Uranium dioxide

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Uranium dioxide
UO2lattice.jpg
Names
IUPAC names
Uranium dioxide
Uranium(IV) oxide
Other names
Urania
Uranous oxide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.014.273 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-700-3
PubChem CID
RTECS number
  • YR4705000
UNII
  • InChI=1S/2O.U
    Key: FCTBKIHDJGHPPO-UHFFFAOYSA-N
  • O=[U]=O
Properties
UO2
Molar mass 270.03 g/mol
Appearanceblack powder
Density 10.97 g/cm3
Melting point 2,865 °C (5,189 °F; 3,138 K)
insoluble
Structure
Fluorite (cubic), cF12
Fm3m, No. 225
a = 547.1 pm [1]
Tetrahedral (O2−); cubic (UIV)
Thermochemistry
Std molar
entropy
(S298)
78 J·mol−1·K−1 [2]
−1084 kJ·mol−1 [2]
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H300, H330, H373, H410
P260, P264, P270, P271, P273, P284, P301+P310, P304+P340, P310, P314, P320, P321, P330, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazard RA: Radioactive. E.g. plutonium
4
0
0
Radiation warning symbol 3.svg
Flash point N/A
Safety data sheet (SDS) ICSC 1251
Related compounds
Other anions
Uranium(IV) sulfide
Uranium(IV) selenide
Other cations
Protactinium(IV) oxide
Neptunium(IV) oxide
Related uranium oxides
Triuranium octoxide
Uranium trioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Uranium dioxide or uranium(IV) oxide (UO2), also known as urania or uranous oxide, is an oxide of uranium, and is a black, radioactive, crystalline powder that naturally occurs in the mineral uraninite. It is used in nuclear fuel rods in nuclear reactors. A mixture of uranium and plutonium dioxides is used as MOX fuel. Prior to 1960, it was used as yellow and black color in ceramic glazes and glass.

Contents

Production

Uranium dioxide is produced by reducing uranium trioxide with hydrogen.

UO3 + H2 → UO2 + H2O at 700 °C (973 K)

This reaction plays an important part in the creation of nuclear fuel through nuclear reprocessing and uranium enrichment.

Chemistry

Structure

The solid is isostructural with (has the same structure as) fluorite (calcium fluoride), where each U is surrounded by eight O nearest neighbors in a cubic arrangement. In addition, the dioxides of cerium, thorium, and the transuranic elements from neptunium through californium have the same structures. [3] No other elemental dioxides have the fluorite structure. Upon melting, the measured average U-O coordination reduces from 8 in the crystalline solid (UO8 cubes), down to 6.7±0.5 (at 3270 K) in the melt. [4] Models consistent with these measurements show the melt to consist mainly of UO6 and UO7 polyhedral units, where roughly 23 of the connections between polyhedra are corner sharing and 13 are edge sharing. [4]

Oxidation

Uranium dioxide is oxidized in contact with oxygen to the triuranium octaoxide.

3 UO2 + O2 → U3O8 at 700 °C (973 K)

The electrochemistry of uranium dioxide has been investigated in detail as the galvanic corrosion of uranium dioxide controls the rate at which used nuclear fuel dissolves. See spent nuclear fuel for further details. Water increases the oxidation rate of plutonium and uranium metals. [5] [6]

Carbonization

Uranium dioxide is carbonized in contact with carbon, forming uranium carbide and carbon monoxide.

.

This process must be done under an inert gas as uranium carbide is easily oxidized back into uranium oxide.

Uses

Nuclear fuel

UO2 is used mainly as nuclear fuel, specifically as UO2 or as a mixture of UO2 and PuO2 (plutonium dioxide) called a mixed oxide (MOX fuel), in the form of fuel rods in nuclear reactors.

The thermal conductivity of uranium dioxide is very low when compared with uranium, uranium nitride, uranium carbide and zirconium cladding material. This low thermal conductivity can result in localised overheating in the centres of fuel pellets. The graph below shows the different temperature gradients in different fuel compounds. For these fuels, the thermal power density is the same and the diameter of all the pellets are the same.[ citation needed ]

The thermal conductivity of zirconium metal and uranium dioxide as a function of temperature ZrUthermalcond.png
The thermal conductivity of zirconium metal and uranium dioxide as a function of temperature

Color for glass ceramic glaze

Geiger counter (kit without housing) audibly reacting to an orange Fiestaware shard.

Uranium oxide (urania) was used to color glass and ceramics prior to World War II, and until the applications of radioactivity were discovered this was its main use. In 1958 the military in both the US and Europe allowed its commercial use again as depleted uranium, and its use began again on a more limited scale. Urania-based ceramic glazes are dark green or black when fired in a reduction or when UO2 is used; more commonly it is used in oxidation to produce bright yellow, orange and red glazes. [7] Orange-colored Fiestaware is a well-known example of a product with a urania-colored glaze. Uranium glass is pale green to yellow and often has strong fluorescent properties. Urania has also been used in formulations of enamel and porcelain. It is possible to determine with a Geiger counter if a glaze or glass produced before 1958 contains urania.

Other uses

Prior to the realisation of the harmfulness of radiation, uranium was included in false teeth and dentures, as its slight fluorescence made the dentures appear more like real teeth in a variety of lighting conditions.[ citation needed ]

Depleted UO2 (DUO2) can be used as a material for radiation shielding. For example, DUCRETE is a "heavy concrete" material where gravel is replaced with uranium dioxide aggregate; this material is investigated for use for casks for radioactive waste. Casks can be also made of DUO2-steel cermet, a composite material made of an aggregate of uranium dioxide serving as radiation shielding, graphite and/or silicon carbide serving as neutron radiation absorber and moderator, and steel as the matrix, whose high thermal conductivity allows easy removal of decay heat.[ citation needed ]

Depleted uranium dioxide can be also used as a catalyst, e.g. for degradation of volatile organic compounds in gaseous phase, oxidation of methane to methanol, and removal of sulfur from petroleum. It has high efficiency and long-term stability when used to destroy VOCs when compared with some of the commercial catalysts, such as precious metals, TiO2, and Co3O4 catalysts. Much research is being done in this area, DU being favoured for the uranium component due to its low radioactivity. [8]

The use of uranium dioxide as a material for rechargeable batteries is being investigated. The batteries could have high power density and potential of 4.7 V per cell. Another investigated application is in photoelectrochemical cells for solar-assisted hydrogen production where UO2 is used as a photoanode. In earlier times, uranium dioxide was also used as heat conductor for current limitation (URDOX-resistor), which was the first use of its semiconductor properties.[ citation needed ]

Uranium dioxide displays strong piezomagnetism in the antiferromagnetic state, observed at cryogenic temperatures below 30 kelvins. Accordingly, the linear magnetostriction found in UO2 changes sign with the applied magnetic field and exhibits magnetoelastic memory switching phenomena at record high switch-fields of 180,000 Oe. [9] The microscopic origin of the material magnetic properties lays in the face-centered-cubic crystal lattice symmetry of uranium atoms, and its response to applied magnetic fields. [10]

Semiconductor properties

The band gap of uranium dioxide is comparable to those of silicon and gallium arsenide, near the optimum for efficiency vs band gap curve for absorption of solar radiation, suggesting its possible use for very efficient solar cells based on Schottky diode structure; it also absorbs at five different wavelengths, including infrared, further enhancing its efficiency. Its intrinsic conductivity at room temperature is about the same as of single crystal silicon. [11]

The dielectric constant of uranium dioxide is about 22, which is almost twice as high as of silicon (11.2) and GaAs (14.1). This is an advantage over Si and GaAs in the construction of integrated circuits, as it may allow higher density integration with higher breakdown voltages and with lower susceptibility to the CMOS tunnelling breakdown.

The Seebeck coefficient of uranium dioxide at room temperature is about 750 μV/K, a value significantly higher than the 270 μV/K of thallium tin telluride (Tl2SnTe5) and thallium germanium telluride (Tl2GeTe5) and of bismuth-tellurium alloys, other materials promising for thermoelectric power generation applications and Peltier elements.

The radioactive decay impact of the 235U and 238U on its semiconducting properties was not measured as of 2005. Due to the slow decay rate of these isotopes, it should not meaningfully influence the properties of uranium dioxide solar cells and thermoelectric devices, but it may become an important factor for VLSI chips. Use of depleted uranium oxide is necessary for this reason. The capture of alpha particles emitted during radioactive decay as helium atoms in the crystal lattice may also cause gradual long-term changes in its properties.[ citation needed ]

The stoichiometry of the material dramatically influences its electrical properties. For example, the electrical conductivity of UO1.994 is orders of magnitude lower at higher temperatures than the conductivity of UO2.001[ citation needed ].

Uranium dioxide, like U3O8, is a ceramic material capable of withstanding high temperatures (about 2300 °C, in comparison with at most 200 °C for silicon or GaAs), making it suitable for high-temperature applications like thermophotovoltaic devices.

Uranium dioxide is also resistant to radiation damage, making it useful for rad-hard devices for special military and aerospace applications.

A Schottky diode of U3O8 and a p-n-p transistor of UO2 were successfully manufactured in a laboratory. [12]

Toxicity

Uranium dioxide is known to be absorbed by phagocytosis in the lungs. [13]

See also

Related Research Articles

The actinide or actinoid series encompasses at least the 14 metallic chemical elements in the 5f series, with atomic numbers from 89 to 102, actinium through nobelium. Number 103, lawrencium, is also generally included despite being part of the 6d transition series. The actinide series derives its name from the first element in the series, actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide.

A ceramic is any of the various hard, brittle, heat-resistant, and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain, and brick.

<span class="mw-page-title-main">Uranium</span> Chemical element with atomic number 92 (U)

Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium radioactively decays, usually by emitting an alpha particle. The half-life of this decay varies between 159,200 and 4.5 billion years for different isotopes, making them useful for dating the age of the Earth. The most common isotopes in natural uranium are uranium-238 and uranium-235. Uranium has the highest atomic weight of the primordially occurring elements. Its density is about 70% higher than that of lead and slightly lower than that of gold or tungsten. It occurs naturally in low concentrations of a few parts per million in soil, rock and water, and is commercially extracted from uranium-bearing minerals such as uraninite.

<span class="mw-page-title-main">Nuclear fuel cycle</span> Process of manufacturing and using nuclear fuel

The nuclear fuel cycle, also called nuclear fuel chain, is the progression of nuclear fuel through a series of differing stages. It consists of steps in the front end, which are the preparation of the fuel, steps in the service period in which the fuel is used during reactor operation, and steps in the back end, which are necessary to safely manage, contain, and either reprocess or dispose of spent nuclear fuel. If spent fuel is not reprocessed, the fuel cycle is referred to as an open fuel cycle ; if the spent fuel is reprocessed, it is referred to as a closed fuel cycle.

Mixed oxide fuel, commonly referred to as MOX fuel, is nuclear fuel that contains more than one oxide of fissile material, usually consisting of plutonium blended with natural uranium, reprocessed uranium, or depleted uranium. MOX fuel is an alternative to the low-enriched uranium fuel used in the light-water reactors that predominate nuclear power generation.

<span class="mw-page-title-main">Silicon carbide</span> Extremely hard semiconductor

Silicon carbide (SiC), also known as carborundum, is a hard chemical compound containing silicon and carbon. A wide bandgap semiconductor, it occurs in nature as the extremely rare mineral moissanite, but has been mass-produced as a powder and crystal since 1893 for use as an abrasive. Grains of silicon carbide can be bonded together by sintering to form very hard ceramics that are widely used in applications requiring high endurance, such as car brakes, car clutches and ceramic plates in bulletproof vests. Large single crystals of silicon carbide can be grown by the Lely method and they can be cut into gems known as synthetic moissanite.

<span class="mw-page-title-main">Uranium-238</span> Isotope of uranium

Uranium-238 is the most common isotope of uranium found in nature, with a relative abundance of 99%. Unlike uranium-235, it is non-fissile, which means it cannot sustain a chain reaction in a thermal-neutron reactor. However, it is fissionable by fast neutrons, and is fertile, meaning it can be transmuted to fissile plutonium-239. 238U cannot support a chain reaction because inelastic scattering reduces neutron energy below the range where fast fission of one or more next-generation nuclei is probable. Doppler broadening of 238U's neutron absorption resonances, increasing absorption as fuel temperature increases, is also an essential negative feedback mechanism for reactor control.

<span class="mw-page-title-main">Yellowcake</span> Uranium concentrate powder

Yellowcake is a type of powdered uranium concentrate obtained from leach solutions, in an intermediate step in the processing of uranium ores. It is a step in the processing of uranium after it has been mined but before fuel fabrication or uranium enrichment. Yellowcake concentrates are prepared by various extraction and refining methods, depending on the types of ores. Typically, yellowcakes are obtained through the milling and chemical processing of uranium ore, forming a coarse powder that has a pungent odor, is insoluble in water, and contains about 80% uranium oxide, which melts at approximately 2880 °C.

<span class="mw-page-title-main">Thorium dioxide</span> Chemical compound

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in colour. Also known as thoria, it is mainly a by-product of lanthanide and uranium production. Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in an isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points. All thorium compounds, including the dioxide, are radioactive because there are no stable isotopes of thorium.

<span class="mw-page-title-main">PUREX</span> Spent fuel reprocessing process for plutonium and uranium recovery

PUREX is a chemical method used to purify fuel for nuclear reactors or nuclear weapons. PUREX is the de facto standard aqueous nuclear reprocessing method for the recovery of uranium and plutonium from used nuclear fuel. It is based on liquid–liquid extraction ion-exchange.

<span class="mw-page-title-main">Nuclear fuel</span> Material fuelling nuclear reactors

Nuclear fuel refers to any substance, typically fissile material, which is used by nuclear power stations or other nuclear devices to generate energy.

<span class="mw-page-title-main">Plutonium(IV) oxide</span> Chemical compound

Plutonium(IV) oxide, or plutonia, is a chemical compound with the formula PuO2. This high melting-point solid is a principal compound of plutonium. It can vary in color from yellow to olive green, depending on the particle size, temperature and method of production.

DUCRETE is a high density concrete alternative investigated for use in construction of casks for storage of radioactive waste. It is a composite material containing depleted uranium dioxide aggregate instead of conventional gravel, with a Portland cement binder.

<span class="mw-page-title-main">Uranium carbide</span> Chemical compound

Uranium carbide, a carbide of uranium, is a hard refractory ceramic material. It comes in several stoichiometries (x differs in UCx), such as uranium methanide (UC, CAS number 12070-09-6), uranium sesquicarbide (U2C3, CAS number 12076-62-9), and uranium acetylide (UC2, CAS number 12071-33-9).

<span class="mw-page-title-main">Uranium trioxide</span> Chemical compound

Uranium trioxide (UO3), also called uranyl oxide, uranium(VI) oxide, and uranic oxide, is the hexavalent oxide of uranium. The solid may be obtained by heating uranyl nitrate to 400 °C. Its most commonly encountered polymorph is amorphous UO3.

<span class="mw-page-title-main">Spent nuclear fuel</span> Nuclear fuel thats been irradiated in a nuclear reactor

Spent nuclear fuel, occasionally called used nuclear fuel, is nuclear fuel that has been irradiated in a nuclear reactor. It is no longer useful in sustaining a nuclear reaction in an ordinary thermal reactor and, depending on its point along the nuclear fuel cycle, it will have different isotopic constituents than when it started.

This page describes how uranium dioxide nuclear fuel behaves during both normal nuclear reactor operation and under reactor accident conditions, such as overheating. Work in this area is often very expensive to conduct, and so has often been performed on a collaborative basis between groups of countries, usually under the aegis of the Organisation for Economic Co-operation and Development's Committee on the Safety of Nuclear Installations (CSNI).

<span class="mw-page-title-main">Uranium nitrides</span> Chemical compound

Uranium nitrides is any of a family of several ceramic materials: uranium mononitride (UN), uranium sesquinitride (U2N3) and uranium dinitride (UN2). The word nitride refers to the −3 oxidation state of the nitrogen bound to the uranium.

<span class="mw-page-title-main">Corium (nuclear reactor)</span> Material in core during nuclear meltdown

Corium, also called fuel-containing material (FCM) or lava-like fuel-containing material (LFCM), is a material that is created in a nuclear reactor core during a nuclear meltdown accident. Resembling lava in consistency, it consists of a mixture of nuclear fuel, fission products, control rods, structural materials from the affected parts of the reactor, products of their chemical reaction with air, water, steam, and in the event that the reactor vessel is breached, molten concrete from the floor of the reactor room.

Uranium disilicide is an inorganic chemical compound of uranium in oxidation state +4. It is a silicide of uranium. There has been recent interest in using uranium disilicide as an alternative to uranium dioxide for fuel in nuclear reactors. Advantages are higher percentage of uranium and higher thermal conductivity. A direct replacement of UO2 with U3Si2 should enable a reactor to generate more energy from a set of fuel rods and also provide more "coping time" in the case of a LOCA (Loss of Cooling Accident).

References

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  9. Jaime, Marcelo; Saul, Andres; Salamon, Myron B.; Zapf, Vivien; Harrison, Neil; Durakiewicz, Tomasz; Lashley, Jason C.; Andersson, David A.; Stanek, Christopher R.; Smith, James L.; Gofryk, Krysztof (2017). "Piezomagnetism and magnetoelastic memory in uranium dioxide". Nature Communications. 8 (1): 99. Bibcode:2017NatCo...8...99J. doi:10.1038/s41467-017-00096-4. PMC   5524652 . PMID   28740123.
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Further reading