Patent Application
20090035604
The invention relates to a cladding tube made of ferritic/martensitic or austenitic steel for nuclear fuel elements, which is exposed to a metallic coolant. The cladding tubes are for use in reactor arrangements having molten-metal cooling, the molten-metal coolant including lead or lead alloys.
Steel surfaces, such as those of the cladding tubes or internal structures in reactors that are operated with molten lead or lead alloys, are subject to corrosive attack by the molten metal. Gradual destruction of the metal components takes place by dissolution of alloy elements of the steel. This process can be prevented if oxygen is dissolved in the lead or its alloys, specifically at a concentration at which oxide layers form on the surface and suppress the dissolution process. The oxygen concentration, however, preferably does not exceed the value at which oxides of the lead alloys form.
In the presence of lead alloys that contain oxygen at a concentration at which the steel oxidizes but the lead alloys do not, the diffusion of iron ions at the surface produces magnetite layers, and the diffusion of oxygen into the metal produces spinel layers beneath the surface that continually grow over time. This process prevents dissolution attack by the lead alloys, but after an extended time results in a considerable degradation of material properties due to oxidation. In addition, a reliable protective effect is thereby achieved only for temperatures below 500° C. Because higher temperatures may be expected on cladding tubes in a reactor, additional protective layers must be considered for higher temperatures. The use of aluminum-containing alloys that, by the selective formation of thin aluminum oxide layers, represent an outstanding diffusion barrier again dissolution attack by the molten metal and against progressive oxidation of the steel, is very promising in this regard. It is not practical to add aluminum as an alloy to the entire steel matrix, since it is known that aluminum causes severe embrittlement of steel. The aluminum component must therefore be limited to a thin superficial layer. Two methods have been tested for the production of aluminum-containing surface alloys: industrial “pack cementation” and, on a laboratory scale, surface melt alloying using pulsed electron beams (GESA method). “Pack cementation” is a high-temperature diffusion method in which aluminum is diffused at approximately 900° C., in the gas phase, into the steel matrix. In the GESA method, a previously applied aluminum layer or thin film is alloyed into the steel surface with the aid of a pulsed electron beam. The basic protective mechanism has been confirmed on specimens treated with both methods. Transfer of the two methods for use on real thin-walled tubes has, however, been unsatisfactory. Because of the high process temperature for the diffusion method, utilization may be limited to nickel-containing austenitic steels. The dimensional stability of the cladding tubes cannot be guaranteed because of the high temperature. The surface alloy layer furthermore contains nickel. Of all the alloy constituents of steel, nickel has the highest solubility in lead, so that long-term durability in lead and lead alloys becomes questionable. On the other hand, the GESA method has the disadvantage that, because of the limited physical extent of the electron beam, the elongated cladding tube must be treated in overlapping fashion with multiple pulses. A portion of the previously applied aluminum layer can vaporize in the overlap areas, so that locally, insufficient aluminum is alloyed into the steel surface. It is desirable to prevent such local defects.
An aspect of the present invention is to make available a cladding tube made of ferritic/martensitic or austenitic steel for nuclear fuel elements/fuels which are equipped with a protective layer on the surface in contact with coolant, and which still provide a reliable protective effect at temperatures higher than 500° C.
In an embodiment, the present invention provides a cladding tube configured for use with nuclear fuels or nuclear fuel elements and configured for contact with molten lead or molten lead alloys at up to 800° C. The cladding tube includes a tube including at least one of ferritic/martensitic steel and austenitic steel. An alloy layer of up to 50 μm thickness is disposed on a surface of the tube and operable for corrosion resistance. The alloy layer includes 0-25% chromium, 3-15% aluminum and 60-97% iron.
In an embodiment, the invention also provides a method of making the cladding tube that includes the use of a pulsed electron beam to melt the alloy layer on the tube.
The invention will be described in the following with reference to exemplary embodiments and the drawings, in which:
In an embodiment of the present invention FeCrAl is alloyed into the surface of a cladding tube. In the presence of oxygen, this selectively forms thin aluminum oxide layers of up to 50 μm which impede anion and cation diffusion to such an extent that corrosion protection by a very slow-growing oxide layer is produced. In molten lead or lead alloys, the cladding tube is protected by a surface alloy layer against corrosive attack by these molten metals at up to 800° C. The alloy layer in the embodiment is made up of 3 to 15% aluminum and 0 to 25% chromium by weight, with the remainder iron. As compared with a coating method using a protective oxide layer, the surface alloy forming a protective layer has the advantage that defects or cracks in the oxide layer are “healed” by the subsequently diffusing oxide formers; and that the protective layers remain stable, and retain their protective properties, at substantially higher temperatures (800° C.).
Technical implementation of the surface alloy may be carried out by coating using a low-pressure plasma spray (LPPS) method, which is available on an industrial scale. The necessary thin layers can be, however, very rough and porous because of the relatively large spray droplets, and among other characteristics do not have good adhesion, since the substrate temperature must be kept low (<600° C.) in order to ensure dimensional stability of the cladding tubes and, in the case of ferritic/martensitic cladding tubes, to maintain the microstructure of the steel. For these reasons, the FeCrAl layers are undesirable for use in this form. The layer, together with the cladding tube steel layer close to the surface, can therefore be remelted with a pulsed electron beam of approx. 20 to 40 μs duration, an electron energy of 100 to 200 keV, and an energy density of 30 to 50 J/cm2, depending on its thickness. A homogeneous mixing of the alloy elements, together with the thin contact-melted surface layer of the steel, occurs in this context at the transition from the layer to the steel surface. This ensures intimate metallic joining of the alloy layer.
The brief remelting of the FeCrAl layer additionally smoothes and densifies it. Because the FeCrAl layer is very similar to the steel matrix of the cladding tube in terms of its thermophysical properties such as melting point, density, thermal conductivity, and vapor pressure, the remelting can be carried out here without difficulty using overlapping electron-beam pulses.
The melting depth can be extended to as much as 50 μm by way of the electron energy. The use of a pulsed electron beam has the advantage that the material zones of the cladding tube outside the alloy layer experience only slight heating.
The pulsed electron beam of the GESA IV unit (GESA=gepulste Elektronenstrahlanlage [pulsed electron beam system]), which was constructed for the treatment of cladding tubes (
The invention has been described with regard to exemplary embodiments. However, changes and modifications/alterations can be made without hereby leaving the range of protection of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2005 030 231.9 | Jun 2005 | DE | national |
This is a U.S. National Phase application under 35 U.S.C. §371 of International Application No. PCT/EP2006/005877, filed on Jun. 20, 2006, and claims the benefit of German Patent Application No. 10 2005 030 231.9, filed on Jun. 29, 2005. The International Application was published in German on Jan. 4, 2007 as WO 2007/000261 A2 under PCT Article 221(2).
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2006/005877 | 6/20/2006 | WO | 00 | 8/12/2008 |
