Plutonium

Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibits six allotropes and four oxidation states. It reacts with carbon, halogens, nitrogen, silicon, and hydrogen. When exposed to moist air, it forms oxides and hydrides that can expand the sample up to 70% in volume, which in turn flake off as a powder that is pyrophoric. It is radioactive and can accumulate in bones, which makes the handling of plutonium dangerous.

Plutonium was first synthetically produced and isolated in late 1940 and early 1941, by a deuteron bombardment of uranium-238 in the cyclotron at the University of California, Berkeley. First, neptunium-238 ( half-life 2.1 days) was synthesized, which subsequently beta-decayed to form the new element with atomic number 94 and atomic weight 238 (half-life 88 years). Since uranium had been named after the planet Uranus and neptunium after the planet Neptune, element 94 was named after Pluto, which at the time was considered to be a planet as well. Wartime secrecy prevented the University of California team from publishing its discovery until 1948.

Plutonium is the element with the highest atomic number to occur in nature. Trace quantities arise in natural uranium-238 deposits when uranium-238 captures neutrons emitted by decay of other uranium-238 atoms.

Both plutonium-239 and plutonium-241 are fissile, meaning that they can sustain a nuclear chain reaction, leading to applications in nuclear weapons and nuclear reactors. Plutonium-240 exhibits a high rate of spontaneous fission, raising the neutron flux of any sample containing it. The presence of plutonium-240 limits a plutonium sample's usability for weapons or its quality as reactor fuel, and the percentage of plutonium-240 determines its grade ( weapons-grade, fuel-grade, or reactor-grade). Plutonium-238 has a half-life of 87.7 years and emits alpha particles. It is a heat source in radioisotope thermoelectric generators, which are used to power some spacecraft. Plutonium isotopes are expensive and inconvenient to separate, so particular isotopes are usually manufactured in specialized reactors.

Producing plutonium in useful quantities for the first time was a major part of the Manhattan Project during World War II that developed the first atomic bombs. The Fat Man bombs used in the Trinity nuclear test in July 1945, and in the bombing of Nagasaki in August 1945, had plutonium cores. Human radiation experiments studying plutonium were conducted without informed consent, and several criticality accidents, some lethal, occurred after the war. Disposal of plutonium waste from nuclear power plants and dismantled nuclear weapons built during the Cold War is a nuclear-proliferation and environmental concern. Other sources of plutonium in the environment are fallout from numerous above-ground nuclear tests, now banned.

Characteristics

Physical properties

Plutonium, like most metals, has a bright silvery appearance at first, much like nickel, but it oxidizes very quickly to a dull gray, although yellow and olive green are also reported. (public domain text) At room temperature plutonium is in its α (''alpha'') form. This, the most common structural form of the element ( allotrope), is about as hard and brittle as gray cast iron unless it is alloyed with other metals to make it soft and ductile. Unlike most metals, it is not a good conductor of heat or electricity. It has a low melting point () and an unusually high boiling point (). This gives a large range of temperatures (over 2,500 kelvin wide) at which plutonium is liquid, but this range is neither the greatest among all actinides nor among all metals. The low melting point as well as the reactivity of the native metal compared to the oxide leads to plutonium oxides being a preferred form for applications such as nuclear fission reactor fuel (MOX-fuel).

Alpha decay, the release of a high-energy helium nucleus, is the most common form of radioactive decay for plutonium. A 5 kg mass of ²³⁹Pu contains about atoms. With a half-life of 24,100 years, about of its atoms decay each second by emitting a 5.157  MeV alpha particle. This amounts to 9.68 watts of power. Heat produced by the deceleration of these alpha particles makes it warm to the touch. due to its much shorter half life heats up to much higher temperatures and glows red hot with blackbody radiation if left without external heating or cooling. This heat has been used in Radioisotope thermoelectric generators (see below).

Resistivity is a measure of how strongly a material opposes the flow of electric current. The resistivity of plutonium at room temperature is very high for a metal, and it gets even higher with lower temperatures, which is unusual for metals. This trend continues down to 100  K, below which resistivity rapidly decreases for fresh samples. Resistivity then begins to increase with time at around 20 K due to radiation damage, with the rate dictated by the isotopic composition of the sample.

Because of self-irradiation, a sample of plutonium fatigues throughout its crystal structure, meaning the ordered arrangement of its atoms becomes disrupted by radiation with time. Self-irradiation can also lead to annealing which counteracts some of the fatigue effects as temperature increases above 100 K.

Unlike most materials, plutonium increases in density when it melts, by 2.5%, but the liquid metal exhibits a linear decrease in density with temperature. Near the melting point, the liquid plutonium has very high viscosity and surface tension compared to other metals.

Allotropes

Plutonium normally has six allotropes and forms a seventh (zeta, ζ) at high temperature within a limited pressure range. These allotropes, which are different structural modifications or forms of an element, have very similar internal energies but significantly varying densities and crystal structures. This makes plutonium very sensitive to changes in temperature, pressure, or chemistry, and allows for dramatic volume changes following phase transitions from one allotropic form to another. The densities of the different allotropes vary from 16.00 g/cm³ to 19.86 g/cm³.

The presence of these many allotropes makes machining plutonium very difficult, as it changes state very readily. For example, the α form exists at room temperature in unalloyed plutonium. It has machining characteristics similar to cast iron but changes to the plastic and malleable β (''beta'') form at slightly higher temperatures. The reasons for the complicated phase diagram are not entirely understood. The α form has a low-symmetry monoclinic structure, hence its brittleness, strength, compressibility, and poor thermal conductivity.

Plutonium in the δ (''delta'') form normally exists in the 310 °C to 452 °C range but is stable at room temperature when alloyed with a small percentage of gallium, aluminium, or cerium, enhancing workability and allowing it to be welded. The δ form has more typical metallic character, and is roughly as strong and malleable as aluminium. In fission weapons, the explosive shock waves used to compress a plutonium core will also cause a transition from the usual δ phase plutonium to the denser α form, significantly helping to achieve supercriticality. The ε phase, the highest temperature solid allotrope, exhibits anomalously high atomic self-diffusion compared to other elements.

Nuclear fission

Plutonium is a radioactive actinide metal whose isotope, plutonium-239, is one of the three primary fissile isotopes ( uranium-233 and uranium-235 are the other two); plutonium-241 is also highly fissile. To be considered fissile, an isotope's atomic nucleus must be able to break apart or fission when struck by a slow moving neutron and to release enough additional neutrons to sustain the nuclear chain reaction by splitting further nuclei.

Pure plutonium-239 may have a multiplication factor (k_eff) larger than one, which means that if the metal is present in sufficient quantity and with an appropriate geometry (e.g., a sphere of sufficient size), it can form a critical mass. During fission, a fraction of the nuclear binding energy, which holds a nucleus together, is released as a large amount of electromagnetic and kinetic energy (much of the latter being quickly converted to thermal energy). Fission of a kilogram of plutonium-239 can produce an explosion equivalent to . It is this energy that makes plutonium-239 useful in nuclear weapons and reactors.

The presence of the isotope plutonium-240 in a sample limits its nuclear bomb potential, as plutonium-240 has a relatively high spontaneous fission rate (~440 fissions per second per gram—over 1,000 neutrons per second per gram), raising the background neutron levels and thus increasing the risk of predetonation. Plutonium is identified as either weapons-grade, fuel-grade, or reactor-grade based on the percentage of plutonium-240 that it contains. Weapons-grade plutonium contains less than 7% plutonium-240. Fuel-grade plutonium contains from 7% to less than 19%, and power reactor-grade contains 19% or more plutonium-240. Supergrade plutonium, with less than 4% of plutonium-240, is used in U.S. Navy weapons stored in proximity to ship and submarine crews, due to its lower radioactivity. The isotope plutonium-238 is not fissile but can undergo nuclear fission easily with fast neutrons as well as alpha decay. All plutonium isotopes can be "bred" into fissile material with one or more neutron absorptions, whether followed by beta decay or not. This makes non-fissile isotopes of Plutonium a fertile material.

Isotopes and nucleosynthesis

Twenty radioactive isotopes of plutonium have been characterized. The longest-lived are plutonium-244, with a half-life of 80.8 million years, plutonium-242, with a half-life of 373,300 years, and plutonium-239, with a half-life of 24,110 years. All of the remaining radioactive isotopes have half-lives that are less than 7,000 years. This element also has eight metastable states, though all have half-lives less than one second. Plutonium-244 has been found in interstellar space and is has the longest half-life of any non-primordial radioisotope.

The known isotopes of plutonium range in mass number from 228 to 247. The primary decay modes of isotopes with mass numbers lower than the most stable isotope, plutonium-244, are spontaneous fission and alpha emission, mostly forming uranium (92 protons) and neptunium (93 protons) isotopes as decay products (neglecting the wide range of daughter nuclei created by fission processes). The primary decay mode for isotopes with mass numbers higher than plutonium-244 is beta emission, mostly forming americium (95 protons) isotopes as decay products. Plutonium-241 is the parent isotope of the neptunium decay series, decaying to americium-241 via beta emission.

Plutonium-238 and 239 are the most widely synthesized isotopes. Plutonium-239 is synthesized via the following reaction using uranium (U) and neutrons (n) via beta decay (β⁻) with neptunium (Np) as an intermediate:

:
+ -> -> beta^- 3.5 \ \ce -> beta^- .3565 \ \ce d

Neutrons from the fission of uranium-235 are captured by uranium-238 nuclei to form uranium-239; a beta decay converts a neutron into a proton to form neptunium-239 (half-life 2.36 days) and another beta decay forms plutonium-239. Egon Bretscher working on the British Tube Alloys project predicted this reaction theoretically in 1940.

Plutonium-238 is synthesized by bombarding uranium-238 with deuterons (D, the nuclei of heavy hydrogen) in the following reaction:

:$\begin \ce &\ce \\ &\ce \end$

In this process, a deuteron hitting uranium-238 produces two neutrons and neptunium-238, which spontaneously decays by emitting negative beta particles to form plutonium-238. Plutonium-238 can also be produced by neutron irradiation of neptunium-237.

Decay heat and fission properties

Plutonium isotopes undergo radioactive decay, which produces decay heat. Different isotopes produce different amounts of heat per mass. The decay heat is usually listed as watt/kilogram, or milliwatt/gram. In larger pieces of plutonium (e.g. a weapon pit) and inadequate heat removal the resulting self-heating may be significant.

Compounds and chemistry

At room temperature, pure plutonium is silvery in color but gains a tarnish when oxidized. The element displays four common ionic oxidation states in aqueous solution and one rare one:
* Pu(III), as Pu³⁺ (blue lavender)
* Pu(IV), as Pu⁴⁺ (yellow brown)
* Pu(V), as (light pink)
* Pu(VI), as (pink orange)
* Pu(VII), as (green)—the heptavalent ion is rare.

The color shown by plutonium solutions depends on both the oxidation state and the nature of the acid anion. It is the acid anion that influences the degree of complexing—how atoms connect to a central atom—of the plutonium species. Additionally, the formal +2 oxidation state of plutonium is known in the complex (2.2.2-cryptand) u^IICp″₃ Cp″ = C₅H₃(SiMe₃)₂.

A +8 oxidation state is possible as well in the volatile tetroxide . Though it readily decomposes via a reduction mechanism similar to , can be stabilized in alkaline solutions and chloroform.

Metallic plutonium is produced by reacting plutonium tetrafluoride with barium, calcium or lithium at 1200 °C. Metallic plutonium is attacked by acids, oxygen, and steam but not by alkalis and dissolves easily in concentrated hydrochloric, hydroiodic and perchloric acids. Molten metal must be kept in a vacuum or an inert atmosphere to avoid reaction with air. At 135 °C the metal will ignite in air and will explode if placed in carbon tetrachloride.

Plutonium is a reactive metal. In moist air or moist argon, the metal oxidizes rapidly, producing a mixture of oxides and hydrides. If the metal is exposed long enough to a limited amount of water vapor, a powdery surface coating of PuO₂ is formed. Also formed is plutonium hydride but an excess of water vapor forms only PuO₂.

Plutonium shows enormous, and reversible, reaction rates with pure hydrogen, forming plutonium hydride. It also reacts readily with oxygen, forming PuO and PuO₂ as well as intermediate oxides; plutonium oxide fills 40% more volume than plutonium metal. The metal reacts with the halogens, giving rise to compounds with the general formula PuX₃ where X can be F, Cl, Br or I and PuF₄ is also seen. The following oxyhalides are observed: PuOCl, PuOBr and PuOI. It will react with carbon to form PuC, nitrogen to form PuN and silicon to form PuSi₂.

The organometallic chemistry of plutonium complexes is typical for organoactinide species; a characteristic example of an organoplutonium compound is plutonocene. Computational chemistry methods indicate an enhanced covalent character in the plutonium-ligand bonding.

Powders of plutonium, its hydrides and certain oxides like Pu₂O₃
are pyrophoric, meaning they can ignite spontaneously at ambient temperature and are therefore handled in an inert, dry atmosphere of nitrogen or argon. Bulk plutonium ignites only when heated above 400 °C. Pu₂O₃ spontaneously heats up and transforms into PuO₂, which is stable in dry air, but reacts with water vapor when heated.

Crucibles used to contain plutonium need to be able to withstand its strongly reducing properties. Refractory metals such as tantalum and tungsten along with the more stable oxides, borides, carbides, nitrides and silicides can tolerate this. Melting in an electric arc furnace can be used to produce small ingots of the metal without the need for a crucible.

Cerium is used as a chemical simulant of plutonium for development of containment, extraction, and other technologies.

Electronic structure

Plutonium is an element in which the 5f electrons are the transition border between delocalized and localized; it is therefore considered one of the most complex elements. The anomalous behavior of plutonium is caused by its electronic structure. The energy difference between the 6d and 5f subshells is very low. The size of the 5f shell is just enough to allow the electrons to form bonds within the lattice, on the very boundary between localized and bonding behavior. The proximity of energy levels leads to multiple low-energy electron configurations with near equal energy levels. This leads to competing 5fⁿ7s² and 5fⁿ⁻¹6d¹7s² configurations, which causes the complexity of its chemical behavior. The highly directional nature of 5f orbitals is responsible for directional covalent bonds in molecules and complexes of plutonium.

Alloys

Plutonium can form alloys and intermediate compounds with most other metals. Exceptions include lithium, sodium, potassium, rubidium and caesium of the alkali metals; and magnesium, calcium, strontium, and barium of the alkaline earth metals; and europium and ytterbium of the rare earth metals. Partial exceptions include the refractory metals chromium, molybdenum, niobium, tantalum, and tungsten, which are soluble in liquid plutonium, but insoluble or only slightly soluble in solid plutonium. Gallium, aluminium, americium, scandium and cerium can stabilize the δ phase of plutonium for room temperature. Silicon, indium, zinc and zirconium allow formation of metastable δ state when rapidly cooled. High amounts of hafnium, holmium and thallium also allows some retention of the δ phase at room temperature. Neptunium is the only element that can stabilize the α phase at higher temperatures.

Plutonium alloys can be produced by adding a metal to molten plutonium. If the alloying metal is sufficiently reductive, plutonium can be added in the form of oxides or halides. The δ phase plutonium–gallium and plutonium–aluminium alloys are produced by adding plutonium(III) fluoride to molten gallium or aluminium, which has the advantage of avoiding dealing directly with the highly reactive plutonium metal.
* Plutonium–gallium is used for stabilizing the δ phase of plutonium, avoiding the α-phase and α–δ related issues. Its main use is in pits of implosion nuclear weapons.
* Plutonium–aluminium is an alternative to the Pu–Ga alloy. It was the original element considered for δ phase stabilization, but its tendency to react with the alpha particles and release neutrons reduces its usability for nuclear weapon pits. Plutonium–aluminium alloy can be also used as a component of nuclear fuel.
* Plutonium–gallium–cobalt alloy (PuCoGa₅) is an unconventional superconductor, showing superconductivity below 18.5 K, an order of magnitude higher than the highest between heavy fermion systems, and has large critical current.
* Plutonium–zirconium alloy can be used as nuclear fuel.
* Plutonium–cerium and plutonium–cerium–cobalt alloys are used as nuclear fuels.
* Plutonium–uranium, with about 15–30 mol.% plutonium, can be used as a nuclear fuel for fast breeder reactors. Its pyrophoric nature and high susceptibility to corrosion to the point of self-igniting or disintegrating after exposure to air require alloying with other components. Addition of aluminium, carbon or copper does not improve disintegration rates markedly, zirconium and iron alloys have better corrosion resistance but they disintegrate in several months in air as well. Addition of titanium and/or zirconium significantly increases the melting point of the alloy.
* Plutonium–uranium–titanium and plutonium–uranium–zirconium were investigated for use as nuclear fuels. The addition of the third element increases corrosion resistance, reduces flammability, and improves ductility, fabricability, strength, and thermal expansion. Plutonium–uranium–molybdenum has the best corrosion resistance, forming a protective film of oxides, but titanium and zirconium are preferred for physics reasons.
* Thorium–uranium–plutonium was investigated as a nuclear fuel for fast breeder reactors.

Occurrence

Trace amounts of plutonium-238, plutonium-239, plutonium-240, and plutonium-244 can be found in nature. Small traces of plutonium-239, a few parts per trillion, and its decay products are naturally found in some concentrated ores of uranium, such as the natural nuclear fission reactor in Oklo, Gabon. The ratio of plutonium-239 to uranium at the Cigar Lake Mine uranium deposit ranges from to . These trace amounts of ²³⁹Pu originate in the following fashion: on rare occasions, ²³⁸U undergoes spontaneous fission, and in the process, the nucleus emits one or two free neutrons with some kinetic energy. When one of these neutrons strikes the nucleus of another ²³⁸U atom, it is absorbed by the atom, which becomes ²³⁹U. With a relatively short half-life, ²³⁹U decays to ²³⁹Np, which decays into ²³⁹Pu. Finally, exceedingly small amounts of plutonium-238, attributed to the extremely rare double beta decay of uranium-238, have been found in natural uranium samples.

Due to its relatively long half-life of about 80 million years, it was suggested that plutonium-244 occurs naturally as a primordial nuclide, but early reports of its detection could not be confirmed. However, its long half-life ensured its circulation across the solar system before its extinction, and indeed, evidence of the spontaneous fission of extinct ²⁴⁴Pu has been found in meteorites. The former presence of ²⁴⁴Pu in the early Solar System has been confirmed, since it manifests itself today as an excess of its daughters, either ²³² Th (from the alpha decay pathway) or xenon isotopes (from its spontaneous fission). The latter are generally more useful, because the chemistries of thorium and plutonium are rather similar (both are predominantly tetravalent) and hence an excess of thorium would not be strong evidence that some of it was formed as a plutonium daughter. ²⁴⁴Pu has the longest half-life of all transuranic nuclides and is produced only in the r-process in supernovae and colliding neutron stars; when nuclei are ejected from these events at high speed to reach Earth, ²⁴⁴Pu alone among transuranic nuclides has a long enough half-life to survive the journey, and hence tiny traces of live interstellar ²⁴⁴Pu have been found in the deep sea floor. Because ²⁴⁰Pu also occurs in the decay chain of ²⁴⁴Pu, it must thus also be present in secular equilibrium, albeit in even tinier quantities.

Minute traces of plutonium are usually found in the human body due to the 550 atmospheric and underwater nuclear tests that have been carried out, and to a small number of major nuclear accidents. Most atmospheric and underwater nuclear testing was stopped by the Limited Test Ban Treaty in 1963, which of the nuclear powers was signed and ratified by the United States, United Kingdom and