A COMPONENT INCLUDING A ZIRCONIUM ALLOY, A METHOD FOR PRODUCING SAID COMPONENT, AND A NUCLEAR PLANT INCLUDING SAID COMPONENT

Abstract: The present invention relates to a component (1) comprising an element (2), which contains zirconium or a zirconium alloy and which has a surface (3) on which a corrosion protective layer (4) is formed, the oxide layer (4) comprising zirconium oxide. The component (1) is intended to be in an oxidising environment (6) and said oxide layer (4) has an outer surface (5) towards said oxidising environment (6). The element (2) comprises a layer (10), that borders said surface (3) and comprises hydrogen and at least one metal from the group of lanthanum elements and/or from the group platinum metals and/or yttrium which in its elemental form or as an oxide have the ability to effectively dissociate oxygen and H2O. The invention also relates to a method for manufacturing the component (1) and a nuclear facility comprising the component (1).

Description: A COMPONENT IN CL U D ING A ZIRCONIUM ALLOY, A METHOD FOR PRODUCING SAID COMPONENT AND A NUCLEAR PLANT INCLUDING SAID COMPONENT THE BACKGROUND OF THE INVENTION AND PRIOR ART The present invention relates to a component comprising an element, which comprises zirconium or a zirconium alloy and which has a surface on which a corrosion protective oxide layer is formed, whicn oxide layer comprises zirconium oxide, wherein the component is intended to be m an oxidising environment and said oxide layer has an outer surface towards said oxidising environment. The invention also relates to a method for manufacturing a component comprising an element, which comprises zirconium or a zirconium alloy and which has a surface on which a corrosion protective oxide layer is formed, which comprises zirconium oxide, wherein the component intended to be in an oxidising environment and said oxide layer has an outer surface towarαs said oxidising environment, and a nuclear facility comprising a reactor. In a nuclear facility, the reactor core comprises a number of fuel assemblies, which comprise a top plate and a bottom plate with a number of elongated, parallely placed tubular elements extending between the top plate and the bottom plate and a number of spacers axially distributed along and connected to the elongated tubular elements. The fuel assembly also comprises a large number of elongated fuel rods which are kept in place by the spacers between the top plate and the bottom plate according to a specific pattern and on specific distances relative to each other and to the elongated tubular elements. Each fuel rod contains nuclear fuel enclosed m a cladding tube. When the nuclear facility is in operation the reactor core is cooled with the help of a cooling medium being pumped upwarαs through the reactor core . Components in nuclear facilities are often subjected to attacKs caused by hydration and oxidisation hence it may be interesting to deposit a coating on the surface of the components to protect them. Cladding tubes for nuclear fuel is an example of such components. An attack on a cladding tube for nuclear fuel means m the worst possible case that a damage extending througn the entire thickness of the cladding tube occurs so tnat the radioactive nuclear fuel inside the cladding tube leaks out into the cooling water of the reactor. This may be caused by both primary and secondary defects on the cladding tube. Primary defects occur from attacks on the outer surface of the cladding tube and are in particular caused by wear from foreign objects. A primary defect extending through the whole thickness of the cladding tube means that water, steam or a combination of these streams m through the defect so that an area oetween the fuel and the inner surface of the cladding tube is filled with the water, the steam or the combination of these. The presence of the water, the steam or the combination of these m this area means that the cladding tube is m danger of being damaged through attacks on the inside of the tube. This attacK is often caused through hydration. Such a defect --s called a secondary defect and can only occur after a primary defect already has occurred. Both primary defects and secondary defects extending through the entire thickness of the cladding tube means that the nuclear fuel inside the cladding tube, and thus radioactivity, leaks out into the cooling water of the reactor. Secondary defects may occur at relatively long distances from the primary defects and have also usually the shape of long cracks or transverse breaks meaning that they are a serious type of defect. Zirconium is often used in materials for cladding tubes, which enclose the nuclear fuel in reactors because of its low neutron absorption ability and its good corrosion resistance. In order to enhance the mechanical properties of the material and to increase its corrosion resistance the cladding material is alloyed for example with tin with about a percentage of weight and with smaller contents of iron, nickel and chrome. The total content of alloying materials can be about some percentages of weight. During operation the cooling water reacts with the cladding tube and forms zirconium oxide, wherein hydrogen is released. Zirconium oxide is relatively corrosion resistant. In an oxidising environment this depends on the fact that the oxide layer formed can resist further attacks. How efficiently the oxide layer can resist further attacks is mostly governed by the oxygen and hydrogen transport in the oxide. Hydrogen can react with the cladding material and form zirconium hydride, which can lead to large cracks being formed in the cladding material. It should be noted, however, that small amounts of contaminants might exist in the alloy, wherein hydrogen is usually mentioned. A typical content of hydrogen is about 10 ppm by weight. That hydrogen is regarded as a contaminant is based partly on the knowledge of embrittlement of a metal through absorption of large amounts of hydrogen, a so-called hydrogen embrittlement. Hydrogen embrittlement means that the metal cracks more easily during mechanical stress. Hydrogen embrittlement may happen if the metal is heated in a hydrogen rich environment or if hydrogen is formed at the metal surface, for example in connection with corrosion, pickling and electrochemical surface treatment. How efficiently the oxide layer can resist further attacks also depends on the presence of microscopic pores, cavities and cracks m tne oxide layer. An oxide layer that only grows m the interface between the oxide layer and the surrounding gas/liquid by way of metal transport through the oxide layer tends to nave a bad adherence to the metal substrate. Furthermore an oxide layer growing only m the interface between the metal substrate and the oxide layer tends to crack in the interface towards the surrounding gas/liquid. A prerequisite for pores, cavities and cracks to be able to disappear during the growth of the oxide layer is that an oxide is formed at the surfaces adjacent to these pores, cavities and cracks which m turn assumes that oxygen, preferably m dissociated form, and metal are transported to said surfaces . In "Oxidation of Metals, Vol. 51, Nos %, 1999; Hydrogen m Chromium: Influence on the high-temperature Oxidation Kinetics m 0 2 , Oxide-Growth Mechanisms, and Scale Adherence; B Tveten et al . " it has been reported that an increased hydrogen content in chromium leads to increased metal transport and increased oxide growth in the interface between the oxide layer and the surrounding gas phase. It is also reported m said article that the presence of hydrogen m the metal results in less adherence of the oxide layer to the metal through decreased oxidisation m the interface between the metal and the oxide layer. Thus the presence of hydrogen m metal contributes to a decreased corrosion resistance . EMBODIMENTS OF THE INVENTION The purpose with the present invention is to provide a zirconium based alloy with such a composition tnat a sustainable balance between metal and oxygen transport is achieved in the oxide --ayer formed wnen the zirconium oased alloy is present in an oxidising environment. In this way dense and durable oxide layers are obtained whicn can efficiently resist further attacks. In particular these properties shall be optimised in respect of an application where the alloy is subjected to elevated radiation of the type of fast neutrons in a corrosive environment, such as in the reactor core of a nuclear facility. The nuclear facility may comprise a boiling water reactor or a pressure water reactor. The present invention is based on a number of tests made to map out which factors determine the oxidisation and hydration kinetics in zirconium and zirconium alloys, preferably m temperatures about 300-500°C. During these tests the surprising discovery has been made that with the component mentioned m the introduction which has the characteristics defined in the characterising part of claim 1, said metal will contribute to make the oxide layer more dense by oxide growth m the surfaces of the oxide layer which are adjacent to pores, cavities and cracks, wnerein these defects will be minimised. In this way a dense and durable oxide layer will be formed, which will increase the corrosion resistance of the component in oxidising environments. By platinum metals is meant platinum, palladium, rhodium, indium, osmium and ruthenium. Further characteristics of the component are evident from the independent claims, i.e. claims 2 to 15. The purposes are also achieved with the method mentioned in the introduction, whicn is characterised in that the component is treated in such a way that at least one layer of the element which faces said surface comprises hydrogen and at least one metal from the group of lanthanum elements and/or from the group platinum metals and/or yttrium which m its elementary form or as an oxide have the ability to effectively dissociate oxygen and H 2 0. Further characteristics of the method are evident from the independent claims 16 to 31. DESCRIPTION OF THE DRAWINGS In the following description of performed tests the attached drawings will be referred to, m which Fig la-c snows three diagrams illustrating the oxygen occurrence as a function of the oxide depth for samples comprising a zirconium alloy with different hydrogen content, Fig 2 shows a diagram illustrating the oxygen absorption rate as a function of hydrogen content for samples of a zirconium alloy exposed m 20 mbar 0 2 at 450°C, Fig 3 shows a diagram illustrating the oxygen absorption rate as a function of hydrogen content for samples of a zirconium alloy exposed in 20 mbar H 2 0 at 450°C, Fig 4 shows a diagram illustrating the dissociation rate of 0 2 as a function of the reciprocal temperature for different materials exposed in 20 mbar 0 2 , Fig 5 shows a diagram illustrating the oxide growth for samples of zirconium with different hydrogen content which have been exposed in 0 2 at 450°C, wherein two samples have been treated with cerium, Fig 6 shows a diagram illustrating the oxygen absorption rate as a function of the oxide layer thickness for samples, treated with hydrogen, cerium, platinum and ruthenium and exposed in 0 2 at 450°C, and Fig 7a shows now pores, cavities, and cracks may appear in an oxide layer formed on a component, and Fig 7b shows now the pores, cavities, and cracks in Fig 7a have been reduced with the help of oxide growth. DETAILED DESCRIPTION OF THE DRAWINGS Most tests nave been carried out on tubes comprising a zirconium alloy called Zιrcaloy-2. Zιrcaloy-2 comprises about 10 ppm cy weight of hydrogen. When components of zirconium alloys are present m an oxidising environment an oxide layer is formed on the surface being m contact with the environment. In order to map out how, for example, the hydrogen content in a zirconium alloy affects the metal transport in such an oxide layer tests have been carried out on tubes of Zιrcaloy-2 which have been hydrogenated, i.e. been brought to assimilate hydrogen by means of diffusion, of different degrees by being hydrogenated for different times. The hydrogenation has been carried out m two steps, where m a first step the tube of Zιrcaloy-2 in question has been exposed to nydrogen gas n an oven at 400°C during a certain time ano in a second step been placed m a vacuum oven n order to level out possible hydrogen gradients. In this way the tuoes have been brought to contain a certain hydrogen content, at least in a layer closest to the surface of the tube being in contact with the inner atmosphere of the oven. In the following when tubes of Zιrcaloy-2 with hydrogen contents above 10 ppm by weight are mentioned it is assumed that they have been treated m this way. However, when in the following, tubes of Zιrcaloy-2 are mentioned with a hydrogen content <10 ppm ioy weight the tube in question have been degassed of hydrogen at 800°C for a certain time so that at least a layer closest to the surface being in contact with tne environment comprises less than 10 ppm by weight hydrogen. In order to examine how the hydrogen content of a zirconium alloy affects the metal transport in the zirconium oxide a two-step oxidisation was carried out in 0 2 and H 2 0 respectively. The two-step oxidisation is an established method whose purpose is to give information of where oxide is growing in the oxide layer. It is performed so that a sample, in this case a tube of Zιrcaloy-2, first is oxidised m 16 ' 16 0 2 /H 2 0 16 and thereafter in 18 ' 18 0 2 /H 2 0 18 or vice versa. By thereafter determining how 16 0 and 18 0 varies with depth in the oxide layer information can be obtained on where oxide was formed at the latest. Three tests have been carried out on tubes of Zιrcaloy-2 with different hydrogen content. After the oxidisation tests the tubes have been coated with a thin layer of Au in order to avoid charging during the analysis. The horizontal axis indicates the depth in the oxide layer, wherein the interface between the oxide layer and the oxidising environment coincides with the origin and the vertical axis indicates the presence of the respective oxygen isotopes m the oxide layer. In Fig la the results are reported for a tube of ZιrcaIoy-2 with a hydrogen content of about 1 ppm by weight. In a first step the tube is oxidised in 16, 1S 0 2 and m a second step the same tube is oxidised m 18, 18 0 2 . Where the oxide layer borders the tube is marked with a dotted line. As shown in Fig la 18 0 is present mainly close to the interface between the oxide layer and the tube, thus the conclusion is that the oxide transport in the oxide layer towards the tube is higher than the metal transport m the oxide layer towards the oxidising environment. In Fig lb the results are reported for a tube of Zιrcaloy-2 with a hydrogen content of about 15 ppm by weight. In a first step the tube is oxidised m H 2 18 0 and m a second step the same tube is oxidised m H 2 lδ 0. Where the oxide layer borders the tube is marked with a dotted line. As shown in Fig lb the difference between the presence of 16 0 m close vicinity to the interface between the oxide layer and the oxidising environment and the presence of 16 0 in close vicinity of the interface between the oxide layer and the tube is less than the corresponding difference in Fig la. In Fig la it is the difference between the presence of 18 0 that may be studied. Thus the oxide growth in H 2 0 for a tube of Zircaloy-2 with a hydrogen content of about 15 ppm by weight is larger m the vicinity to the interface between the oxide layer and the oxidising environment than on the corresponding place for a tube of Zιrcaloy-2 with a hydrogen content of about 1 weight ppm, which was oxidised in 0 2 . The conclusion one can make of these two tests is that the metal transport has increased in direction towards the interface between the oxide layer and the oxidising environment with increasing hydrogen content. In Fig lc the results are reported for a tube of Zircaloy-2 with a hydrogen content of about 40 ppm by weight. In a first step the tube is oxidised in 16, 16 0 and in a second step the same tube is oxidised in 18 ' 18 0. Where the oxide layer borders the tube is marked with a dotted line. As shown in Fig lc the presence of 18 0 m the vicinity to the interface between the tube and the oxide layer is essentially equal to the presence of 18 0 in the vicinity of the interface between the oxide layer and the oxidising environment . The conclusion from the test series being reported in connection with Fig la-c is that an increased hydrogen content in a zirconium alloy leads to an increased oxide growth m the interface between the oxide layer and the oxidising environment because of an increased metal transport m the oxide layer. For a component comprising a zirconium alloy and being designed to be in a nuclear reactor one strives for a slow oxidisation rate. Tests have been carried out on tubes of Zircaloy-2 where the hydrogen content have varied from essentially 0 to a few hundred ppm by weight and where the tubes have been exposed m 20mbar 0 2 at 450°C. The result is illustrated m a diagram in Fig 2. The horizontal axis indicates the hydrogen content in ppm by weight and the vertical axis indicates the oxygen absorption rate in μmolO/cm 2 , hour . The oxide thickness has been between 20- 30μm. The conclusion one can make from this test series is that the oxygen absorption rate, i.e. the oxidisation rate is larger for a tube of Zircaloy-2 without presence of hydrogen than for a tube of Zircaloy-2 with a hydrogen content of about 10 ppm by weight. In order to have an oxide growth in vicinity of the contact surface between the oxide layer and the oxidising environment it is constructive if a zirconium alloy comprises hydrogen, compare with the reports of the tests in connection with fig la-c. If however, the oxide growth primarily takes place m vicinity of the interface between the oxide layer and the oxidising environment the adherence of the oxide layer to the zirconium alloy may deteriorate and lead to cracking and m the worst case flaking, so called scaling, wherein the corrosion rate increases and therewith the consumption of metal increases. Furthermore the oxide growth on a component comprising a zirconium alloy and intended to be in a nuclear reactor where the cooling medium comprises water means that hydrogen gas is produced during the oxidisation, wherein hydrogen may be absorbed by the zirconium alloy, i.e. the hydrogen content m the component will increase during operation. Thus there is an upper limit of the content of hydrogen m the zirconium alloy in an introductory phase, i.e. an upper content of hydrogen that deliberately was added to the component. In one test series tubes of Zircaloy-2 with different contents of hydrogen have been exposed m 20 mbar H 2 0 at 450°C. The result of this test series is reported in Fig 3. The horizontal axis indicates the hydrogen content m ppm by weight and the vertical axis indicates the oxygen absorption rate in μmolO/cm 2 , hour . A conclusion one can make from this test series is that tne oxygen absorption rate, i.e. the oxidisation rate, decreases with increased hydrogen content until a hydrogen content of about 200 ppm by weight, after which the oxidisation rate increases. Thus the hydrogen content m a component comprising a zirconium alloy should not m an introductory phase surpass 200 ppm by weight when oxidised m H 2 0, i.e. at the most 200 ppm by weight of hydrogen should deliberately be added to the component. The oxide layer of a component, m this case a component comprising a zirconium based alloy, can effectively resist the corrosion attack when the component is in an oxidising environment if the zirconium based alloy has such a composition that a durable balance between metal and oxygen transport is ontained in the oxide layer. It is thus necessary that it exists partly an oxygen transport and partly a metal transport towards the surfaces of the oxide layer which are adjacent to pores, cavities and cracks m the oxide layer so that oxide can be formed at these surfaces and therewith decrease the size of said pores, cavities and cracks, wherein a denser oxide layer is formed. One can roughly separate three areas from where it is desirable with formation of oxide, namely m connection to cavities present in the oxide layer where the latter borders the component, m connection to pores in the oxide layer and in connection to the cracks present in the oxide layer where the oxide layer adjoins the oxidising environment, cf. Fig 7a-b. As reported in connection to Fig la-lc a better metal transport in the oxide layer is obtained if the zirconium alloy comprises nydroσen. However it has been shown m the tests performed that zirconium oxide does not dissociate oxygen sufficiently efficiently to obtain a sufficiently good balance between tne transport of dissociated oxygen and the transport of metal in the oxide layer, wherein a dense and durable oxide layer which effectively can resist further attacks is not obtained. Above all this s true for temperatures <500°C. In a light water reactor m operation the temperature in the reactor is less than 500°C. The temperature m the reactor is rather arounα 300°C. A prerequisite to obtain oxide growth in the vicinity of the interface between the oxide layer and the zirconium alloy is that oxygen is transported thereto through for example grain boundaries or channels m the oxide layer. If oxygen is transported in tne form of 0 and/or 0 2 in the oxide layer the 0 2 -molecules first have to dissociate. To examine whether the 0 2 -molecules dissociate, a mixture of 16 ' 16 0 2 and 18 ' 1 0 2 may be used during the oxidisation, wherein one can follow the kinetics of the formation of 16, 18 0 V 2 -molecule . Tests have been performed where the rate of formation of 1 c no ' 0 2 have been measured when exposing different materials in 16, 16 02 and 18, 18 0 2 at 20 mbar, wherein the temperature has been varied. The test series is reported m Fig 4. The horizontal axis indicates the reciprocal temperature in 1/K and the vertical axis indicates the logarithm of the dissociation rate of 0 2 in μmol 0/cm 2 ,hour. On the topside of Fig 4 the temperature in °C is given. Six samples have been analysed, a first sample comprising zirconium oxide, a second sample comprising cerium oxide, a third sample of platinum, a fourth sample comprising rhodium, a fifth sample comprising indium and a sixth sample comprising ruthenium, and more precisely ruthenium oxide applied onto zirconium oxide. The oxygen molecules are dissociated at the interface to the surrounding atmospnere. As snown in Fig 4 the oxygen dissociation rate is high for zirconium or rather its oxide at temperatures > about 800°C. At temperatures < 500°C the oxygen dissociation rate is higher for cerium oxide, platinum, rhodium, indium and ruthenium oxide than for zirconium oxide. The conclusion one can make from this test series is that at low temperatures (<500°C) an increased transport of dissociated oxygen is made possible oγ the presence of cerium oxide and m particular of platinum, rnodium, indium and ruthenium oxide. In Fig 5 the results are reported from a test series made on a sample of zirconium being exposed in 20 mbar 0 2 at 450°C. The samples have been polished mechanically with SiC-paper to 1200 mesh. Three samples have been analysed, namely zirconium with a hydrogen content of about 50 ppm by weight, zirconium with a hydrogen content of about 50 ppm by weight coated with cerium oxide and zirconium with a hydrogen content of about 200 weight-ppm coated with cerium oxide. The coating can for example be applied by painting the sample with cerium oxide together with an indifferent carrier, after which a drying is carried out, preferably at an elevated temperature. Alternatively the coating can be applied by dipping the sample in a liquid medium containing cerium oxide, after which drying is carried out, preferably at an elevated temperature. The horizontal axis indicates the oxidisation time and the vertical axis indicates the oxygen absorption in μmolO/cm 2 . As shown m Fig 5 the oxygen absorption rate, i.e. the oxidisation rate of the sample with 200 ppm by weight hydrogen with presence of cerium oxide is lower than the oxidisation rate of the sample with 50 ppm by weight of hydrogen both with and without the presence of cerium oxide. The conclusion one can make from this test series is that the best balance between the oxygen transport and the metal transport concerning the oxidation in Fig 5 is obtained in the oxide layer of the sample with a hydrogen content of about 200 ppm by weight, which have been treated with cerium oxide. In Fig 6 a test series is reported which has been performed in order to analyse the influence from hydrogen, cerium, platinum and ruthenium. The horizontal axis indicates the oxygen absorption m μmolO/crrr and the vertical axis indicates the oxygen absorption rate in μmolO/cm 2 ,hour . The starting-point of the test series was two samples of zirconium, which have been polished mechanically with a SiC- paper to 1200 mesh. The samples originally comprised hydrogen to a content of about 200 ppm by weight and was treated with cerium. The samples were exposed in 20 mbar 0 2 at 450°C. In a second step aoout 100 ppm by weight of hydrogen has been added to the samples, wherein the samples thus comprised about 300 ppm by weight hydrogen. The sample was then exposed in 20 mbar 0 2 at 450°C. In a third and fourth step the first sample has again been treated with cerium, wherein this sample after each respective step was exposed n 20 mbar 0 2 at 450°C. In a fifth and last step this sample has been treated with platinum followed by exposure m 20 mbar 0 2 at 450°C. The second sample, whicn also comprised 300 ppm by weight of hydrogen was exposed in 20 mbar 0 2 at 450°C to an oxide thickness of about 170 μmolO/cm 2 , whereafter the sample was treated with ruthenium. Thereafter, the sample was again exposed in 20 mbar 0 2 at 450°C. As shown in Fig 6 the best corrosion resistance i.e. the lowest oxidation rate, for the sample is obtained when it was treated with ruthenium. Tests have shown that the oxide on a sample of zirconium which have been treated with platinum protects more effectively against both oxygen absorption and hydrogen absorption than the oxide on a sample of zirconium which has not been treated with platinum, i.e. for the platinum treated sample ooth the oxidisation rate and the hydration rate is lower than for the non- platinum treated sample. This despite tne fact that the platinum treated sample contained more nydrogen from the beginning than the non- platinum treated sample. The platinum treated sample contained 300 ppm by weight hydrogen and the non-platinum treated sample contained 180 ppm by weight hydrogen. The results from the tests are reported m the table below. The dissociation rate of 0 2 is also reported m the table below, where it is clear that the high dissociation rate can be coupled to the low oxygen absorption rate, which is consistent with earlier reported tests. In the table below the reaction data for zirconium samples exposed n 20 mpar 0 2 and 20 mbar H 2 respectively at 450°C are shown. The oxide thickness of the samples was about 15 μm. Sample 1 contained 180 ppm by weight hydrogen and sample 2 contained 300 ppm by weight hydrogen. Furthermore sample 2 was treated with platinum. Oxygen Oxygen Hydrogen dissociation absorption absorption rate rate rate μmolO/cτr-, hour μmolO/cm 2 ,hour μ o1H/cm 2 , hour Sample 1 <0,02 0,085 0,54 Sample 2 13 0,045 0,15 In a further experiment, an about 2 mm wide area was coated with platinum mteriourly m a Zircaloy tube naving a length of 1 mm. Thereafter, the tube was exposed mteriourly at 370°C n about 10 mbar water during 72 hours, whereafter an analysis of the absorption of hydrogen and oxygen was performed. On a platinum-coated area, an approximately 40% lower oxygen absorption and an approximately 80% lower hydrogen absorption than on a non-coated area. In Fig 7a a part of a component 1 is shown comprising an element 2, whicn can contain zirconium or a zirconium alloy. The element 2 has a surface 3 upon which a corrosion protective layer 4 is formed. The oxide layer 4 comprises zirconium oxide. The oxide layer 4 has an outer surface 5 facing an oxidising environment 6. In the oxide layer 4 there are pores 7. Furthermore there are cavities 8 m the oxide layer 4 wnere the oxide layer borders the surface 3 and cracks 9 in the oxide layer 4 where the oxide layer faces the oxidising environment 6. As a basis for the present invention and as already mentioned the surprising discovery lies m the contribution of hydrogen and certain metals such as cerium, platinum and ruthenium to making the oxide layer formed on a component 1 of the type described m connection with Fig 7a more dense. Thus at least one layer 10 of the element 2 has to comprise hydrogen and at least some metal, such as cerium or platinum. With a component 1 of tne type described in connection to Fig 7a it is possible to ootam a lasting balance between the metal and oxygen transport through the whole oxide layer 4. As shown m Fig 7a there is a surface 11 facing the pores 7, a surface 12 facing the cavity 8 and a surface 13 facing the crack 9. A durable balance between metal and oxide transport through the whole oxide layer 4 means that an oxide w ll be formed on the surfaces 11, 12 and 13, wherein the size of the pores, cavities, and cracks will be reduced, cf. Fig 7b. Cerium belongs to the metal group of lanthanum elements, wherein the layer 10 may contain any of the metals in said group. Furthermore platinum belongs to the group of platinum metals, wherein the layer 10 may comprise any of the platinum metals, i.e. platinum, palladium, indium, rhodium, osmium and ruthenium. Furthermore oxygen is more easily dissociated with yttrium than with zirconium, wherein the layer 10 may comprise yttrium. Said metals may be applied on the component 1 by painting the component 1 with the metal together with an indifferent carrier, after which drying takes place, preferably at an elevated temperature. Alternatively the coating may be applied by dipping the component 1 in a liquid medium containing the metal, after which drying takes place, preferably at an elevated temperature. It is also possible to add the metal in connection with manufacturing of the component 1 through mixture of the metal, zirconium and possible other alloying substances in a melted state, i.e. the metal is alloyed into the component. For the last mentioned method for addition of the metal the metal will exist homogeneously throughout the component . The present invention is not limited to the shown embodiment but can be varied and modified within the scope of the following claims.

Claims: Claims 1. A component I I ) comprising an element (2), which contains zirconium or a zirconium alloy and which nas a surface (3) on which a corrosion protective oxide layer (4) is formed, which oxide layer (4) comprises zirconium oxide, wherein the component (1) is intended to be m an oxidising environment (6) and said oxide layer (4) has an outer surface (5) towards said oxidising environment (6), characterised in that the element (2) comprises at least one layer (10) that borders said surface (3) and which comprises hydrogen and at least a metal from the group of lanthanum elements and/or from the group of platinum metals and/or yttrium which in its elementary form or as an oxide has the ability to effectively dissociate 0 2 and H 2 0. 2. A component (1) according to claim 1, characterised m that said metal from the group of platinum metals in pure oxygen at an absolute pressure of 20 mbar has an oxygen- dissociating capability, which is substantially equal to or higher than this capability of platinum. 3. A component (1) according to claim 1, characterised n that said hydrogen is arranged to promote a transport of zirconium inside the oxide layer (4) towards said outer surface (5) . 4. A component (1) according to any one of the preceding claims, characterised in that said metal is established to effectively dissociate oxygen and/or H 2 0 at said outer surface (5) . 5. A component (1) according to any one of the preceding claims, characterised in that said layer (19) of the element (2) comprises initially at least about 8 ppm by weight hydrogen. 6. A component (1) according to any one of the preceding claims, characterised in tnat said layer (10) of the element (2) comprises initially at least 20 ppm by weight hydrogen. 7. A component (1) according to any one of the preceding claims, characterised in that said layer (10) of the element (2) comprises initially at the most 100 ppm by weight hydrogen. 8. A component (1) according to any one of the preceding claims, characterised in that said layer (10) of the element (2) comprises initially at the most 200 ppm by weight hydrogen. 9. A component (1) according to any one of the preceding claims, characterised n that said layer (10) of the element (2) comprises initially about 50 ppm by weight hydrogen. 10. A component (1) according to any one of the preceding claims, characterised in that the layer (10) of the element (2) comprises as much of said metal that the dissociation leads to an increased concentration of free oxygen atoms and/or oxygen ions in the oxide layer (4) . 11. A component (1) according to any one of the preceding claims, characterised m that said metal comprises cerium. 12. A component (1) according to one any of the preceding claims, characterised in that said metal comprises platinum. 13. A component (1) according to any one of the preceding claims, characterised m that said metal comprises ruthenium. 14. A component (1) according to any one of the preceding claims, characterised in that said metal comprises iridium. 15. A component (1) according to any one of the preceding claims, characterised in that said metal comprises rhodium. 16. A method for manufacturing of a component (1) comprising an element (2), which contains zirconium or a zirconium alloy and which has a surface (3) on which a corrosion protective oxide layer (4) is formed, which comprises zirconium oxide, wherein the component (1) is intended to be in an oxidising environment (6) and said oxide layer (4) has an outer surface (5) towards said oxidising environment (6), characterised in that the component (1) is treated in such a way that at least one layer (10) of the element (2) that borders said surface (3) comprises hydrogen and at least one metal from the group of lanthanum elements and/or from the group platinum metals and/or yttrium which in its elemental form have the ability to effectively dissociate 0 2 and H 2 0. 17. A method according to claim 16, characterised in that said layer (10) of the element (2) initially comprises as much hydrogen that a transport of zirconium in oxide layer (4) towards said outer surface (5) is promoted. 18. A method according to any one of the claims 16 to 17, characterised in that said layer (10) of the element (2) comprises as much of said metal that oxygen and/or H 2 0 effectively dissociates at said outer surface (5) . 19. A method according to any one of the claims 16 to 18, characterised in that the component (1) is treated in such a way that said layer (10) of the element (2) comprises initially at least 10 ppm by weight hydrogen. 20. A method according to any one of the claims 16 to 19, characterised m that the component (1) is treated m such a way that said layer (10) of the element (2) comprises initially at least 20 ppm by weight hydrogen. 21. A method according to any one of the claims 16 to 20, characterised in that the component (1) is treated in such a way that said layer (10) of the element (2) comprises initially at the most 100 ppm by weight hydrogen. 22. A method according to any one of the claims 16 to 21, characterised m that the component (1) is treated in such a way that said layer (10) of the element (2) comprises initially at the most 200 ppm by weight hydrogen. 23. Method according to any one of the claims 16 to 22, characterised n that the component (1) is treated in such a way that said layer (10) of the element (2) comprises initially about 50 ppm by weight hydrogen. 24. A method according to any one of the claims 16 to 23, characterised in that said hydrogen in said layer (10) is added by exposing the component (1) in hydrogen gas at an elevated temperature . 25. A method according to claim 24, characterised m that the component (1) is exposed m hydrogen gas at said elevated temperature for as long a time that said hydrogen content is reached. 26. A method according to any one of the claims 24 and 25, characterised in that said temperature is about 400°C. 27. A method according to any one of the claims 16 to 26, characterised in that said metal is added mainly to said layer (10) of the element (2) by applying the metal on the component (1) . 28. A method according to claim 27, characterised n that said metal is applied on said outer surface (5) . 29. A method according to any one of the claims 16 to 26, characterised in that said metal is added to the component by mixing the metal with said zirconium or zirconium alloy, wherein both the metal and said zirconium or said zirconium alloy is present in an essentially melted condition when they are mixed. 30. A nuclear facility comprising a reactor, characterised in that the reactor comprises at least one component (1) according to any one of the claims 1 - 15. 31. A nuclear facility according to claim 30, characterised in that the component (1) is a cladding tube for nuclear fuel.

Inventors: HULTQUIST GUNNAR, LIMBAECK MAGNUS, WIKMARK GUNNAR, HULTQUIST, GUNNAR, LIMBAECK, MAGNUS, WIKMARK, GUNNAR
Applicants: HULTQUIST GUNNAR, LIMBAECK MAGNUS, WESTINGHOUSE ATOM AB, WIKMARK GUNNAR, HULTQUIST, GUNNAR, LIMBAECK, MAGNUS, WIKMARK, GUNNAR
Application year: 2001
Main classification: G21C3
IPC codes: C22C16, C23C8, C23C30, G21C3