Patent Application
20060203952
This invention relates generally to nuclear reactors, and more particularly, to zirconium alloy nuclear fuel assemblies and methods to reduce hydrogen absorption in zirconium alloys.
A reactor pressure vessel (RPV) of a boiling water reactor (BWR) typically has a generally cylindrical shape and is closed at both ends, e.g., by a bottom head and a removable top head. A core assembly is contained within the RPV and includes the core support plate, fuel assemblies, control rod blades and a top guide. A core shroud typically surrounds the core assembly and is supported by a shroud support structure. Particularly, the shroud has a generally cylindrical shape and surrounds both the core plate and the top guide. There is a space or annulus located between the cylindrical reactor pressure vessel and the cylindrically shaped shroud.
The core of the reactor includes an array of fuel assemblies. The fuel assemblies include fuel rods, fuel spacers, fuel channels, and water rods that are typically formed from zirconium alloys. The service life of a boiling water reactor (BWR) fuel channel is generally limited by the ability of the channel to resist longitudinal bowing, creep and corrosion. Channels used in the nuclear energy industry are typically formed from zirconium alloys, for example, Zircaloy-2 and Zircaloy-4, which exhibit exceptional resistance to corrosion due to a natural formation of a dense, adherent and stable surface oxide. However, such zirconium alloys are susceptible to corrosion by reacting with high temperature steam and water that are used as the cooling and heat transfer media in the reactor. A by-product of the zirconium alloy corrosion reaction is hydrogen. The corrosion-induced hydrogen is absorbed into the zirconium alloy and forms a zirconium hydride which can induce brittleness and reduce the ductility of the zirconium alloy fuel assembly components. Another problem is that the corrosion-induced hydrogen that is absorbed into the zirconium alloy can cause bowing of the fuel channels which can interfere with the control rod action.
New zirconium-based alloys have been introduced that appear to improve hydrogen absorption characteristics, but there are no known zirconium-based alloys that prevent hydrogen absorption completely. U.S. Pat. No. 5,475,723 to Marlowe describes that alloying the zirconium inner lining of barrier fuel cladding with palladium or platinum promotes hydrogen absorption. However, U.S. Pat. No. 5,805,656 to Adamson describes adding platinum or palladium to the zirconium alloy that forms the outer layers of a fuel channel to serve as a catalyst favoring recombination of hydrogen and oxygen to reduce hydrogen levels in the coolant water of the reactor.
In one aspect, a method of reducing hydrogen absorption in fuel assembly components fabricated from zirconium alloys in a nuclear reactor is provided. The method includes depositing at least one noble metal on at least one surface of the fuel assembly components. Depositing at least one noble metal includes exposing the zirconium alloy fuel assembly components, outside the nuclear reactor, to an aqueous solution including at least one compound containing at least one noble metal.
In another aspect, a method of manufacturing a fuel assembly for a nuclear reactor is provided. The fuel assembly includes a plurality of components formed from a zirconium alloy. The method includes exposing at least one zirconium alloy fuel assembly component, outside the nuclear reactor, to an aqueous solution at a temperature of about 50° C. to about 320° C., the aqueous solution comprising at least one compound containing at least one noble metal.
A method of reducing the rate of corrosion-induced hydrogen absorption in zirconium (Zr) based nuclear fuel assembly components exposed to high temperature water and steam is described below in detail. The method includes depositing noble metal(s) on the outer surface of the Zr-based fuel assembly components in an out-of-reactor liquid coating process. In alternate embodiments, the noble metal(s) is deposited, for example, by alloying of the fuel cladding during fabrication, or by surface treatment following cladding fabrication by electroplating/electrodeposition, electroless plating, chemical or physical vapor deposition, sputtering, and laser alloying. The noble metal(s) is deposited on the components in a range of about 0.01 μg/cm2 to about 1000 μg/cm2. The noble metal deposits decrease the rate of hydrogen absorption into the Zr-based fuel assembly components which prevents an increase in brittleness of the zirconium alloy fuel assembly components, thereby extending the operational lifetimes of the fuel assembly components. The term “noble metal” as used herein means platinum group metals, for example, platinum, palladium, osmium, ruthenium, iridium, rhodium and mixtures thereof.
Referring to the drawings,
Thermal power is generated within core 22, which includes fuel assemblies 46 of fissionable material. Water circulated up through core 22 is at least partially converted to steam. Steam separators 48 separates steam from water, which is recirculated. Residual water is removed from the steam by steam dryers 50. The steam exits RPV 10 through a steam outlet 52 near vessel top head 14.
The amount of thermal power generated in core 22 is regulated by inserting and withdrawing control rods 54 of neutron absorbing material, such as for example, boron carbide. To the extent that control rod 54 is inserted into core 22 between fuel assemblies 46, it absorbs neutrons that would otherwise be available to promote the chain reaction which generates thermal power in core 22. Control rod guide tubes 56 maintain the vertical motion of control rods 54 during insertion and withdrawal. Control rod drives 58 effect the insertion and withdrawal of control rods 54. Control rod drives 58 extend through bottom head 12.
Fuel assemblies 46 are aligned by a core plate 60 located at the base of core 22. A top guide 62 aligns fuel bundles 46 as they are lowered into core 22. Core plate 60 and top guide 62 are supported by core shroud 20.
Fuel channels 70 are hollow elongated components having generally square-shaped cross-sections. Fuel channels 70 are formed, for example, by rolling strips of a Zr-based alloy, such as a Zircaloy alloy, bending the strips into U-shaped channel sections, and then seam welding two channel sections together to form a single fuel channel. Fuel channels 70 also serve to confine the coolant water flow through the core to a predictable flow path around the fuel rods 72. In a boiling water reactor, the coolant water is turned to steam by the heat released during fission. Accordingly, the fuel channels 70 are exposed to a hostile corrosive and radiation environment. In alternate embodiments, fuel channels 70 can have other shapes, for example, tubular.
To reduce the rate of corrosion-induced hydrogen absorption in Zr-based fuel assembly 46 components, for example, fuel channels 70, that are exposed to high temperature water and steam in reactor pressure vessel 10, the fuel assembly components are coated, in an exemplary embodiment, with at least one noble metal in an out-of-reactor process. The fuel assembly components are exposed to an aqueous solution that includes at least one noble metal containing compound at a temperature of about 50° C. to about 320° C., and in another embodiment, from about 90° C. to about 285° C. The fuel assembly components are exposed for a sufficient amount of time to permit the deposition of about 0.01 μg/cm2 to about 1000 μg/cm2, in another embodiment, from about 0.1 μg/cm2 to about 100 μg/cm2, in another embodiment, from about 0.1 μg/cm2 to about 60 μg/cm2, and in another embodiment from 1 μg/cm2 to about 30 μg/cm2.
The concentration of the noble metal compounds in the aqueous solution are such that the amount of noble metal in the solution is about 0.1 parts per billion (ppb) to about 2000 ppb, in another embodiment, from about 1 ppb to about 500 ppb, and in another embodiment, from about 5 ppb to about 100 ppb.
Suitable noble metal containing compounds include, but are not limited to, palladium acetyl acetonate, palladium nitrate, palladium acetate, platinum acetyl acetonate, hexahydroxyplatinic acid, Na2Pt(OH)6, Pt(NH3)4(NO3)2, K3Ir(NO2)6, K3Rh(NO2)6, platinum(W)oxide (Pt(IV)O2), platinum(IV)oxide-hydrate (Pt(IV)O2.xH2O, where x is 1-10), rhodium(II)acetate (Rh(II)ac2), Rh(III)nitrate (Rh(III)(NO3)3), rhodium(III)oxide (Rh(III)2O3), rhodium(III)oxide-hydrate (Rh(III)2O3.xH2O, where x is 1-10), rhodium(II)phosphate (Rh(III)PO4) and rhodium(III)sulphate (Rh(III)2(SO4)3).
The invention will be further described by reference to the following example which is presented for the purpose of illustration only and are not intended to limit the scope of the invention.
An unirradiated Zircaloy-2 tubing test sample was exposed for 48 hours to an aqueous solution containing 100 ppb Pt and 100 ppb Rh. The solution was maintained at 135° C. This coating procedure resulted in a coating containing approximately 7 μg/cm2 Pt and 0.7 μg/cm2 Rh. The coated test sample and an uncoated test sample were exposed to a 400° C. steam corrosion test for 360 days. Corrosion weight gain data and hydrogen content data were obtained periodically between 3 and 360 days as shown in
Treatment of zircaloy with noble metal lowers the hydrogen absorption into the zircaloy cladding. It is believed that the hydrogen absorption is lowered because of a recombination of hydrogen with oxygen on the catalytic zircaloy surface. In the above example, the total noble metal loading on the zircaloy surface is relatively low at 7.7 μg/cm2. Higher noble metal loadings will provide greater catalytic activity, resulting in lower levels of hydrogen absorption by the cladding materials. By adjusting/optimizing the amount of noble metal on the Zircaloy cladding it is possible to further reduce the hydrogen pickup fraction.
While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.
