Plutonium
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Plutonium 94Pu
|
General properties |
Name, symbol |
plutonium, Pu |
Pronunciation |
//
ploo-TOH-nee-əm |
Appearance |
silvery white, tarnishing to dark gray in air |
Plutonium in the periodic table |
|
Atomic number |
94 |
Standard atomic weight |
(244) |
Element category |
actinide |
Group, period, block |
group n/a, period 7, f-block |
Electron configuration |
[Rn] 5f6 7s2
per shell: 2, 8, 18, 32, 24, 8, 2 |
Physical properties |
Phase |
solid |
Melting point |
912.5 K (639.4 °C, 1182.9 °F) |
Boiling point |
3505 K (3228 °C, 5842 °F) |
Density (near r.t.) |
19.816 g·cm−3 (at 0 °C, 101.325 kPa) |
Liquid density |
at m.p.: 16.63 g·cm−3 |
Heat of fusion |
2.82 kJ·mol−1 |
Heat of vaporization |
333.5 kJ·mol−1 |
Molar heat capacity |
35.5 J·mol−1·K−1 |
Vapor pressure
P (Pa) |
1 |
10 |
100 |
1 k |
10 k |
100 k |
at T (K) |
1756 |
1953 |
2198 |
2511 |
2926 |
3499 |
|
Atomic properties |
Oxidation states |
8, 7, 6, 5, 4, 3, 2, 1 (an amphoteric oxide) |
Electronegativity |
1.28 (Pauling scale) |
Ionization energies |
1st: 584.7 kJ·mol−1 |
Atomic radius |
empirical: 159 pm |
Covalent radius |
187±1 pm |
Miscellanea |
Crystal structure |
monoclinic
|
Speed of sound |
2260 m·s−1 |
Thermal expansion |
46.7 µm·m−1·K−1 (at 25 °C) |
Thermal conductivity |
6.74 W·m−1·K−1 |
Electrical resistivity |
at 0 °C: 1.460 µΩ·m |
Magnetic ordering |
paramagnetic[1] |
Young's modulus |
96 GPa |
Shear modulus |
43 GPa |
Poisson ratio |
0.21 |
CAS Number |
7440-07-5 |
History |
Naming |
after dwarf planet Pluto, itself named after classical god of the underworld Pluto |
Discovery |
Glenn T. Seaborg, Arthur Wahl, Joseph W. Kennedy, Edwin McMillan (1940–1) |
Most stable isotopes |
Main article: Isotopes of plutonium |
|
· references |
Plutonium is a
transuranic 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 expand the sample up to 70% in volume, which in turn flake off as a powder that can
spontaneously ignite. It is
radioactive and can accumulate in the
bones. These properties make the handling of plutonium dangerous.
Plutonium is the heaviest
primordial element by virtue of its most stable
isotope,
plutonium-244, whose
half-life of about 80 million years is just long enough for the element to be found in trace quantities in nature.
[3] Plutonium is mostly a byproduct of
nuclear reactions in reactors where some of the
neutrons released by the
fission process convert uranium-238 nuclei into plutonium.
[4]
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 88 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.
A team led by
Glenn T. Seaborg and
Edwin McMillan at the
University of California, Berkeley, first synthesized plutonium in 1940 by bombarding
uranium-238 with
deuterons.
Trace amounts of plutonium were subsequently discovered in nature.
Producing plutonium in useful quantities for the first time was a major
part of the
Manhattan Project during
World War II, which developed the first atomic bombs. The first
nuclear test, "
Trinity" (July 1945), and the second atomic bomb used to destroy a city (
Nagasaki, Japan, in August 1945), "
Fat Man", both had cores of plutonium-239.
Human radiation experiments studying plutonium were conducted without
informed consent, and several
criticality accidents, some lethal, occurred during and 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.
[5][6] At room temperature plutonium is in its
α form (
alpha). This, the most common structural form of the element (
allotrope), is about as hard and brittle as
grey 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 (640 °C) and an unusually high
boiling point (3,228 °C).
[5]
Alpha decay, the release of a high-energy
helium nucleus, is the most common form of
radioactive decay for plutonium.
[7] A 5 kg mass of
239Pu contains about
12.5×1024 atoms. With a half-life of 24,100 years, about
11.5×1012 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.
[8][9]
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.
[10] This trend continues down to 100
K, below which resistivity rapidly decreases for fresh samples.
[10]
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.
[10]
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.
[11] Self-irradiation can also lead to
annealing which counteracts some of the fatigue effects as temperature increases above 100 K.
[12]
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.
[10] Near the melting point, the liquid plutonium has also very high
viscosity and
surface tension as compared to other metals.
[11]
Allotropes
Plutonium has six allotropes at ambient pressure:
alpha (α),
beta (β),
gamma (γ),
delta (δ),
delta prime (δ'), &
epsilon (ε)
[13]
Plutonium normally has six allotropes and forms a seventh (zeta, ζ) at high temperature within a limited pressure range.
[13] 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.
[11] The densities of the different allotropes vary from 16.00 g/cm
3 to 19.86 g/cm
3.
[14]
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 form (
beta) at slightly higher temperatures.
[15] 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.
[13]
Plutonium in the δ 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.
[15] The delta form has more typical metallic character, and is roughly as strong and malleable as aluminium.
[13] In fission weapons, the explosive
shock waves
used to compress a plutonium core will also cause a transition from the
usual delta phase plutonium to the denser alpha form, significantly
helping to achieve
supercriticality.
[16] The ε phase, the highest temperature solid allotrope, exhibits anomalously high atomic
self-diffusion compared to other elements.
[11]
Nuclear fission
Plutonium is a radioactive
actinide metal whose
isotope,
plutonium-239, is one of the three primary
fissile isotopes
[17] (
uranium-233 and
uranium-235 are the other two);
[18] 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.
[19] During fission, a fraction of the
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 21,000
tons of TNT (88,000
GJ).
[8] 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),
[20] raising the background neutron levels and thus increasing the risk of
predetonation.
[21] Plutonium is identified as either
weapons-grade,
fuel grade, or power 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.
[22] The isotope
plutonium-238 is not
fissile but can undergo nuclear fission easily with
fast neutrons as well as
alpha decay.
[8]
Isotopes and synthesis
Uranium-plutonium and thorium-uranium chains
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.
[7]
The 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
α 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
β 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 β or electron emission.
[7][23]
Plutonium-238 and 239 are the most widely synthesized isotopes.
[8] Plutonium-239 is synthesized via the following reaction using uranium (U) and neutrons (n) via beta decay (β
−) with neptunium (Np) as an intermediate:
[24]
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 Np-239 (half-life 2.36 days) and another beta decay forms plutonium-239.
[25] Workers on the
Tube Alloys project had 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:
[26]
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.
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
case of larger pieces of plutonium (e.g. a weapon pit) and inadequate
heat removal the resulting self-heating may be significant. All isotopes
produce weak gamma on decay.
Decay heat of plutonium isotopes[27]
Isotope |
Decay mode |
Half-life (years) |
Decay heat (W/kg) |
Spontaneous fission neutrons (1/(g·s)) |
Comment |
238Pu |
alpha to 234U |
87.74 |
560 |
2600 |
Very high decay heat. Even in small amounts can cause significant self-heating. Used on its own in radioisotope thermoelectric generators. |
239Pu |
alpha to 235U |
24100 |
1.9 |
0.022 |
The principal fissile isotope in use. |
240Pu |
alpha to 236U, spontaneous fission |
6560 |
6.8 |
910 |
The principal impurity in samples of the 239Pu isotope. The plutonium grade is usually listed as percentage of 240Pu. High spontaneous fission hinders use in nuclear weapons. |
241Pu |
beta-minus, to 241Am |
14.4 |
4.2 |
0.049 |
Decays to americium-241; its buildup presents a radiation hazard in older samples. |
242Pu |
alpha to 238U |
376000 |
0.1 |
1700 |
|
Americium-241,
the decay product of plutonium-241, has half-life of 430 years, 1.2
spontaneous fissions per gram per second, and decay heat of 114 watts
per kilogram. As its decay produces highly penetrative gamma rays, its
presence in plutonium, determined by the original concentration of
plutonium-241 and the sample age, increases the radiation exposure of
surrounding structures and personnel.
Compounds and chemistry
Various oxidation states of plutonium in solution
At room temperature, pure plutonium is silvery in color but gains a tarnish when oxidized.
[28] The element displays four common ionic
oxidation states in
aqueous solution and one rare one:
[14]
- Pu(III), as Pu3+ (blue lavender)
- Pu(IV), as Pu4+ (yellow brown)
- Pu(V), as PuO+
2 (light pink)[note 1]
- Pu(VI), as PuO2+
2 (pink orange)
- Pu(VII), as PuO3−
5 (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.
[29] It is the acid anion that influences the degree of
complexing—how atoms connect to a central atom—of the plutonium species.
Metallic plutonium is produced by reacting
plutonium tetrafluoride with
barium,
calcium or
lithium at 1200 °C.
[30] It is attacked by
acids,
oxygen, and steam but not by
alkalis and dissolves easily in concentrated
hydrochloric,
hydroiodic and
perchloric acids.
[31] Molten metal must be kept in a
vacuum or an
inert atmosphere to avoid reaction with air.
[15] At 135 °C the metal will ignite in air and will explode if placed in
carbon tetrachloride.
[32]
Plutonium
pyrophoricity can cause it to look like a glowing ember under certain conditions.
Twenty micrograms of pure plutonium hydroxide.
[33]
Plutonium is a reactive metal. In moist air or moist
argon, the metal oxidizes rapidly, producing a mixture of
oxides and
hydrides.
[5] If the metal is exposed long enough to a limited amount of water vapor, a powdery surface coating of
PuO2 is formed.
[5] Also formed is
plutonium hydride but an excess of water vapor forms only PuO
2.
[31]
Plutonium shows enormous, and reversible, reaction rates with pure hydrogen, forming
plutonium hydride.
[11] It also reacts readily with oxygen, forming PuO and PuO
2 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 PuX
3 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 PuSi
2.
[14][32]
Powders of plutonium, its hydrides and certain oxides like Pu
2O
3 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. Pu
2O
3 spontaneously heats up and transforms into PuO
2, which is stable in dry air, but reacts with water vapor when heated.
[34]
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.
[15]
Cerium is used as a chemical simulant of plutonium for development of containment, extraction, and other technologies.
[35]
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.
[36]
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 5f
n7s
2 and 5f
n−16d
17s
2
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.
[11]
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.
[31] 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.
[31] 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 retaining some of the δ phase at room temperature.
Neptunium is the only element that can stabilize the α phase at higher temperatures.
[11]
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.
[37]
- 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.[38]
- 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.[39]
- Plutonium-gallium-cobalt alloy (PuCoGa5) is an unconventional superconductor, showing superconductivity below 18.5 kelvin, an order of magnitude higher than the highest between heavy fermion systems, and has large critical current.[36][40]
- Plutonium-zirconium alloy can be used as nuclear fuel.[41]
- Plutonium-cerium and plutonium-cerium-cobalt alloys are used as nuclear fuels.[42]
- 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 did 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.[43]
- 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.[43]
- Thorium-uranium-plutonium was investigated as a nuclear fuel for fast breeder reactors.[43]
Occurrence
Trace amounts of at least three plutonium isotopes (plutonium-238,
239, and 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,
[44] such as the
natural nuclear fission reactor in
Oklo,
Gabon.
[45] The ratio of plutonium-239 to uranium at the
Cigar Lake Mine uranium deposit ranges from
2.4×10−12 to
44×10−12.
[46] Even smaller amounts of
primordial plutonium-244 occur naturally due to its relatively long half-life of about 80 million years.
[47] 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
neptunium-239 (
239Np), and then
239Np decays into
239Pu.
Since the relatively long-lived isotope plutonium-240 occurs in the
decay chain
of plutonium-244 it should also be present, albeit 10,000 times rarer
still. 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.
[48]
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 was signed and ratified by the United States, the United Kingdom, the
Soviet Union, and other nations. Continued atmospheric nuclear weapons testing since 1963 by non-treaty nations included those by
China (
atomic bomb test above the
Gobi Desert in 1964,
hydrogen bomb
test in 1967, and follow-on tests), and France (tests as recently as
the 1990s). Because it is deliberately manufactured for nuclear weapons
and nuclear reactors, plutonium-239 is the most abundant isotope of
plutonium by far.
[32]
History
Discovery
Enrico Fermi and a team of scientists at the
University of Rome reported that they had discovered element 94 in 1934.
[49] Fermi called the element
hesperium and mentioned it in his Nobel Lecture in 1938.
[50] The sample was actually a mixture of
barium,
krypton, and other elements, but this was not known at the time because
nuclear fission had not been discovered yet.
[51]
The breakthrough with plutonium was at the
Cavendish Laboratory,
Cambridge by
Egon Bretscher and
Norman Feather.
They realized that a slow neutron reactor fuelled with uranium would
theoretically produce substantial amounts of plutonium-239 as a
by-product. This is because U-238 absorbs
slow neutrons and forms a new isotope U-239. The new isotope's nucleus rapidly emits an electron through
beta decay
producing a new element with a mass of 239 and an atomic number of 93.
This element's nucleus then also emits an electron and becomes a new
element of mass 239 but with an atomic number 94 and a much greater
half-life. Bretscher and Feather showed theoretically feasible grounds
that element 94 would be readily 'fissionable' by both slow and fast
neutrons, and had the added advantage of being chemically different from
uranium, and could easily be separated from it.
This new development was also confirmed in independent work by
Edwin M. McMillan and
Philip Abelson at
Berkeley Radiation Laboratory also in 1940.
Nicholas Kemmer of the Cambridge team proposed the names
neptunium
for the new element 93 and plutonium for 94 by analogy with the outer
planets Neptune and Pluto beyond Uranus (uranium being element 92). The
Americans fortuitously suggested the same names.
Plutonium (specifically, plutonium-238) was first produced and
isolated on December 14, 1940, and chemically identified on February 23,
1941, by Dr.
Glenn T. Seaborg,
Edwin M. McMillan,
J. W. Kennedy, and
A. C. Wahl by
deuteron bombardment of uranium in the 60-inch (150 cm)
cyclotron at the
University of California, Berkeley.
[52][53] In the 1940 experiment,
neptunium-238 was created directly by the bombardment but decayed by
beta emission with a half-life of a little over two days, which indicated the formation of element 94.
[32]
A paper documenting the discovery was prepared by the team and sent to the journal
Physical Review in March 1941.
[32]
The paper was withdrawn before publication after the discovery that an
isotope of the new element (plutonium-239) could undergo nuclear fission
in a way that might be useful in an
atomic bomb. Publication was delayed until a year after the end of
World War II due to security concerns.
[17]
Edwin McMillan had recently named the first transuranium element after the planet
Neptune and suggested that element 94, being the next element in the series, be named for what was then considered the next planet,
Pluto.
[8][note 2] Seaborg originally considered the name "plutium", but later thought that it did not sound as good as "plutonium."
[54] He chose the letters "Pu" as a joke, which passed without notice into the periodic table.
[note 3]
Alternative names considered by Seaborg and others were "ultimium" or
"extremium" because of the erroneous belief that they had found the last
possible
element on the
periodic table.
[55]
Early research
The basic chemistry of plutonium was found to resemble uranium after a few months of initial study.
[32] Early research was continued at the secret
Metallurgical Laboratory of the
University of Chicago.
On August 20, 1942, a trace quantity of this element was isolated and
measured for the first time. About 50 micrograms of plutonium-239
combined with uranium and fission products was produced and only about
1 microgram was isolated.
[44][56] This procedure enabled chemists to determine the new element's atomic weight.
[57][note 4]
In November 1943 some
plutonium trifluoride was reduced to create the first sample of plutonium metal: a few micrograms of metallic beads.
[44] Enough plutonium was produced to make it the first synthetically made element to be visible with the unaided eye.
[58]
The nuclear properties of plutonium-239 were also studied;
researchers found that when it is hit by a neutron it breaks apart
(fissions) by releasing more neutrons and energy. These neutrons can hit
other atoms of plutonium-239 and so on in an exponentially fast
chain reaction. This can result in an explosion large enough to destroy a city if enough of the isotope is concentrated to form a
critical mass.
[32]
Production during the Manhattan Project
During World War II the U.S. government established the
Manhattan Project,
which was tasked with developing an atomic bomb. The three primary
research and production sites of the project were the plutonium
production facility at what is now the
Hanford Site, the
uranium enrichment facilities at
Oak Ridge, Tennessee, and the weapons research and design laboratory, now known as
Los Alamos National Laboratory.
[59]
The Hanford
B Reactor face under construction—the first plutonium-production reactor.
The
Hanford site
represents two-thirds of the nation's high-level radioactive waste by
volume. Nuclear reactors line the riverbank at the Hanford Site along
the
Columbia River in January 1960.
The first production reactor that made plutonium-239 was the
X-10 Graphite Reactor. It went online in 1943 and was built at a facility in Oak Ridge that later became the
Oak Ridge National Laboratory.
[32][note 5]
On April 5, 1944,
Emilio Segrè at Los Alamos received the first sample of reactor-produced plutonium from Oak Ridge.
[60]
Within ten days, he discovered that reactor-bred plutonium had a higher
concentration of the isotope plutonium-240 than cyclotron-produced
plutonium. Plutonium-240 has a high
spontaneous fission rate, raising the overall background neutron level of the plutonium sample. The original
gun-type plutonium weapon, code-named "
Thin Man", had to be abandoned as a result—the increased number of spontaneous neutrons meant that nuclear pre-detonation (a
fizzle) would be likely.
The entire plutonium weapon design effort at Los Alamos was soon changed to the more complicated implosion device, code-named "
Fat Man." With an implosion weapon, a solid (or, in later designs, hollow)
sphere of plutonium
is compressed to a high density with explosive lenses—a technically
more daunting task than the simple gun-type design, but necessary to use
plutonium for weapons purposes. (
Enriched uranium, by contrast, can be used with either method.)
[60]
Construction of the Hanford
B Reactor,
the first industrial-sized nuclear reactor for the purposes of material
production, was completed in March 1945. B Reactor produced the fissile
material for the plutonium weapons used during World War II.
[note 6]
B, D and F were the initial reactors built at Hanford, and six
additional plutonium-producing reactors were built later at the site.
[61]
In the 2013 book,
Plutopia: Nuclear Families, Atomic Cities, and the Great Soviet and American Plutonium Disasters (Oxford),
Kate Brown
explores the health of affected citizens in the United States, and the
“slow-motion disasters” that still threaten the environments where the
plutonium production plants are located. According to Brown, the plants
at Hanford (and Mayak in the USSR), over a period of four decades, “both
released more than 200 million curies of radioactive isotopes into the
surrounding environment -- twice the amount expelled in the
Chernobyl disaster in each instance”.
[62] Most of this
radioactive contamination
over the years were part of normal operations, but unforeseen accidents
did occur and plant management kept this secret, as the pollution
continued unabated. Even today, as pollution threats to health and the
environment persist, the government keeps knowledge about the associated
risks from the public.
[62]
In 2004, a
safe was discovered during excavations of a burial trench at the
Hanford nuclear site.
Inside the safe were various items, including a large glass bottle
containing a whitish slurry which was subsequently identified as the
oldest sample of weapons-grade plutonium known to exist. Isotope
analysis by
Pacific Northwest National Laboratory indicated that the plutonium in the bottle was manufactured in the
X-10 reactor at
Oak Ridge during 1944.
[63][64][65]
Trinity and Fat Man atomic bombs
Because of the presence of plutonium-240 in reactor-bred plutonium, the implosion design was developed for the "
Fat Man" and "
Trinity" weapons
The first atomic bomb test, codenamed
"Trinity" and detonated on July 16, 1945, near
Alamogordo, New Mexico, used plutonium as its fissile material.
[44] The implosion design of "
the gadget",
as the Trinity device was code-named, used conventional explosive
lenses to compress a sphere of plutonium into a supercritical mass,
which was simultaneously showered with neutrons from the
"Urchin", an initiator made of
polonium and
beryllium (
neutron source:
(α, n) reaction).
[32]
Together, these ensured a runaway chain reaction and explosion. The
overall weapon weighed over 4 tonnes, although it used just 6.2 kg of
plutonium in its core.
[66]
About 20% of the plutonium used in the Trinity weapon underwent
fission, resulting in an explosion with an energy equivalent to
approximately 20,000
tons of TNT.
[67][note 7]
An identical design was used in the "
Fat Man" atomic bomb dropped on
Nagasaki,
Japan, on August 9, 1945, killing 70,000 people and wounding another 100,000.
[32] The "
Little Boy" bomb dropped on
Hiroshima three days earlier used
uranium-235, not plutonium. Japan capitulated on August 15 to General
Douglas MacArthur. Only after the announcement of the first atomic bombs was the existence of plutonium made public.
Cold War use and waste
Large stockpiles of
weapons-grade plutonium were built up by both the
Soviet Union and the United States during the
Cold War. The U.S. reactors at Hanford and the
Savannah River Site in South Carolina produced 103 tonnes,
[68] and an estimated 170 tonnes of military-grade plutonium was produced in USSR.
[69][note 8] Each year about 20 tonnes of the element is still produced as a by-product of the
nuclear power industry.
[14]
As much as 1000 tonnes of plutonium may be in storage with more than
200 tonnes of that either inside or extracted from nuclear weapons.
[32] SIPRI
estimated the world plutonium
stockpile in 2007 as about 500 tons, divided equally between weapon and civilian stocks.
[70]
Since the end of the Cold War these stockpiles have become a focus of
nuclear proliferation concerns. In the U.S., some plutonium extracted from dismantled nuclear weapons is melted to form glass logs of
plutonium oxide that weigh two tonnes.
[32] The glass is made of
borosilicates mixed with
cadmium and
gadolinium.
[note 9] These logs are planned to be encased in
stainless steel and stored as much as 4 km (2 mi) underground in bore holes that will be back-filled with
concrete.
[32] As of 2008, the only facility in the U.S. that was scheduled to store plutonium in this way was the
Yucca Mountain nuclear waste repository, which is about 100 miles (160 km) north-east of
Las Vegas, Nevada.
[71]
Local and state opposition to this plan delayed efforts to store
nuclear waste at Yucca Mountain. In March 2010, the Department of Energy
withdrew its license application for the Yucca Mountain repository
"with prejudice" and eliminated funding for the Office of Civilian
Radioactive Waste Management, which had managed the Yucca Mountain site
for 25 years, canceling the program.
[72]
Medical experimentation
During and after the end of World War II, scientists working on the
Manhattan Project and other nuclear weapons research projects conducted
studies of the effects of plutonium on laboratory animals and human
subjects.
[73] Animal studies found that a few milligrams of plutonium per kilogram of tissue is a lethal dose.
[74]
In the case of human subjects, this involved injecting solutions
containing (typically) five micrograms of plutonium into hospital
patients thought to be either terminally ill, or to have a life
expectancy of less than ten years either due to age or chronic disease
condition.
[73]
This was reduced to one microgram in July 1945 after animal studies
found that the way plutonium distributed itself in bones was more
dangerous than
radium.
[74] Many of these experiments resulted in strong mutation.
[citation needed] Most of the subjects,
Eileen Welsome says, were poor, powerless, and sick.
[75]
From 1945 to 1947, eighteen human test subjects were injected with plutonium without
informed consent.
The tests were used to create diagnostic tools to determine the uptake
of plutonium in the body in order to develop safety standards for
working with plutonium.
[73] Other experiments directed by the
United States Atomic Energy Commission and the Manhattan Project continued into the 1970s.
The Plutonium Files
chronicles the lives of the subjects of the secret program by naming
each person involved and discussing the ethical and medical research
conducted in secret by the scientists and doctors. The episode is now
considered to be a serious breach of
medical ethics and of the
Hippocratic Oath.
[76]
The government covered up most of these radiation mishaps until 1993, when President
Bill Clinton
ordered a change of policy and federal agencies then made available
relevant records. The resulting investigation was undertaken by the
president’s
Advisory Committee on Human Radiation Experiments,
and it uncovered much of the material about plutonium research on
humans. The committee issued a controversial 1995 report which said that
"wrongs were committed" but it did not condemn those who perpetrated
them.
[75]
Applications
Explosives
The isotope plutonium-239 is a key fissile component in
nuclear weapons, due to its ease of fission and availability. Encasing the bomb's
plutonium pit in a
tamper (an optional layer of dense material) decreases the amount of plutonium needed to reach
critical mass by
reflecting escaping neutrons
back into the plutonium core. This reduces the amount of plutonium
needed to reach criticality from 16 kg to 10 kg, which is a sphere with a
diameter of about 10 centimeters (4 in).
[77] This critical mass is about a third of that for uranium-235.
[8]
The "
Fat Man"–type plutonium bombs produced during the
Manhattan Project
used explosive compression of plutonium to obtain significantly higher
densities than normal, combined with a central neutron source to begin
the reaction and increase efficiency. Thus only 6.2 kg of plutonium was
needed for an
explosive yield equivalent to 20 kilotons of
TNT.
[67][78] (See also
nuclear weapon design.)
Hypothetically, as little as 4 kg of plutonium—and maybe even
less—could be used to make a single atomic bomb using very sophisticated
assembly designs.
[78]
Mixed oxide fuel
Spent nuclear fuel from normal
light water reactors
contains plutonium, but it is a mixture of plutonium-242, 240, 239 and
238. The mixture is not sufficiently enriched for efficient nuclear
weapons, but can be used once as
MOX fuel. Accidental
neutron capture
causes the amount of plutonium-242 and 240 to grow each time the
plutonium is irradiated in a reactor with low-speed "thermal" neutrons,
so that after the second cycle, the plutonium can only be consumed by
fast neutron reactors.
If fast neutron reactors are not available (the normal case), excess
plutonium is usually discarded, and forms the longest-lived component of
nuclear waste. The desire to consume this plutonium and other
transuranic fuels and reduce the radiotoxicity of the waste is the usual reason nuclear engineers give to make fast neutron reactors.
The most common chemical process,
PUREX (
Plutonium–
URanium
EXtraction)
reprocesses spent nuclear fuel to extract plutonium and uranium which can be used to form a mixed oxide "
MOX fuel" for reuse in nuclear reactors. Weapons grade plutonium can be added to the fuel mix. MOX fuel is used in
light water reactors
and consists of 60 kg of plutonium per tonne of fuel; after four years,
three-quarters of the plutonium is burned (turned into other elements).
[32] Breeder reactors are specifically designed to create more fissionable material than they consume.
MOX fuel has been in use since the 1980s and is widely used in Europe.
[79] In September 2000, the United States and the
Russian Federation signed a Plutonium Management and Disposition Agreement by which each agreed to dispose of 34 tonnes of weapon grade plutonium.
[80] The
U.S. Department of Energy
plans to dispose of 34 tonnes of weapon grade plutonium in the United
States before the end of 2019 by converting the plutonium to a MOX fuel
to be used in commercial nuclear power reactors.
[80]
MOX fuel improves total burnup. A fuel rod is reprocessed after three
years of use to remove waste products, which by then account for 3% of
the total weight of the rods.
[32] Any uranium or plutonium isotopes produced during those three years are left and the rod goes back into production.
[note 10] The presence of up to 1%
gallium per mass in weapon grade
plutonium alloy has the potential to interfere with long-term operation of a
light water reactor.
[81]
Plutonium recovered from spent reactor fuel poses a less significant
proliferation hazard, because of excessive contamination with non-fissile
plutonium-240 and
plutonium-242. Separation of the isotopes is not feasible. A dedicated reactor operating on very low
burnup
(hence minimal exposure of newly formed Pu-239 to additional neutrons
which causes it to be transformed to heavier isotopes of plutonium) is
generally required to produce material suitable for use in efficient
nuclear weapons.
While 'weapons-grade' plutonium is defined to contain at least 92%
plutonium-239 (of the total plutonium), the United States have managed
to detonate an
under-20Kt device using plutonium believed to contain only about 85% plutonium-239, so called 'fuel-grade' plutonium.
[82]
The 'reactor grade' plutonium produced by a regular LWR burnup cycle
typically contains less than 60% Pu-239, with up to 30% parasitic
Pu-240/Pu-242, and 10–15% fissile Pu-241.
[82]
It's unknown if a device using plutonium obtained from reprocessed
civil nuclear waste can be detonated, however such a device could
hypothetically
fizzle and spread radioactive materials over a large urban area. The
IAEA
conservatively classifies plutonium of all isotopic vectors as
"direct-use" material, that is, "nuclear material that can be used for
the manufacture of nuclear explosives components without transmutation
or further enrichment".
[82]
241Am
has recently been suggested for use as a denaturing agent in plutonium
reactor fuel rods to further limit its proliferation potential.
[83]
Power and heat source
A glowing cylinder of
238PuO
2
The isotope
plutonium-238 has a half-life of 87.74 years.
[84] It emits a large amount of
thermal energy with low levels of both
gamma rays/particles and
spontaneous neutron rays/particles.
[85]
Being an alpha emitter, it combines high energy radiation with low
penetration and thereby requires minimal shielding. A sheet of paper can
be used to shield against the alpha particles emitted by plutonium-238.
One
kilogram of the isotope can generate about 570 watts of heat.
[8][85]
These characteristics make it well-suited for electrical power
generation for devices which must function without direct maintenance
for timescales approximating a human lifetime. It is therefore used in
radioisotope thermoelectric generators and
radioisotope heater units such as those in the
Cassini,
Voyager, and
New Horizons space probes.
The twin
Voyager
spacecraft were launched in 1977, each containing a 500 watt plutonium
power source. Over 30 years later, each source is still producing about
300 watts which allows limited operation of each spacecraft.
[86] An earlier version of the same technology powered five
Apollo Lunar Surface Experiment Packages, starting with Apollo 12 in 1969.
[32]
Plutonium-238 has also been used successfully to power artificial heart
pacemakers, to reduce the risk of repeated surgery.
[87][88] It has been largely replaced by
lithium-based
primary cells, but as of 2003 there were somewhere between 50 and 100 plutonium-powered pacemakers still implanted and functioning in living patients.
[89] Plutonium-238 was studied as a way to provide supplemental heat to
scuba diving.
[90] Plutonium-238 mixed with beryllium is used to generate neutrons for research purposes.
[32]
Precautions
Toxicity
There are two aspects to the harmful effects of plutonium: the radioactivity and the
heavy metal poison effects.
Isotopes and compounds of plutonium are radioactive and accumulate in
bone marrow. Contamination by plutonium oxide has resulted from
nuclear disasters and radioactive incidents, including military nuclear accidents where nuclear weapons have burned.
[91]
Studies of the effects of these smaller releases, as well as of the
widespread radiation poisoning sickness and death following the
atomic bombings of Hiroshima and Nagasaki, have provided considerable information regarding the dangers, symptoms and prognosis of
radiation poisoning, which in the case of the Japanese
Hibakusha/survivors was largely unrelated to direct plutonium exposure.
[92]
During the decay of plutonium, three types of radiation are
released—alpha, beta, and gamma. Alpha radiation can travel only a short
distance and cannot travel through the outer, dead layer of human skin.
Beta radiation can penetrate human skin, but cannot go all the way
through the body. Gamma radiation can go all the way through the body.
[93] Alpha, beta, and gamma radiation are all forms of
ionizing radiation. Either acute or longer-term exposure carries a danger of
serious health outcomes including
radiation sickness,
genetic damage,
cancer, and death. The danger increases with the amount of exposure.
Even though alpha radiation cannot penetrate the skin, ingested or inhaled plutonium does irradiate internal organs.
[32] The
skeleton, where plutonium accumulates, and the
liver, where it collects and becomes concentrated, are at risk.
[31] Plutonium is not absorbed into the body efficiently when ingested; only 0.04% of plutonium oxide is absorbed after ingestion.
[32] Plutonium absorbed by the body is excreted very slowly, with a
biological half-life of 200 years.
[94]
Plutonium passes only slowly through cell membranes and intestinal
boundaries, so absorption by ingestion and incorporation into bone
structure proceeds very slowly.
[95][96]
Plutonium is more dangerous when inhaled than when ingested. The risk of
lung cancer increases once the total radiation
dose equivalent of inhaled plutonium exceeds 400
mSv.
[97] The U.S. Department of Energy estimates that the lifetime cancer risk from inhaling 5,000 plutonium particles, each about 3
µm wide, to be 1% over the background U.S. average.
[98] Ingestion or inhalation of large amounts may cause acute
radiation poisoning
and death; no human is known to have died because of inhaling or
ingesting plutonium, and many people have measurable amounts of
plutonium in their bodies.
[82]
The "
hot particle"
theory in which a particle of plutonium dust radiates a localized spot
of lung tissue is not supported by mainstream research — such particles
are more mobile than originally thought and toxicity is not measurably
increased due to particulate form.
[95]
When inhaled, plutonium can pass into the bloodstream. Once in the
bloodstream, plutonium moves throughout the body and into the bones,
liver, or other body organs. Plutonium that reaches body organs
generally stays in the body for decades and continues to expose the
surrounding tissue to radiation and thus may cause cancer.
[99]
A commonly cited quote by
Ralph Nader[100]
states that a pound of plutonium dust spread into the atmosphere would
be enough to kill 8 billion people. However, calculations show that one
pound of plutonium could kill no more than 2 million people by
inhalation. This makes the toxicity of plutonium roughly equivalent with
that of
nerve gas.
[101] Nader's views were challenged in 1976 by
Bernard Cohen, as described in the book
Nuclear Power, Both Sides: The Best Arguments for and Against the Most Controversial Technology. Cohen's own estimate is that a dose of 200 micrograms would likely be necessary to cause cancer.
[102]
Several populations of people who have been exposed to plutonium dust (e.g. people living down-wind of Nevada test sites,
Nagasaki survivors,
nuclear facility workers, and "terminally ill" patients injected with
Pu in 1945–46 to study Pu metabolism) have been carefully followed and
analyzed. These studies generally do not show especially high plutonium
toxicity or plutonium-induced cancer results, such as
Albert Stevens who survived into old age after being injected with plutonium.
[95]
"There were about 25 workers from Los Alamos National Laboratory who
inhaled a considerable amount of plutonium dust during 1940s; according
to the hot-particle theory, each of them has a 99.5% chance of being
dead from lung cancer by now, but there has not been a single lung
cancer among them."
[101][103]
Plutonium has a metallic taste.
[104]
Criticality potential
A sphere of simulated plutonium surrounded by neutron-reflecting
tungsten carbide blocks in a re-enactment of Harry Daghlian's 1945 experiment
Toxicity issues aside, care must be taken to avoid the accumulation of amounts of plutonium which approach
critical mass, particularly because plutonium's critical mass is only a third of that of uranium-235.
[8] A critical mass of plutonium emits lethal amounts of neutrons and
gamma rays.
[105] Plutonium in solution is more likely to form a critical mass than the solid form due to
moderation by the hydrogen in water.
[14]
Criticality accidents have occurred in the past, some of them with lethal consequences. Careless handling of
tungsten carbide bricks around a 6.2 kg plutonium sphere resulted in a fatal dose of radiation at
Los Alamos on August 21, 1945, when scientist
Harry K. Daghlian, Jr. received a dose estimated to be 5.1
Sievert (510
rems) and died 25 days later.
[106][107] Nine months later, another Los Alamos scientist,
Louis Slotin, died from a similar accident involving a beryllium reflector and the same plutonium core (the so-called "
demon core") that had previously claimed the life of Daghlian.
[108] These incidents were fictionalized in the 1989 film
Fat Man and Little Boy.
In December 1958, during a process of purifying plutonium at Los
Alamos, a critical mass was formed in a mixing vessel, which resulted in
the death of a chemical operator named
Cecil Kelley.
[109] Other
nuclear accidents have occurred in the
Soviet Union,
Japan, the United States, and many other countries.
[109]
Flammability
Metallic plutonium is a fire hazard, especially if the material is
finely divided. In a moist environment, plutonium forms hydrides on its
surface, which are
pyrophoric
and may ignite in air at room temperature. Plutonium expands up to 70%
in volume as it oxidizes and thus may break its container.
[34] The radioactivity of the burning material is an additional hazard.
Magnesium oxide sand is probably the most effective material for extinguishing a plutonium fire. It cools the burning material, acting as a
heat sink, and also blocks off oxygen. Special precautions are necessary to store or handle plutonium in any form; generally a dry
inert gas atmosphere is required.
[34][note 11]