Uranium metal

Finely divided uranium metal, being pyrophoric, presents a fire hazard. 

Seawater. The world s oceans contain ca 4 X 10 t of uranium (32). Because the uranium concentration is very low, approximately 3.34 ppm, vast amounts of water would be required to recover significant amount of uranium metal, ie, 10 m of seawater for each metdc ton of U. Significant engineering development and associated environmental concerns have limited the development of an economic means of uranium extraction from seawater (32) (see Ocean RAWMATORiALs). 

De-enrichment of HEU from approximately 93% to 3% can be accompHshed using the depleted tails from the original enrichment process. These tails contain on the average 0.20% U. The de-enrichment of 11 of HEU uses 32 t of tads, yielding approximately 33 t of fuel having an enrichment of 3% U. Producing the same amount of 3% enriched uranium from natural sources would requite approximately 180 t of natural uranium metal. Therefore, 1 t of HEU is equivalent to 180 t of natural uranium. 

The amount of HEU that becomes avadable for civdian use through the 1990s and into the twenty-first century depends on the number of warheads removed from nuclear arsenals and the amount of HEU in the weapons complex that is already outside of the warheads, ie, materials stockpdes and spent naval reactor fuels. An illustrative example of the potential amounts of weapons-grade materials released from dismanded nuclear weapons is presented in Table 7 (36). Using the data in Table 7, a reduction in the number of warheads in nuclear arsenals of the United States and Russia to 5000 warheads for each country results in a surplus of 1140 t of HEU. This inventory of HEU is equivalent to 205,200 t of natural uranium metal, or approximately 3.5 times the 1993 annual demand for natural uranium equivalent. 

Several components are required in the practical appHcation of nuclear reactors (1 5). The first and most vital component of a nuclear reactor is the fuel, which is usually uranium slightly enriched in uranium-235 [15117-96-1] to approximately 3%, in contrast to natural uranium which has 0.72% Less commonly, reactors are fueled with plutonium produced by neutron absorption in uranium-238 [24678-82-8]. Even more rare are reactors fueled with uranium-233 [13968-55-3] produced by neutron absorption in thorium-232 (see Nuclear reactors, nuclear fuel reserves). The chemical form of the reactor fuel typically is uranium dioxide, UO2, but uranium metal and other compounds have been used, including sulfates, siUcides, nitrates, carbides, and molten salts. 

In this process, uranium metal is electrodeposited at the cathode, while plutonium and other transuranium elements remain in the molten salt as trichlorides. Plutonium is reduced in a second step at a metallic cathode to produce Cd—Pu intermetallics. The refined plutonium and uranium metals can then be refabricated into metallic fuel (137). 

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

Properties. Uranium metal is a dense, bright silvery, ductile, and malleable metal. Uranium is highly electropositive, resembling magnesium, and tarnishes rapidly on exposure to air. Even a poHshed surface becomes coated with a dark-colored oxide layer in a short time upon exposure to air. At elevated temperatures, uranium metal reacts with most common metals and refractories. Finely divided uranium reacts, even at room temperature, with all components of the atmosphere except the noble gases. The silvery luster of freshly cleaned uranium metal is rapidly converted first to a golden yellow, and then to a black oxide—nitride film within three to four days. Powdered uranium is usually pyrophoric, an important safety consideration in the machining of uranium parts. The corrosion characteristics of uranium have been discussed in detail (28). 

In the sohd state, uranium metal exists in three aHotropic modifications. The transformation temperatures and the enthalpies of transformation are given in Table 5. The thermodynamic properties of uranium metal have been deterrnined with great accuracy and have been discussed (50). 

Uranium metal is weaMy paramagnetic, with a magnetic susceptibility of 1.740 X 10 A/g at 20°C, and 1.804 x 10 A/g (A = 10 emu) at 350°C (51). Uranium is a relatively poor electrical conductor. Superconductivity has been observed in a-uranium, with the value of the superconducting temperature, being pressure-dependent. This was shown to be a result of the fact that there are actually three transformations within a-uranium (37,52). 

Preparation of Uranium Metal. Uranium is a highly electropositive element, and extremely difficult to reduce. As such, elemental uranium caimot be prepared by reduction with hydrogen. Instead, uranium metal must be prepared using a number of rather forcing conditions. Uranium metal can be prepared by reduction of uranium oxides (UO2 [1344-59-8] or UO [1344-58-7] with strongly electropositive elements (Ca, Mg, Na), reduction of uranium halides (UCl [10025-93-1], UCl [10026-10-5] UF [10049-14-6] with electropositive metals (Li, Na, Mg, Ca, Ba), electro deposition from molten... 

In practice, uranium ore concentrates are first purified by solvent extraction with tributyl phosphate in kerosene to give uranyl nitrate hexahydrate. The purified uranyl nitrate is then decomposed thermally to UO (eq. 10), which is reduced with H2 to UO2 (eq. 11), which in turn is converted to UF by high temperature hydrofluorination (eq. 12). The UF is then converted to uranium metal with Mg (eq. 19). 

Fig. 4. Bomb reactor for the reduction of UF with Mg by the Ames process (capacity 144.2 kg uranium metal) A, steel cover flange with lifting eye B, bolt and nut C, top flange of bomb D, graphite cover E, liner of fused dolomitic oxide F, steel bomb, and G, charge, where represents steel, D liner, ...

The main technological uses for UO2 are found in the nuclear fuel cycle as the principal component for light and heavy water reactor fuels. Uranium dioxide is also a starting material for the synthesis of UF [10049-14-6] 6 (both critical for the production of pure uranium metal and... 

Fluorides. Uranium fluorides play an important role in the nuclear fuel cycle as well as in the production of uranium metal. The dark purple UF [13775-06-9] has been prepared by two different methods neither of which neither have been improved. The first involves a direct reaction of UF [10049-14-6] and uranium metal under elevated temperatures, while the second consists of the reduction of UF [10049-14-6] by UH [13598-56-6]. The local coordination environment of uranium in the trifluoride is pentacapped trigonal prismatic with an 11-coordinate uranium atom. The trifluoride is... 

Uranium hexafluoride [7783-81-5], UF, is an extremely corrosive, colorless, crystalline soHd, which sublimes with ease at room temperature and atmospheric pressure. The complex can be obtained by multiple routes, ie, fluorination of UF [10049-14-6] with F2, oxidation of UF with O2, or fluorination of UO [1344-58-7] by F2. The hexafluoride is monomeric in nature having an octahedral geometry. UF is soluble in H2O, CCl and other chlorinated hydrocarbons, is insoluble in CS2, and decomposes in alcohols and ethers. The importance of UF in isotopic enrichment and the subsequent apphcations of uranium metal cannot be overstated. The U.S. government has approximately 500,000 t of UF stockpiled for enrichment or quick conversion into nuclear weapons had the need arisen (57). With the change in pohtical tides and the downsizing of the nation s nuclear arsenal, debates over releasing the stockpiles for use in the production of fuel for civiUan nuclear reactors continue. 

Bromides and Iodides. The red-brown tribromide, UBr [13470-19-4], and the black tniodide, Ul [13775-18-3], may both be prepared by direct interaction of the elements, ie, uranium metal with X2 (X = Br, I). The tribromide has also been prepared by interaction of UH and HBr, producing H2 as a reaction product. The tribromide and tniodide complexes are both polymeric soflds with a local bicapped trigonal prismatic coordination geometry. The tribromide is soluble in H2O and decomposes in alcohols. 

M. H. West, M. M. Maitinez, J. B. Nielson, D. C. Court, and Q. D. Appeit, Synthesis of Uranium Metal UsingEaser-InitiatedTeduction of Uranium Tetrafluoride by Calcium Metal, LA-12996-MS, Los Alamos National Laboiatoiy, N.M., 1995. 

Uran-metail, n. uranium metal, -nitrat, n. uranium nitrate. 

The chemical similarity between lanthanide and actinide metals suggests that C2H I2 might also react with actinide metals. Preliminary experiments found no reaction between thorium or uranium metals and a THF solution of Plutonium and neptunium... 

One of the most important examples of the fluorination of oxides is the fluorination of uranium dioxide. Uranium tetrafluoride (UF4) is the intermediate compound which is reduced to uranium metal. The gaseous higher fluoride, uranium hexafluoride (UF6) is used for the separation of uranium isotopes to obtain enriched uranium (i.e., uranium containing a higher proportion of the isotope, U235, than natural uranium). 

Notwithstanding the Iraqi lesson learned that the possibility of undeclared nuclear activities must be taken seriously and their possible existence sought out, the concern with undeclared activities as a proliferation risk is not new and their possible existence has always been recognized, indeed, presumed, in ary serious analysis of safeguards. Even purified plutonium or highly enriched uranium metals are harmless in bulk form. Further steps, specifically fabrication into weapons components, are necessary before these materials can result in proliferation and these steps, while perhaps not demanding, are not trivial. They are necessarily presumed to exist if the diversion of separated plutonium or HEU is discovered, since no reliable means for their detection are available. 

CP-1 was assembled in an approximately spherical shape with the purest graphite in the center. About 6 tons of uranium metal fuel was used, in addition to approximately 40.5 tons of uranium oxide fuel. The lowest point of the reactor rested on the floor and the periphery was supported on a wooden structure. The whole pile was surrounded by a tent of rubberized balloon fabric so that neutron absorbing air could be evacuated. About 75 layers of 10.48-cm (4.125-in.) graphite bricks would have been required to complete the 790-cm diameter sphere. However, criticality was achieved at layer 56 without the need to evacuate the air, and assembly was discontinued at layer 57. The core then had an ellipsoidal cross section, with a polar radius of 209 cm and an equatorial radius of309 cm [20], CP-1 was operated at low power (0.5 W) for several days. Fortuitously, it was found that the nuclear chain reaction could be controlled with cadmium strips which were inserted into the reactor to absorb neutrons and hence reduce the value of k to considerably less than 1. The pile was then disassembled and rebuilt at what is now the site of Argonne National Laboratory, U.S.A, with a concrete biological shield. Designated CP-2, the pile eventually reached a power level of 100 kW [22],... 

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