Patent Application
20200373022
The present invention refers generally to doping of tubular ceramic SiC and SiC—SiC components, such as flow channels and cladding tubes in fuel assemblies, for nuclear reactors, especially water reactors, such as Boiling Water Reactors, BWR, and Pressurized Water Reactors, PWR. The invention could also be applicable to fast reactors, such as lead fast reactors.
In particular, the present invention refers to a tubular ceramic component suitable for being used in a nuclear reactor, comprising an inner layer of silicon carbide, an intermediate layer of silicon carbide fibres in a fill material of silicon carbide, the intermediate layer adjoining the inner layer, and an outer layer of silicon carbide, the outer layer adjoining the intermediate layer.
It is known to use silicon carbide or silicon carbide composites in nuclear components, such as fuel assemblies and flow channels.
US 2006/0039524 discloses a multi-layered cladding tube comprising an inner layer of monolithic silicon carbide, a central layer of silicon carbide fibres surrounded by a silicon carbide matrix, and an outer layer of silicon carbide.
WO 2011/134757 discloses a flow channel for a fuel assembly. The flow channel comprises an inner layer of silicon carbide, a central layer of silicon carbide fibres surrounded by a filler material of silicon carbide, and an outer layer of silicon carbide.
Pure silicon carbide, or substantially pure silicon carbide, grows isotropically when exposed to irradiation and high temperatures. The growth is due to impurities (secondary phases) in the crystalline silicon carbide, and to the formation of defects in the crystalline silicon carbide.
In a nuclear reactor, a relatively rapid growth of a silicon carbide component will occur during an initial phase up to a certain level which then remains relatively constant during the lifetime of the component. This is a problem in cladding tubes of silicon carbide. Since the fuel in the cladding tubes swells continuously during the lifetime of the fuel, it is difficult to maintain a constant pellet-cladding gap.
The growth due to impurities may be avoided by securing a small amount of secondary phases, which may be possible by choosing a suitable manufacturing method.
The growth due to the formation of defects occurs in the temperature interval 250-400° C. through the formation of point defects, i.e. atoms of Si or C are moved to interstitial positions in the crystalline structure.
An object of the present invention is to overcome the problems discussed above. In particular, the invention aims at a reduced and more uniform growth, or swelling, of the tubular ceramic component upon exposure to a neutron flux during operation in a nuclear reactor.
This object is achieved by the tubular ceramic component initially defined, which is characterized in that the silicon carbide of the inner layer, the fill material and the outer layer is doped and comprises at least one dopant in solid solution within crystals of the silicon carbide.
The silicon carbide of the inner layer, the fill material and the outer layer may thus comprise pure crystalline silicon carbide, or substantially pure crystalline silicon carbide, with the dopant or dopants in solid solution in the silicon carbide crystals and with very small quantities of secondary phases, for instance less than 1% of secondary phases.
By adding one or more dopants to the silicon carbide of the inner layer, the fill material and the outer layer, the growth of the cladding tube during operation in the nuclear reactor may be reduced and modified to be more uniform. Especially during the initial phase of the operation, the relatively rapid growth of non-doped silicon carbide components may be significantly reduced.
The dopant or dopants will provide a pre-swelling or growth of the silicon carbide, before the operation of the tubular ceramic component in the nuclear reactor. The change in connectivity due to the presence of the dopant or dopants in solid solution in the crystal structure of the silicon carbide will mean that a population of defects will exist within the structure that will enhance mobility of certain defects and promote additional defects to recombine, preventing further swelling or growth.
The dopant or dopants will provide a possibility to control the defect-related growth and the formation of point defects. The main part of the defect-related growth is due to the displacement of C-atoms. This displacement creates internal stresses and deformation. At sufficiently high internal stresses (which increase with reduced temperature), the growth stops (since new point defects are not any longer stable), i.e. the saturation growth is highest at low temperatures.
According to an embodiment of the invention, the dopant comprises at least one of the substances B, N, Al, P, O, Be, Li, S, Ti, Ge, P2O3, P2O5, Al2O3, AlN, Al4C3 and TiC1-x.
Doping of the silicon carbide may thus be achieved by adding one or more of the elements B, N, Al, P, O, Be, Li, S, Ti, Ge, and/or one or more of the compounds P2O3, P2O5, Al2O3, AlN, Al4C3 and TiC1-x during the manufacturing of the tubular ceramic component.
These dopants may have following properties making them suitable in the silicon carbide of the tubular ceramic component; Low neutron cross-section minimizing the absorption of neutrons; Larger size of the element than C increasing the formation of internal stresses. The smaller of the dopants may replace the C-atoms in the silicon carbide, whereas the larger of the elements, e.g. S and Ge, may replace the Si-atoms in the silicon carbide. Some of the dopants may replace both Si and C to different degrees;
Strong repulsive interaction to interstitials leading to saturation at a lower degree of growth.
According to an embodiment of the invention, the concentration of the dopant in the silicon carbide is 1-1000 ppm.
According to an embodiment of the invention, the concentration of the dopant in the silicon carbide is 10-1000 ppm.
According to an embodiment of the invention, the concentration of the dopant in the silicon carbide is 50-1000 ppm.
According to an embodiment of the invention, the dopant comprises at least N, wherein the nitrogen is enriched to contain a higher percentage of the isotope 15N than natural N.
According to an embodiment of the invention, the dopant comprises at least B, wherein the boron is enriched to contain a higher percentage of the isotope 11B than natural B.
According to an embodiment of the invention, the silicon carbide of the inner layer, the fill material and the outer layer has a concentration of secondary phases that is less than 1%, preferably less than 0.8%, more preferably less than 0.6%, and most preferably less than 0.4%.
According to an embodiment of the invention, the tubular ceramic component forms a cladding tube of a fuel rod and encloses a pile of nuclear fuel pellets.
According to an embodiment of the invention, the tubular ceramic component forms flow channel of a fuel assembly and encloses a plurality of fuel rods.
The invention is now to be explained more closely through a description of various embodiments and with reference to the drawings attached hereto.
Furthermore, the fuel assembly 1 comprises, when intended to be used in a BWR, a flow channel 6 that surrounds and encloses the fuel rods 4.
The inner layer 21 consists of homogeneous, preferably monolithic, silicon carbide. The intermediate layer 22 consists of silicon carbide fibres 25, 26 in a fill material 27 of homogeneous silicon carbide. The outer layer 23 consists of homogeneous, preferably monolithic, silicon carbide.
As can be seen in
It should be noted that the intermediate layer 22 also may comprise only one sublayer with silicon carbide fibres 25, 26, or more than two sublayers with silicon carbide fibres 25, 26.
The silicon carbide of the inner layer 21, of the fill material 27 and of the outer layer 23 is crystalline and doped with one or more dopants.
The dopants are present in solid solution within crystals of the crystalline silicon carbide of the inner layer 21, of the fill material 27 and of the outer layer 23.
The dopant, or dopants, may be added to the silicon carbide in various ways. For instance the dopants can be added during the process of depositing the silicon carbide onto the silicon carbide fibres 25, 26 and onto the intermediate layer 22.
In a first step, silicon carbide fibres 25, 26 may be wound in one or more sublayers to a tubular shape, for instance on a suitable form.
In a second step, silicon carbide may be deposited on the silicon fibres 25, 26 of the intermediate layer 22 to form the fill material 27. During the deposition process, the silicon carbide will penetrate the interspaces between the silicon carbide fibres 25, 26. The silicon carbide may be deposited by any suitable method such as sputtering, physical vapour deposition, PVD, chemical vapour deposition, CVD, etc. The dopant may then be added in advance to the silicon carbide to be deposited, or be mixed with the silicon carbide during the depositing process.
In a third step, the silicon carbide may be deposited to the intermediate layer 22 to form the inner layer 21 onto the intermediate layer 22 by any of the depositing methods mentioned above. The dopant may then be added in the same way as to the silicon carbide of intermediate layer 22.
In a fourth step, the silicon carbide may be deposited to the intermediate layer 22 to form the outer layer 23 onto the intermediate layer 22 by any of the depositing methods mentioned above. The dopant may then be added in the same way as to the silicon carbide of intermediate layer 22. The outer layer 23 may be deposited after or before the deposition of the inner layer 21.
According to another method, the dopant or dopants may be supplied during the manufacturing of the silicon carbide, for instance by adding the dopant or dopants to SiO2 and C in a so called Acheson furnace.
The concentration of the dopants in the silicon carbide of the inner layer 21, of the fill material 27 and of the outer layer 23 may be 1-1000 ppm, preferably 10-1000 ppm, more preferably 50-1000 ppm, and most preferably 50-500 ppm.
The silicon carbide of the inner layer 21, of the fill material 27 and of the outer layer 23 may contain a balance of possible residual substances in addition to the dopant or dopants.
The silicon carbide of the inner layer 21, of the fill material 27 and of the outer layer 23 has a concentration of secondary phases that is less than 1%.
The silicon carbide fibres 25, 26 are made of pure, or substantially pure, silicon carbide being free of dopants. A balance of possible residual substances may be present in the silicon carbide fibres 25, 26.
The dopants to be added to and comprised by the silicon carbide comprise at least one of the substances B, N, Al, P, O, Be, Li, S, Ti, Ge, P2O3, P2O5, Al2O3, AlN, Al4C3 and TiC1-x.
The silicon carbide may be doped by the addition of one of these substances, or with a combination of two or more of these substances.
B is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Preferably, the boron is enriched to contain a higher percentage of the isotope 11B than natural B in order to reduce the neutron absorption cross-section. B may be added as an element, for instance by sputtering, PVD or CVD.
N is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Preferably, the nitrogen is enriched to contain a higher percentage of the isotope 15N than natural N in order to reduce the neutron absorption cross-section. N may be added as an element, for instance by sputtering, PVD or CVD. The element N is larger than C, and thus N may be effective to replace C-atoms in the silicon carbide.
Al is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Al may be added as an element, for instance by sputtering, PVD or CVD. Al may also be added as one of the compounds Al2O3, MN and Al4C3. Also in these cases, Al will be contained as an element in solid solution in the crystals of the silicon carbide. The element Al is larger than C, and thus Al may be effective to replace C-atoms in the silicon carbide.
P is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. P may be added as an element, for instance by sputtering, PVD or CVD. P may also be added as one of the compounds P2O3 and P2O5. Also in these cases, P will be contained as an element in solid solution in the crystals of the silicon carbide. The element P is larger than C, and thus P may be effective to replace C-atoms in the silicon carbide.
O is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. O may be added as an element, for instance by sputtering, PVD or CVD. O may also be added as one of the compounds P2O3, P2O5 and Al2O3. Also in these cases, O will be contained as an element in solid solution in the crystals of the silicon carbide. The element O is larger than C, and thus O may be effective to replace C-atoms in the silicon carbide.
Be is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Be may be added as an element, for instance by sputtering, PVD or CVD.
Li is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Li may be added as an element, for instance by sputtering, PVD or CVD.
S is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. S may be added as an element, for instance by sputtering, PVD or CVD. The element S is larger than both C and Si, and thus S may be effective to replace C-atoms and Si-atoms in the silicon carbide.
Ti is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Ti may be added as an element, for instance by sputtering, PVD or CVD. Ti may also be added as the compound TiC1-x. Also in this case, Ti will be contained as an element in solid solution in the crystals of the silicon carbide. The element Ti is larger than both C and Si, and thus Ti may be effective to replace C-atoms and Si-atoms in the silicon carbide.
Ge is a possible dopant which may be contained in solid solution in crystals of the silicon carbide. Ge may be added as an element, for instance by sputtering, PVD or CVD. The element Ge is larger than both C and Si, and thus Ge may be effective to replace C-atoms and Si-atoms in the silicon carbide.
The present invention is not limited to the embodiments disclosed and discussed above, but may be varied and modified within the scope of the following claims.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/065343 | 6/11/2018 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62624420 | Jan 2018 | US |
