Uranium dioxide

Uranium dioxide

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Uranium dioxide or uranium(IV) oxide (2), also known as urania or uranous oxide, is an oxide
Oxide
An oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....

 of uranium
Uranium
Uranium is a silvery-white metallic chemical element in the actinide series of the periodic table, with atomic number 92. It is assigned the chemical symbol U. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons...

, and is a black, radioactive, crystalline powder that naturally occurs in the mineral uraninite
Uraninite
Uraninite is a radioactive, uranium-rich mineral and ore with a chemical composition that is largely UO2, but also contains UO3 and oxides of lead, thorium, and rare earth elements...

. It is used in nuclear fuel
Nuclear fuel
Nuclear fuel is a material that can be 'consumed' by fission or fusion to derive nuclear energy. Nuclear fuels are the most dense sources of energy available...

 rods in nuclear reactors. A mixture of uranium and plutonium
Plutonium
Plutonium is a transuranic radioactive chemical element with the chemical symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, forming a dull coating when oxidized. The element normally exhibits six allotropes and four oxidation...

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

. Prior to 1960 it was used as yellow and black color in ceramic
Ceramic
A ceramic is an inorganic, nonmetallic solid prepared by the action of heat and subsequent cooling. Ceramic materials may have a crystalline or partly crystalline structure, or may be amorphous...

 glaze
Ceramic glaze
Glaze is a layer or coating of a vitreous substance which has been fired to fuse to a ceramic object to color, decorate, strengthen or waterproof it.-Use:...

s and glass
Glass
Glass is an amorphous solid material. Glasses are typically brittle and optically transparent.The most familiar type of glass, used for centuries in windows and drinking vessels, is soda-lime glass, composed of about 75% silica plus Na2O, CaO, and several minor additives...

.

Production


Uranium dioxide is produced by reducing uranium trioxide
Uranium trioxide
Uranium trioxide , also called uranyl oxide, uranium 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, γ-UO3, is a yellow-orange powder.-Production and use:There are three methods...

 with hydrogen
Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H. With an average atomic weight of , hydrogen is the lightest and most abundant chemical element, constituting roughly 75% of the Universe's chemical elemental mass. Stars in the main sequence are mainly...

.
UO3 + H2 → UO2 + H2O at 700 °C (970 K)


This reaction takes part in the reprocessing of nuclear fuel
Nuclear reprocessing
Nuclear reprocessing technology was developed to chemically separate and recover fissionable plutonium from irradiated nuclear fuel. Reprocessing serves multiple purposes, whose relative importance has changed over time. Originally reprocessing was used solely to extract plutonium for producing...

 and enrichment of uranium
Enriched uranium
Enriched uranium is a kind of uranium in which the percent composition of uranium-235 has been increased through the process of isotope separation. Natural uranium is 99.284% 238U isotope, with 235U only constituting about 0.711% of its weight...

 for nuclear fuel.

Structure


The solid is isostructural
Isostructural
The term isostructural is used for chemical compounds that have similar chemical structures, and also with the meaning of isomorphous when used in relation to crystal structures...

 with (has the same structure as) fluorite
Fluorite
Fluorite is a halide mineral composed of calcium fluoride, CaF2. It is an isometric mineral with a cubic habit, though octahedral and more complex isometric forms are not uncommon...

 (calcium fluoride
Calcium fluoride
Calcium fluoride is the inorganic compound with the formula CaF2. This ionic compound of calcium and fluorine occurs naturally as the mineral fluorite . It is the source of most of the world's fluorine. This insoluble solid adopts a cubic structure wherein calcium is coordinated to eight fluoride...

). In addition, the dioxides of plutonium
Plutonium
Plutonium is a transuranic radioactive chemical element with the chemical symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, forming a dull coating when oxidized. The element normally exhibits six allotropes and four oxidation...

 and neptunium
Neptunium
Neptunium is a chemical element with the symbol Np and atomic number 93. A radioactive metal, neptunium is the first transuranic element and belongs to the actinide series. Its most stable isotope, 237Np, is a by-product of nuclear reactors and plutonium production and it can be used as a...

 have the same structures.

Oxidation


Uranium dioxide is oxidized in contact with oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

 to the triuranium octaoxide
Triuranium octaoxide
Triuranium octoxide is a compound of uranium. It is present as an olive green to black, odorless solid. In spite of its color, it is one of the more popular forms of yellowcake and is shipped between mills and refineries in this form....

.
3 UO2 + O2 → U3O8 at 700 °C (970 K)


The electrochemistry
Electrochemistry
Electrochemistry is a branch of chemistry that studies chemical reactions which take place in a solution at the interface of an electron conductor and an ionic conductor , and which involve electron transfer between the electrode and the electrolyte or species in solution.If a chemical reaction is...

 of uranium dioxide has been investigated in detail as the galvanic corrosion of uranium dioxide controls the rate at which used nuclear fuel
Nuclear fuel
Nuclear fuel is a material that can be 'consumed' by fission or fusion to derive nuclear energy. Nuclear fuels are the most dense sources of energy available...

 dissolves. See the spent nuclear fuel
Spent nuclear fuel
Spent nuclear fuel, occasionally called used nuclear fuel, is nuclear fuel that has been irradiated in a nuclear reactor...

 page for further details. Water
Water
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...

 increases the oxidation rate of plutonium
Plutonium
Plutonium is a transuranic radioactive chemical element with the chemical symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, forming a dull coating when oxidized. The element normally exhibits six allotropes and four oxidation...

 and uranium
Uranium
Uranium is a silvery-white metallic chemical element in the actinide series of the periodic table, with atomic number 92. It is assigned the chemical symbol U. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons...

 metals.

Nuclear fuel


UO2 is used mainly as nuclear fuel
Nuclear fuel
Nuclear fuel is a material that can be 'consumed' by fission or fusion to derive nuclear energy. Nuclear fuels are the most dense sources of energy available...

, specifically as UO2 or as a mixture of UO2 and PuO2 (plutonium dioxide
Plutonium dioxide
Plutonium oxide is the 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....

) called a mixed oxide (MOX fuel
MOX fuel
Mixed oxide fuel, commonly referred to as MOX fuel, is nuclear fuel that contains more than one oxide of fissile material. MOX fuel contains plutonium blended with natural uranium, reprocessed uranium, or depleted uranium. MOX fuel is an alternative to the low-enriched uranium fuel used in the...

) for fuel rods in nuclear reactor
Nuclear reactor
A nuclear reactor is a device to initiate and control a sustained nuclear chain reaction. Most commonly they are used for generating electricity and for the propulsion of ships. Usually heat from nuclear fission is passed to a working fluid , which runs through turbines that power either ship's...

s.

Note that the thermal conductivity
Thermal conductivity
In physics, thermal conductivity, k, is the property of a material's ability to conduct heat. It appears primarily in Fourier's Law for heat conduction....

 of uranium dioxide is very low when compared with uranium
Uranium
Uranium is a silvery-white metallic chemical element in the actinide series of the periodic table, with atomic number 92. It is assigned the chemical symbol U. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons...

, uranium nitride
Uranium nitride
Uranium nitride refers to a family of several ceramic compounds: uranium mononitride , uranium sesquinitride , which exists in either an alpha or beta phase, and uranium dinitride ....

, uranium carbide
Uranium carbide
Uranium carbide, a carbide of uranium, is a hard refractory ceramic material. It comes in several stoichiometries , such as uranium monocarbide , uranium sesquicarbide ,...

 and zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...

 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.


Image:ZrUthermalcond.png|The thermal conductivity of zirconium metal and uranium dioxide as a function of temperature
Image:rim200pd250rad1000fueltemp.jpg|This is a 20 mm diameter fuel pellet, note that the central temperature is very different for the different fuel solid.

Color for ceramics glaze


All uranium oxides were used to color glass and ceramics. Uranium oxide-based ceramics become green or black when fired in a reducing atmosphere and yellow to orange when fired with oxygen. Orange-colored Fiestaware
Fiestaware
Fiesta is a line of ceramic dinnerware glazed in differing solid colors manufactured and marketed by the Homer Laughlin China Company of Newell, West Virginia....

 is a well-known example of a product with a uranium-based glaze. Uranium oxide has also been used in formulations of enamel
Vitreous enamel
Vitreous enamel, also porcelain enamel in U.S. English, is a material made by fusing powdered glass to a substrate by firing, usually between 750 and 850 °C...

, uranium glass
Uranium glass
Uranium glass is glass which has had uranium, usually in oxide diuranate form, added to a glass mix before melting. The proportion usually varies from trace levels to about 2% by weight uranium, although some 19th-century pieces were made with up to 25% uranium.Uranium glass was once made into...

, and porcelain
Porcelain
Porcelain is a ceramic material made by heating raw materials, generally including clay in the form of kaolin, in a kiln to temperatures between and...

.

Prior to 1960, uranium oxides were used as colored glazes. It is possible to determine with a Geiger counter
Geiger counter
A Geiger counter, also called a Geiger–Müller counter, is a type of particle detector that measures ionizing radiation. They detect the emission of nuclear radiation: alpha particles, beta particles or gamma rays. A Geiger counter detects radiation by ionization produced in a low-pressure gas in a...

 if a glaze or glass contains uranium oxides.

Other use


Depleted
Depleted uranium
Depleted uranium is uranium with a lower content of the fissile isotope U-235 than natural uranium . Uses of DU take advantage of its very high density of 19.1 g/cm3...

 UO2 (DUO2) can be used as a material for radiation shielding. For example, DUCRETE
Ducrete
DUCRETE is a high density concrete alternative investigated for use in construction of casks for storage of radioactive waste...

 is a "heavy concrete
Concrete
Concrete is a composite construction material, composed of cement and other cementitious materials such as fly ash and slag cement, aggregate , water and chemical admixtures.The word concrete comes from the Latin word...

" material where gravel
Gravel
Gravel is composed of unconsolidated rock fragments that have a general particle size range and include size classes from granule- to boulder-sized fragments. Gravel can be sub-categorized into granule and cobble...

 is replaced with uranium dioxide aggregate; this material is investigated for use for cask
CASK
Peripheral plasma membrane protein CASK is a protein that in humans is encoded by the CASK gene. This gene is also known by several other names: CMG 2 , calcium/calmodulin-dependent serine protein kinase 3 and membrane-associated guanylate kinase 2.-Genomics:This gene is located on the short arm of...

s for radioactive waste
Radioactive waste
Radioactive wastes are wastes that contain radioactive material. Radioactive wastes are usually by-products of nuclear power generation and other applications of nuclear fission or nuclear technology, such as research and medicine...

. Casks can be also made of DUO2-steel
Steel
Steel is an alloy that consists mostly of iron and has a carbon content between 0.2% and 2.1% by weight, depending on the grade. Carbon is the most common alloying material for iron, but various other alloying elements are used, such as manganese, chromium, vanadium, and tungsten...

 cermet
Cermet
A cermet is a composite material composed of ceramic and metallic materials. A cermet is ideally designed to have the optimal properties of both a ceramic, such as high temperature resistance and hardness, and those of a metal, such as the ability to undergo plastic deformation. The metal is used...

, a composite material
Composite material
Composite materials, often shortened to composites or called composition materials, are engineered or naturally occurring materials made from two or more constituent materials with significantly different physical or chemical properties which remain separate and distinct at the macroscopic or...

 made of an aggregate
Aggregate (composite)
Aggregate is the component of a composite material that resists compressive stress and provides bulk to the composite material. For efficient filling, aggregate should be much smaller than the finished item, but have a wide variety of sizes...

 of uranium dioxide serving as radiation shielding, graphite
Graphite
The mineral graphite is one of the allotropes of carbon. It was named by Abraham Gottlob Werner in 1789 from the Ancient Greek γράφω , "to draw/write", for its use in pencils, where it is commonly called lead . Unlike diamond , graphite is an electrical conductor, a semimetal...

 and/or silicon carbide
Silicon carbide
Silicon carbide , also known as carborundum, is a compound of silicon and carbon with chemical formula SiC. It occurs in nature as the extremely rare mineral moissanite. Silicon carbide powder has been mass-produced since 1893 for use as an abrasive...

 serving as neutron radiation
Neutron radiation
Neutron radiation is a kind of ionizing radiation which consists of free neutrons. A result of nuclear fission or nuclear fusion, it consists of the release of free neutrons from atoms, and these free neutrons react with nuclei of other atoms to form new isotopes, which, in turn, may produce...

 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 compound
Volatile organic compound
Volatile organic compounds are organic chemicals that have a high vapor pressure at ordinary, room-temperature conditions. Their high vapor pressure results from a low boiling point, which causes large numbers of molecules to evaporate or sublimate from the liquid or solid form of the compound and...

s in gaseous phase, oxidation of methane
Methane
Methane is a chemical compound with the chemical formula . It is the simplest alkane, the principal component of natural gas, and probably the most abundant organic compound on earth. The relative abundance of methane makes it an attractive fuel...

 to methanol
Methanol
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a chemical with the formula CH3OH . It is the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a distinctive odor very similar to, but slightly sweeter than, ethanol...

, and removal of sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...

 from petroleum
Petroleum
Petroleum or crude oil is a naturally occurring, flammable liquid consisting of a complex mixture of hydrocarbons of various molecular weights and other liquid organic compounds, that are found in geologic formations beneath the Earth's surface. Petroleum is recovered mostly through oil drilling...

. It has high efficiency and long-term stability when used to destroy VOCs when compared with some of the commercial catalysts, such as precious metal
Precious metal
A precious metal is a rare, naturally occurring metallic chemical element of high economic value.Chemically, the precious metals are less reactive than most elements, have high lustre, are softer or more ductile, and have higher melting points than other metals...

s, TiO2
Titanium dioxide
Titanium dioxide, also known as titanium oxide or titania, is the naturally occurring oxide of titanium, chemical formula . When used as a pigment, it is called titanium white, Pigment White 6, or CI 77891. Generally it comes in two different forms, rutile and anatase. It has a wide range of...

, and Co3O4
Cobalt oxide
Cobalt oxide may refer to*Cobalt oxide - CoO*Cobalt oxide - Co2O3*Cobalt oxide - Co3O4...

 catalysts. Much research is being done in this area, DU being favoured for the uranium component due to its low radioactivity.

The use of uranium dioxide as a material for rechargeable batteries
Rechargeable battery
A rechargeable battery or storage battery is a group of one or more electrochemical cells. They are known as secondary cells because their electrochemical reactions are electrically reversible. Rechargeable batteries come in many different shapes and sizes, ranging anything from a button cell to...

 is being investigated. The batteries could have high power density
Power density
Power density is the amount of power per unit volume....

 and potential of 4.7 V per cell. Another investigated application is in photoelectrochemical cell
Photoelectrochemical cell
Photoelectrochemical cells or PECs are solar cells which generate electrical energy from light, including visible light. Some photoelectrochemical cells simply produce electrical energy, while others produce hydrogen in a process similar to the electrolysis of water.-Photogeneration cell:In this...

s 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.

Semiconductor properties


The band gap
Band gap
In solid state physics, a band gap, also called an energy gap or bandgap, is an energy range in a solid where no electron states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference between the top of the valence band and the...

 of uranium dioxide is comparable to these of silicon
Silicon
Silicon is a chemical element with the symbol Si and atomic number 14. A tetravalent metalloid, it is less reactive than its chemical analog carbon, the nonmetal directly above it in the periodic table, but more reactive than germanium, the metalloid directly below it in the table...

 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 cell
Solar cell
A solar cell is a solid state electrical device that converts the energy of light directly into electricity by the photovoltaic effect....

s based on Schottky diode
Schottky diode
The Schottky diode is a semiconductor diode with a low forward voltage drop and a very fast switching action...

 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
Single crystal
A single crystal or monocrystalline solid is a material in which the crystal lattice of the entire sample is continuous and unbroken to the edges of the sample, with no grain boundaries...

 silicon.

The dielectric constant
Dielectric constant
The relative permittivity of a material under given conditions reflects the extent to which it concentrates electrostatic lines of flux. In technical terms, it is the ratio of the amount of electrical energy stored in a material by an applied voltage, relative to that stored in a vacuum...

 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 construction of integrated circuit
Integrated circuit
An integrated circuit or monolithic integrated circuit is an electronic circuit manufactured by the patterned diffusion of trace elements into the surface of a thin substrate of semiconductor material...

s, as it may allow higher density integration with higher breakdown voltage
Breakdown voltage
The breakdown voltage of an insulator is the minimum voltage that causes a portion of an insulator to become electrically conductive.The breakdown voltage of a diode is the minimum reverse voltage to make the diode conduct in reverse...

s and with lower susceptibility to the CMOS
CMOS
Complementary metal–oxide–semiconductor is a technology for constructing integrated circuits. CMOS technology is used in microprocessors, microcontrollers, static RAM, and other digital logic circuits...

 tunneling 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
Bismuth
Bismuth is a chemical element with symbol Bi and atomic number 83. Bismuth, a trivalent poor metal, chemically resembles arsenic and antimony. Elemental bismuth may occur naturally uncombined, although its sulfide and oxide form important commercial ores. The free element is 86% as dense as lead...

-tellurium alloys, other materials promising for thermopower
Thermopower
The thermopower, or thermoelectric power of a material is a measure of the magnitude of an induced thermoelectric voltage in response to a temperature difference across that material...

 applications and Peltier elements.

The radioactive decay
Radioactive decay
Radioactive decay is the process by which an atomic nucleus of an unstable atom loses energy by emitting ionizing particles . The emission is spontaneous, in that the atom decays without any physical interaction with another particle from outside the atom...

 impact of the235U and238U on its semiconducting properties was not measured . 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
Very-large-scale integration
Very-large-scale integration is the process of creating integrated circuits by combining thousands of transistors into a single chip. VLSI began in the 1970s when complex semiconductor and communication technologies were being developed. The microprocessor is a VLSI device.The first semiconductor...

 chips. Use of depleted uranium
Depleted uranium
Depleted uranium is uranium with a lower content of the fissile isotope U-235 than natural uranium . Uses of DU take advantage of its very high density of 19.1 g/cm3...

 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.

The stoichiometry
Stoichiometry
Stoichiometry is a branch of chemistry that deals with the relative quantities of reactants and products in chemical reactions. In a balanced chemical reaction, the relations among quantities of reactants and products typically form a ratio of whole numbers...

 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.

Uranium dioxide, like U3O8, is a ceramic
Ceramic
A ceramic is an inorganic, nonmetallic solid prepared by the action of heat and subsequent cooling. Ceramic materials may have a crystalline or partly crystalline structure, or may be amorphous...

 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
Radiation
In physics, radiation is a process in which energetic particles or energetic waves travel through a medium or space. There are two distinct types of radiation; ionizing and non-ionizing...

 damage, making it useful for rad-hard
Radiation hardening
Radiation hardening is a method of designing and testing electronic components and systems to make them resistant to damage or malfunctions caused by ionizing radiation , such as would be encountered in outer space, high-altitude flight, around nuclear reactors, particle accelerators, or during...

 devices for special military and aerospace
Aerospace
Aerospace comprises the atmosphere of Earth and surrounding space. Typically the term is used to refer to the industry that researches, designs, manufactures, operates, and maintains vehicles moving through air and space...

 applications.

A Schottky diode
Schottky diode
The Schottky diode is a semiconductor diode with a low forward voltage drop and a very fast switching action...

 of U3O8
Yellowcake
Yellowcake is a kind of uranium concentrate powder obtained from leach solutions, in an intermediate step in the processing of uranium ores. Yellowcake concentrates are prepared by various extraction and refining methods, depending on the types of ores...

 and a p-n-p transistor of UO2 were successfully manufactured in a laboratory.

External links