et al. (2007) Performance of Home Smoke Alarms Analysis of the Response of Several Available Technologies in Residential Fire Settings , NIST Technical Note 1455-1
Another proposed space-related application of americium is a fuel for space ships with nuclear propulsion. It relies on the very high rate of nuclear fission of 242mAm, which can be maintained even in a micrometer-thick foil. Small thickness avoids the problem of self-absorption of emitted radiation. This problem is pertinent to uranium or plutonium rods, in which only surface layers provide alpha-particles. The fission products of 242mAm can either directly propel the spaceship or they can heat a thrusting gas. They can also transfer their energy to a fluid and generate electricity through a magnetohydrodynamic generator.
One more proposal which utilizes the high nuclear fission rate of 242mAm is a nuclear battery. Its design relies not on the energy of the emitted by americium alpha particles, but on their charge, that is the americium acts as the self-sustaining "cathode". A single 3.2 kg 242mAm charge of such battery could provide about 140 kW of power over a period of 80 days.Genuth, Iddo Americium Power Source , The Future of Things, 3 October 2006, Retrieved 28 November 2010 Even with all the potential benefits, the current applications of 242mAm are as yet hindered by the scarcity and high price of this particular nuclear isomer.
In 2019, researchers at the UK National Nuclear Laboratory and the University of Leicester demonstrated the use of heat generated by americium to illuminate a small light bulb. This technology could lead to systems to power missions with durations up to 400 years into interstellar space, where solar panels do not function.
The most widespread use of 241AmBe neutron sources is a neutron probe – a device used to measure the quantity of water present in soil, as well as moisture/density for quality control in highway construction. 241Am neutron sources are also used in well logging applications, as well as in neutron radiography, tomography and other radiochemical investigations.
Irradiation of 241Am by 12C or 22Ne ions yields the isotopes 247Es (einsteinium) or 260Db (dubnium), respectively. Furthermore, the element berkelium (243Bk isotope) had been first intentionally produced and identified by bombarding 241Am with alpha particles, in 1949, by the same Berkeley group, using the same 60-inch cyclotron. Similarly, nobelium was produced at the Joint Institute for Nuclear Research, Dubna, Russia, in 1965 in several reactions, one of which included irradiation of 243Am with 15N ions. Besides, one of the synthesis reactions for lawrencium, discovered by scientists at Berkeley and Dubna, included bombardment of 243Am with 18O.
If consumed, most of the americium is excreted within a few days, with only 0.05% absorbed in the blood, of which roughly 45% goes to the liver and 45% to the bones, and the remaining 10% is excreted. The uptake to the liver depends on the individual and increases with age. In the bones, americium is first deposited over cortical and surfaces and slowly redistributes over the bone with time. The biological half-life of 241Am is 50 years in the bones and 20 years in the liver, whereas in the (testicles and ovaries) it remains permanently; in all these organs, americium promotes formation of cancer cells as a result of its radioactivity.Frisch, Franz Crystal Clear, 100 x energy, Bibliographisches Institut AG, Mannheim 1977, , p. 184
Americium often enters landfills from discarded . The rules associated with the disposal of smoke detectors are relaxed in most jurisdictions. In 1994, 17-year-old David Hahn extracted the americium from about 100 smoke detectors in an attempt to build a breeder nuclear reactor.Ken Silverstein, The Radioactive Boy Scout: When a teenager attempts to build a breeder reactor. Harper's Magazine, November 1998 There have been a few cases of exposure to americium, the worst case being that of chemical operations technician Harold McCluskey, who at the age of 64 was exposed to 500 times the occupational standard for americium-241 as a result of an explosion in his lab. McCluskey died at the age of 75 of unrelated pre-existing disease.
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