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. It has been used as an orange, yellow, green, and black color in ceramic glazes and glass.
Production Uranium dioxide is produced by reducing uranium trioxide with hydrogen. This reaction often creates triuranium octoxide as an intermediate.
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. 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. Models consistent with these measurements show the melt to consist mainly of UO6 and UO7 polyhedral units, where roughly 2⁄3 of the connections between polyhedra are corner sharing and 1⁄3 are edge sharing.
Oxidation Uranium dioxide is oxidized in contact with oxygen to form triuranium octoxide:
3 UO2 + O2 → U3O8 at 250 °C (523 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.
Reaction with carbon Uranium dioxide reacts with carbon at high temperatures, forming uranium carbide and carbon monoxide.
UO2 + 4 C → UC2 + 2 CO 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 elemental uranium, uranium nitride, uranium carbide and zircaloy cladding material as well as most uranium-based alloys. 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.
Color for glass ceramic glaze
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. 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.
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. 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. 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. As of 2013, the use of uranium dioxide as a material for rechargeable batteries is being investigated. The batteries could have a high power density and a reduction potential of -4.7 V per cell. 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. 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.
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