EP1693855A2 - Fuel element for a fast neutron reactor (variants) and a cladding for the production thereof - Google Patents
Fuel element for a fast neutron reactor (variants) and a cladding for the production thereof Download PDFInfo
- Publication number
- EP1693855A2 EP1693855A2 EP04793751A EP04793751A EP1693855A2 EP 1693855 A2 EP1693855 A2 EP 1693855A2 EP 04793751 A EP04793751 A EP 04793751A EP 04793751 A EP04793751 A EP 04793751A EP 1693855 A2 EP1693855 A2 EP 1693855A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- cladding
- steel
- carbides
- ferrite
- fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005253 cladding Methods 0.000 title claims abstract description 54
- 239000000446 fuel Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 87
- 239000010959 steel Substances 0.000 claims abstract description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 33
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 32
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 31
- 239000011651 chromium Substances 0.000 claims abstract description 31
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 31
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010937 tungsten Substances 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 15
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 14
- -1 chromium carbides Chemical class 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000006104 solid solution Substances 0.000 claims abstract description 8
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 229910000604 Ferrochrome Inorganic materials 0.000 claims abstract description 5
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 239000003758 nuclear fuel Substances 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- FEBJSGQWYJIENF-UHFFFAOYSA-N nickel niobium Chemical compound [Ni].[Nb] FEBJSGQWYJIENF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005496 tempering Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- NDUKHFILUDZSHZ-UHFFFAOYSA-N [Fe].[Zr] Chemical compound [Fe].[Zr] NDUKHFILUDZSHZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- LBDSXVIYZYSRII-IGMARMGPSA-N alpha-particle Chemical compound [4He+2] LBDSXVIYZYSRII-IGMARMGPSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009377 nuclear transmutation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005258 radioactive decay Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
Definitions
- the present invention relates to nuclear engineering range, specifically, to materials used in nuclear engineering and might be applied to fabricating fuel elements and components of fast nuclear reactor cores (below - BN reactors).
- Low activation irradiation resistant steel is known (see RU patent N 2135623) that contains carbon, silicon, manganese, chromium, nickel, vanadium, copper, molybdenum, cobalt, tungsten, yttrium, niobium, aluminum and iron at the following ratio between components, percent by weight: carbon - 0.13-0.18; silicon 0.20-0.35; manganese - 0.30-0.60; chromium - 2.0-3.5; tungsten - 1.0-2.0; vanadium - 0.10-0.35; molybdenum 0 0.01-0.05; nickel - 0.01-0.05; cobalt - 0.01-0.05; copper - 0.01-0.10; aluminum - 0.01-0.10; niobium - 0.01-0.05; yttrium - 0.05-0.15; the balance being iron.
- the total content of nickel, cobalt, molybdenum, niobium and copper makes up not more than 0.2 percent by weight, while the ratio (V+0.3W)C varies within 3 to 6.
- This steel has low induced activity, however, is not heat resistant at a temperature exceeding 500°C (see M.V.Zakharov, A.M.Zakharov. Heat Resistant Alloys, M.: Metallurgy, 1972).
- low activation heat resistant (up to 550°C) steel (according to RU patent N 2033461) that contains carbon, silicon, manganese, chromium, tungsten, vanadium, boron, titanium, cerium and iron at the following ratio between components, mass %: carbon - 0.10-0.20; silicon - 0.02-1.00; manganese - 0.50-2.0; chromium - 10.0-13.9; tungsten - 0.8-2.9; vanadium - 0.05-0.45; titanium - 0.01-0.10; boron - 0.0005-0.008; cerium - 0.001-0.100, the balance being iron.
- EP823 steel A steel that in terms of composition of ingredients and functioning approaches most closely the claimed one is EP823 steel the composition and properties of which are described in the paper by M.I.Solonin., F.G.Reshetnicov, A.G.Ioltukhovsky and others "Novel Structural Materials for Cores of Nuclear Power Installations", in journal “Physics and Chemistry of Material Processing", 2001, N4, pp.17-27.
- the steel contains, percent by weight: carbon -0.14-0.18; silicon - 1.1-1.3; manganese -0.5-0.8; chromium - 10.0-12.0; nickel - 0.5-0.8; vanadium - 0.2-0.4; molybdenum - 0.6-0.9; tungsten - 0.5-0.8; niobium - 0.2-0.4; boron - 0.006 (as calculated) cerium - not more than 0.1; nitrogen - not more than 0.05; sulphur - not more than 0.010; phosphorus - not more than 0.015; the balance being iron.
- the major disadvantages of this steel are its high activation ability under neutron irradiation via neutron reactions on Ni, Mo, Nb, Cu, Co and other elements to form long-lived radioactive isotopes as well as low heat resistance at a temperature not lower than 650°C and propensity for LTIE within 270-400°C.
- the technical objective of the invention is to create a BN reactor fuel element with a cladding having the following properties: low induced activity and a higher rate of its decay after exposure to neutrons, higher resistance to embrittlement in the temperature range from 270 to 400°C under neutron irradiation and a high heat resistance at temperatures up to 700°C.
- the technical result is to create a fuel element with a cladding having a high resistance to embrittlement in the temperature range from 270 to 400°C as well as a higher level of heat resistance at temperatures up to 700°C and high performance.
- the set up objective pertaining to the first version of realizing a BN reactor fuel element is put in practice via fabricating its cladding from ferritic-martensitic class steel having a non-uniform structure along a cladding length that consists of at least two zones; with the steel structure in the top zone of a fuel element providing its higher heat resistance and in the bottom zone enhancing its resistance to low temperature irradiation embrittlement.
- the set up objective pertaining to the second version of realizing a BN reactor fuel element is put in practice via fabricating its cladding from low activation steel containing carbon, silicon, manganese, chromium, vanadium, tungsten, boron, cerium and/or yttrium, titanium, tantalum, zirconium, nitrogen, iron and unavoidable impurities at the following ratio between components, percent by weight:
- the structure of the steel along a cladding length consists of at least two zones; with the steel structure in the top zone of a fuel element providing its higher heat resistance and containing ⁇ -ferrite, ⁇ - ferrite, sorbite, chromium carbides M 23 C 6 and M 6 C, carbides and carbonitrides of the steel components (V, Ta, Ti, Zr, W and others), intermetallics of the Fe 2 (W) type while the structure in the bottom zone enhancing its resistance to low temperature irradiation embrittlement consists of sorbite, ⁇ -ferrite, ⁇ -ferrite, residual austenite, carbides and carbonitrides of steel components (Cr, V, Na, W and others); in this case high-angle boundaries of grains are occupied by carbides M 23 C 6 and M 6 C while grains of both sorbite and ⁇ -fer
- the set up objective is also put in practice via fabricating a cladding for a fast reactor fuel element from low activation steel containing carbon, silicon, manganese, chromium, vanadium, tungsten, boron, cerium and/or yttrium, titanium, tantalum, zirconium, nitrogen, iron and unavoidable impurities at the following ratio of components, percent by weight:
- the steel structure along a cladding length consists of at least two zones: with the steel structure in the top zone of a fuel element providing its higher heat resistance and containing ⁇ -ferrite, sorbite, chromium carbides M 23 C 6 and M 6 C, carbides and carbonitrides of steel components (V, Ta, Ti, Zr, W and others), intermetallics of the Fe 2 (W) type while the structure in the bottom zone enhancing its resistance to low temperature irradiation embrittlement consists of sorbite, ⁇ -ferrite, ⁇ -ferrite, residual austenite, carbides and carbonitrides of steel components (Cr, V, Ta, W and others); in this case high-angle boundaries of grains are occupied by carbides M 23 C 6 and M 6 C while grains of both sorbite and ⁇ -ferrite have but individual precipitates of carbides and
- the structure of a steel along a cladding length consists of three zones; with the middle zone structure having intermediate values of heat resistance and resistance to low temperature irradiation embrittlement in comparison to those in the bottom and top zones.
- the total content of impurities of high activation metals viz., molybdenum, niobium, nickel, copper and cobalt, does not exceed 0.1 %mass. This serves to reduce neutron irradiation induced activation and to accelerate the decay rate of induced activation of steel.
- the essence of the invention consists in the fact that the steel structure along a cladding length is made non-uniform and is brought in conformity with the actual temperature drop along the length of the BN reactor core which makes up several hundred degrees. That is why, the claimed invention puts in practice a novel principle of placing different requirements for the properties and structure of a fuel cladding along its length.
- the steel structure in the bottom (low temperature) zone of a fuel cladding includes sorbite, ⁇ -ferrite, residual austenite, carbides of likely strong carbide forming components of the steel (Cr, V, Ti, Ta, W and others), nitrides and carbonitrides of the above mentioned elements; boundaries of large-angle grains are basically free from precipitates of carbides M 23 C 6 and M 6 C and have an intragranular coagulated carbide phase.
- the low temperature zone of a fuel element is subjected to cycling (up to 10 cycles) which comprises heating to the temperature A C1 + 20°C and cooling to room temperature; in this case the rate of product cooling after tempering and in the process of cycling and after it is finished has not to be below 50°C/min upon cooling in air.
- the steel is subjected to complex alloying with elements having a prompt decay of irradiation induced activity to attain a specified ratio between ⁇ -stabilizing elements (C, N, Mn) and ⁇ -stabilizing ones (Cr, W, V, Ta, Ti, Zr, Mo, Nb and others).
- a stable martensitic - ferritic structure of a cladding that contains solid solution strengthening interstitial elements (C,N,B) and substitutional elements (W, V, Cr), strengthening carbide (MC, M 2 C, M 23 C 6 and others), nitride (MN, M 2 N) and carbonitride (MCN) phases as well as Laves phases of the Fe(W) type.
- This structure in the high temperature zone of a fuel cladding is formed via quenching at a temperature of 1050-1150°C for 40 min followed by tempering at 680-760°C.
- An increase in the content of tungsten that is introduced in place of molybdenum at an approximately equivalent ratio provides a lower irradiation induced activation of a cladding and its prompt decay with time after neutron exposure due to a lower section of neutron interaction with tungsten nuclei and a lower half-life of irradiation produced isotopes of tungsten, respectively.
- An increase in the content of tungsten also promotes preservation of a high level of long-term and short-term strength of steel.
- Cerium and/or yttrium introduced in the quantity of 0.001-0.10 %mass promotes the refining and atomizing of steel grains. In this case cerium and yttrium being low activation elements do not increase the induced activity of the steel claimed.
- the low levels of cerium and/or yttrium content correspond to the minimal concentration at which its favourable influence on steel refining is noted.
- the value of the upper limit of cerium and/or yttrium content promotes preservation of the adequate processability by steel at a hot stage.
- the low limit of zirconium content is determined by the need of binding a part of nitrogen into finely dispersed and thermodynamically stable particles of zirconium nitride.
- the upper limit of zirconium content is determined by the feasible formation of low melting zirconium-iron eutectic which might reduce the processability of steel.
- the low limit of titanium content is determined by the need of binding a part of carbon into thermodynamically stable finely dispersed carbides of titanium.
- the upper level of titanium content is determined by feasible redistribution of nitrogen between zirconium and titanium which is not desired because of a possible decrease in long-term strength of steel.
- the low level of tantalum content is determined by the need of binding a part of carbon into thermodynamically stable tantalum carbides and ensuring its content in solid solution at the level of ultimate solubility.
- the upper limit of tantalum content is determined by feasible formation of globular carbide inclusions that reduce the processability of steel.
- the low limit of nitrogen content is determined by the need of binding zirconium into finely dispersed particles of zirconium nitride.
- the restriction of the nitrogen upper limit is required to provide the processability of steel during welding: zirconium and tantalum being low activation elements do not increase the induced activity of the claimed steel.
- Nitrogen as an isotope 14 N becomes activated under neutron irradiation to form a long-lived isotope 14 C that upon decaying (half-life of 5.7x10 3 years) produces ⁇ -particle (stable isotope 6 He) without resulting in ⁇ -radiation, i.e., the availability of nitrogen does not influence the decay of steel radiation activity determined by ⁇ -radiation.
- the content of silicon ranges from 0.1 to 0.8 to ensure deoxidation of steel.
- the content of manganese is kept at the level of 0.5-2.0 percent by weight.
- the chromium content of the claimed steel is kept at the level of 10-13.5 percent by weight.
- the carbon content of the claimed steel ranges within 0.10-0.21 percent by weight to provide for the high level of structural stability and heat resistance via the process of martensitic transformation.
- Ingots 25 kg in mass were forged into billets 35 mm in the diameter that were then forged into plates 10mm thick and a bar 12mm in the diameter.
- Ingots 500kg in mass were forged into billets 90mm in the diameter that were then rolled to produce a sheet 6mm thick and a bar 12mm in the diameter.
- the bar, sheet and plates were heat treated under the standard conditions, namely, normalizing and tempering.
- the heat treated metal was used to fabricate cylindrical samples with the effective part size ⁇ 5x25 mm to be tested for long-term strength and creep in compliance with GOST( ⁇ OCT) 10145-81 and GOST( ⁇ OCT) 3248-81.
- Tensile properties also after irradiation were determined using standard samples in tensile tests according to GOST ( ⁇ OCT) 10446-80.
- the indicated samples had to simulate the condition of the metal in the high temperature part of a fuel cladding at the operating temperature not lower than 600°C.
- the samples were subjected to cycling, i.e., heating to the temperature A C1 +20°C, 10 min holding and cooling to room temperature at a rate of not less than 50°C/min within 600 to 20°C. Altogether 10 cycles were carried out. After the cyclic treatment the samples were subjected to tempering at 720°C for 2 h followed by accelerated cooling (not less than 50°C/min) to room temperature.
- the claimed steel was neutron irradiated in research fast neutron reactor BOR-60 at a temperature of 345-365°C to the fluence of (1.14-2.0) 10 22 n/cm 2 (E>0.1MeV) at the damage dose of 5.8-8.0 dpa.
- Tensile tests were conducted using remotely operated breaking machine 1794-Y5 in air at a strain rate of ⁇ 1 mm/min. Under the indicated conditions samples were irradiated that had been heat treated under the standard conditions as well as samples that had been subjected to the cyclic heat treatment.
- the claimed fuel element cladding is usable in cores of fast neutron reactors.
- the use of a fuel element with a cladding having the claimed properties shall provide for high cost-effectiveness due to a more prompt decay of induced activity and have high properties of heat resistance and resistance to low temperature irradiation embrittlement. This cost-effectiveness effect will manifest in lower contamination of environment effected by operating nuclear power facilities of novel generation and in feasibility of re-using structural materials. Table 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Heat Treatment Of Steel (AREA)
- Powder Metallurgy (AREA)
- Materials For Medical Uses (AREA)
Abstract
Description
- The present invention relates to nuclear engineering range, specifically, to materials used in nuclear engineering and might be applied to fabricating fuel elements and components of fast nuclear reactor cores (below - BN reactors).
- Steels used to fabricate fuel element claddings and other components of BN reactors have to meet a series of rigid requirements for characteristics of heat resistance, resistance to low temperature irradiation effected embrittlement, resistance to vacancy effected swelling, processability, weldability and others. Recently much importance has been also attached to requirement for prompt decay of induced radioactivity of steels after their discharge from neutron field of BN reactor core, in other words, to designing so-called low activation steels. One of promising materials for fuel claddings is chromium steels that feature favourable properties, particularly, those that are insignificantly subject to irradiation induced swelling,
- Low activation irradiation resistant steel is known (see RU patent N 2135623) that contains carbon, silicon, manganese, chromium, nickel, vanadium, copper, molybdenum, cobalt, tungsten, yttrium, niobium, aluminum and iron at the following ratio between components, percent by weight: carbon - 0.13-0.18; silicon 0.20-0.35; manganese - 0.30-0.60; chromium - 2.0-3.5; tungsten - 1.0-2.0; vanadium - 0.10-0.35; molybdenum 0 0.01-0.05; nickel - 0.01-0.05; cobalt - 0.01-0.05; copper - 0.01-0.10; aluminum - 0.01-0.10; niobium - 0.01-0.05; yttrium - 0.05-0.15; the balance being iron.
- Here, the total content of nickel, cobalt, molybdenum, niobium and copper makes up not more than 0.2 percent by weight, while the ratio (V+0.3W)C varies within 3 to 6.
- This steel has low induced activity, however, is not heat resistant at a temperature exceeding 500°C (see M.V.Zakharov, A.M.Zakharov. Heat Resistant Alloys, M.: Metallurgy, 1972).
- Also known is low activation heat resistant (up to 550°C) steel (according to RU patent N 2033461) that contains carbon, silicon, manganese, chromium, tungsten, vanadium, boron, titanium, cerium and iron at the following ratio between components, mass %: carbon - 0.10-0.20; silicon - 0.02-1.00; manganese - 0.50-2.0; chromium - 10.0-13.9; tungsten - 0.8-2.9; vanadium - 0.05-0.45; titanium - 0.01-0.10; boron - 0.0005-0.008; cerium - 0.001-0.100, the balance being iron.
- In the described invention the irradiation properties of this steel are not given. However, as it is revealed by investigations (A.G.Ioltukhovsky, M.V.Leont'eva-Smimova, V.S.Ageev and others "Influence of Original Structure State on Propensity of 12% Chromium Steels for Irradiation Effected Embrittlement". Collected papers of 3 d Interbranch Conference on Reactor Materials Science, Dimitrovgrad, 1994, v.1, p.51) a steel that has such a composition has to be subject to low temperature irradiation embrittlement (below LTIE) because of 40-50% of δ-ferrite available in its structure. Hence, the major disadvantages of this steel that is most close to the claimed steel are insufficient heat resistance at a temperature higher than 550°C and a lower resistance to LTIE.
- A steel that in terms of composition of ingredients and functioning approaches most closely the claimed one is EP823 steel the composition and properties of which are described in the paper by M.I.Solonin., F.G.Reshetnicov, A.G.Ioltukhovsky and others "Novel Structural Materials for Cores of Nuclear Power Installations", in journal "Physics and Chemistry of Material Processing", 2001, N4, pp.17-27.
- The steel contains, percent by weight: carbon -0.14-0.18; silicon - 1.1-1.3; manganese -0.5-0.8; chromium - 10.0-12.0; nickel - 0.5-0.8; vanadium - 0.2-0.4; molybdenum - 0.6-0.9; tungsten - 0.5-0.8; niobium - 0.2-0.4; boron - 0.006 (as calculated) cerium - not more than 0.1; nitrogen - not more than 0.05; sulphur - not more than 0.010; phosphorus - not more than 0.015; the balance being iron.
- The major disadvantages of this steel are its high activation ability under neutron irradiation via neutron reactions on Ni, Mo, Nb, Cu, Co and other elements to form long-lived radioactive isotopes as well as low heat resistance at a temperature not lower than 650°C and propensity for LTIE within 270-400°C.
- The technical objective of the invention is to create a BN reactor fuel element with a cladding having the following properties: low induced activity and a higher rate of its decay after exposure to neutrons, higher resistance to embrittlement in the temperature range from 270 to 400°C under neutron irradiation and a high heat resistance at temperatures up to 700°C.
- The technical result is to create a fuel element with a cladding having a high resistance to embrittlement in the temperature range from 270 to 400°C as well as a higher level of heat resistance at temperatures up to 700°C and high performance.
- The set up objective pertaining to the first version of realizing a BN reactor fuel element is put in practice via fabricating its cladding from ferritic-martensitic class steel having a non-uniform structure along a cladding length that consists of at least two zones; with the steel structure in the top zone of a fuel element providing its higher heat resistance and in the bottom zone enhancing its resistance to low temperature irradiation embrittlement.
- The set up objective pertaining to the second version of realizing a BN reactor fuel element is put in practice via fabricating its cladding from low activation steel containing carbon, silicon, manganese, chromium, vanadium, tungsten, boron, cerium and/or yttrium, titanium, tantalum, zirconium, nitrogen, iron and unavoidable impurities at the following ratio between components, percent by weight:
- carbon
- - 0.10-0.21;
- silicon
- - 0.1-0.8;
- manganese
- - 0.5-2.0;
- chromium
- - 10.0-13.5;
- tungsten
- - 0.8-2.5;
- vanadium
- - 0.05-0.4;
- titanium
- - 0.03-0.3;
- boron
- - 0.001-0.008;
- cerium and/or yttrium in total
- - 0.001-0.10;
- zirconium
- - 0.05-0.2;
- tantalum
- - 0.05-0.2;
- nitrogen
- - 0.02-0.15;
- iron
- - the balance
- at the ratio of the total content of vanadium, titanium, zirconium and tantalum to the total content of carbon and nitrogen being from 2 to 9; the structure of the steel along a cladding length consists of at least two zones; with the steel structure in the top zone of a fuel element providing its higher heat resistance and containing α -ferrite, δ - ferrite, sorbite, chromium carbides M23C6 and M6C, carbides and carbonitrides of the steel components (V, Ta, Ti, Zr, W and others), intermetallics of the Fe2(W) type while the structure in the bottom zone enhancing its resistance to low temperature irradiation embrittlement consists of sorbite, δ-ferrite, α-ferrite, residual austenite, carbides and carbonitrides of steel components (Cr, V, Na, W and others); in this case high-angle boundaries of grains are occupied by carbides M23C6 and M6C while grains of both sorbite and δ -ferrite have but individual precipitates of carbides and carbonitrides VC, V(CN), Ti(CN) and Ta(CN) and the other elements (Fe, Mn, Mo, W, Si and others) enter into the compositions of either complex carbides M23C6 and M6C or a FeCr solid solution.
- The set up objective is also put in practice via fabricating a cladding for a fast reactor fuel element from low activation steel containing carbon, silicon, manganese, chromium, vanadium, tungsten, boron, cerium and/or yttrium, titanium, tantalum, zirconium, nitrogen, iron and unavoidable impurities at the following ratio of components, percent by weight:
- carbon
- - 0.10-0.21;
- silicon
- - 0.1-0.8;
- manganese
- - 0.5-2.0;
- chromium
- - 10.0-13.5;
- tungsten
- - 0.8-2.5;
- vanadium
- - 0.05-0.4;
- titanium
- - 0.03-0.3;
- boron
- - 0.001-0.008;
- cerium and/or yttrium in total -
- 0.001-0.10;
- zirconium
- - 0.05-0.2;
- tantalum
- - 0.05-0.2;
- nitrogen
- - 0.02-0.15;
- iron
- - the balance
- at the ratio of the total content of vanadium, titanium, zirconium and tantalum to the total content of carbon and nitrogen being from 2 to 9; the steel structure along a cladding length consists of at least two zones: with the steel structure in the top zone of a fuel element providing its higher heat resistance and containing α-ferrite, sorbite, chromium carbides M23C6 and M6C, carbides and carbonitrides of steel components (V, Ta, Ti, Zr, W and others), intermetallics of the Fe2(W) type while the structure in the bottom zone enhancing its resistance to low temperature irradiation embrittlement consists of sorbite, δ -ferrite, α -ferrite, residual austenite, carbides and carbonitrides of steel components (Cr, V, Ta, W and others); in this case high-angle boundaries of grains are occupied by carbides M23C6 and M6C while grains of both sorbite and δ -ferrite have but individual precipitates of carbides and carbonitrides VC, V(CN), Ti(CN) and Ta(CN) and the other elements (Fe, Mn, Mo, W, Si and others) enter into the compositions of either complex carbides M23C6 and M6C or a FeCr solid solution.
- In a particular case of the first version of a fuel element realization the structure of a steel along a cladding length consists of three zones; with the middle zone structure having intermediate values of heat resistance and resistance to low temperature irradiation embrittlement in comparison to those in the bottom and top zones.
- In one of special cases of the second version of fabricating a fuel cladding the contents of unavoidable impurities are limited by concentrations:
- nickel
- - not more than 0.1;
- niobium
- - not more than 0.01;
- molybdenum
- - not more than 0.01;
- copper
- - not more than 0.1;
- cobalt
- - not more than 0.01;
- sulphur
- - not more than 0.008;
- phosphorus
- - not more than 0.008;
- oxygen
- - not more than 0.005.
- In another special case of fabricating a cladding the total content of impurities of high activation metals, viz., molybdenum, niobium, nickel, copper and cobalt, does not exceed 0.1 %mass. This serves to reduce neutron irradiation induced activation and to accelerate the decay rate of induced activation of steel.
- In another special case of fabricating a cladding the total content of impurities of low-melting metals, viz., lead, bithmuth, tin, antimony and arsenic, dots not exceed 0.05 %mass. This serves to enhance the resistance of steel to low temperature irradiation embrittlement under neutron irradiation.
- The essence of the invention consists in the fact that the steel structure along a cladding length is made non-uniform and is brought in conformity with the actual temperature drop along the length of the BN reactor core which makes up several hundred degrees. That is why, the claimed invention puts in practice a novel principle of placing different requirements for the properties and structure of a fuel cladding along its length.
- The steel structure in the bottom (low temperature) zone of a fuel cladding includes sorbite, α -ferrite, residual austenite, carbides of likely strong carbide forming components of the steel (Cr, V, Ti, Ta, W and others), nitrides and carbonitrides of the above mentioned elements; boundaries of large-angle grains are basically free from precipitates of carbides M23C6 and M6C and have an intragranular coagulated carbide phase. As a result of formation of such a structure a solid solution is depleted in chromium and is not capable of irradiation effected precipitation of embrittling phases (υ- phase, α- phase and others) which increases the resistance of a cladding to LTIE processes in its low temperature bottom zone.
- To create such a structure the low temperature zone of a fuel element is subjected to cycling (up to 10 cycles) which comprises heating to the temperature AC1 + 20°C and cooling to room temperature; in this case the rate of product cooling after tempering and in the process of cycling and after it is finished has not to be below 50°C/min upon cooling in air.
- As it follows from the above said to ensure the optimal structure of a fuel cladding in high - and low ―temperature zones and provide it with low activation as well as heat and irradiation resistances the steel is subjected to complex alloying with elements having a prompt decay of irradiation induced activity to attain a specified ratio between γ-stabilizing elements (C, N, Mn) and α -stabilizing ones (Cr, W, V, Ta, Ti, Zr, Mo, Nb and others).
- In a high temperature zone of a fuel element where the operating temperature of a cladding is not lower than 600°C the high level of heat resistance is reached through forming a stable martensitic - ferritic structure of a cladding that contains solid solution strengthening interstitial elements (C,N,B) and substitutional elements (W, V, Cr), strengthening carbide (MC, M2C, M23C6 and others), nitride (MN, M2N) and carbonitride (MCN) phases as well as Laves phases of the Fe(W) type.
- This structure in the high temperature zone of a fuel cladding is formed via quenching at a temperature of 1050-1150°C for 40 min followed by tempering at 680-760°C.
- An increase in the content of tungsten that is introduced in place of molybdenum at an approximately equivalent ratio provides a lower irradiation induced activation of a cladding and its prompt decay with time after neutron exposure due to a lower section of neutron interaction with tungsten nuclei and a lower half-life of irradiation produced isotopes of tungsten, respectively. An increase in the content of tungsten also promotes preservation of a high level of long-term and short-term strength of steel.
- Through introducing zirconium, tantalum and nitrogen the short-term and long-term strength of steel remains at an adequately high level.
- Through introducing nitrogen and limiting within 2 to 9 the ratio of the total contents of titanium, tantalum, zirconium and vanadium to the total contents of carbon and nitrogen the resistance of steel to low temperature irradiation effected embrittlement under neutron irradiation increases.
- Cerium and/or yttrium introduced in the quantity of 0.001-0.10 %mass promotes the refining and atomizing of steel grains. In this case cerium and yttrium being low activation elements do not increase the induced activity of the steel claimed.
- The low levels of cerium and/or yttrium content correspond to the minimal concentration at which its favourable influence on steel refining is noted. The value of the upper limit of cerium and/or yttrium content promotes preservation of the adequate processability by steel at a hot stage.
- The low limit of zirconium content is determined by the need of binding a part of nitrogen into finely dispersed and thermodynamically stable particles of zirconium nitride.
- The upper limit of zirconium content is determined by the feasible formation of low melting zirconium-iron eutectic which might reduce the processability of steel.
- The low limit of titanium content is determined by the need of binding a part of carbon into thermodynamically stable finely dispersed carbides of titanium.
- The upper level of titanium content is determined by feasible redistribution of nitrogen between zirconium and titanium which is not desired because of a possible decrease in long-term strength of steel.
- The low level of tantalum content is determined by the need of binding a part of carbon into thermodynamically stable tantalum carbides and ensuring its content in solid solution at the level of ultimate solubility.
- The upper limit of tantalum content is determined by feasible formation of globular carbide inclusions that reduce the processability of steel.
- The low limit of nitrogen content is determined by the need of binding zirconium into finely dispersed particles of zirconium nitride. The restriction of the nitrogen upper limit is required to provide the processability of steel during welding: zirconium and tantalum being low activation elements do not increase the induced activity of the claimed steel.
- Nitrogen as an isotope 14N (99% content) becomes activated under neutron irradiation to form a long-lived isotope 14C that upon decaying (half-life of 5.7x103 years) produces α-particle (stable isotope 6He) without resulting in γ-radiation, i.e., the availability of nitrogen does not influence the decay of steel radiation activity determined by γ-radiation.
- The content of silicon ranges from 0.1 to 0.8 to ensure deoxidation of steel.
- To provide for the processability of steel and to lower down the quantity of δ-ferrite the content of manganese is kept at the level of 0.5-2.0 percent by weight.
- To provide for heat and irradiation resistance the chromium content of the claimed steel is kept at the level of 10-13.5 percent by weight.
- The carbon content of the claimed steel ranges within 0.10-0.21 percent by weight to provide for the high level of structural stability and heat resistance via the process of martensitic transformation.
- In a vacuum induction furnace two steel ingots 25 kg each as well as two ingots 500 kg each were produced for use as claddings of the claimed fuel element. Ingots 25 kg in mass were forged into billets 35 mm in the diameter that were then forged into plates 10mm thick and a bar 12mm in the diameter. Ingots 500kg in mass were forged into billets 90mm in the diameter that were then rolled to produce a sheet 6mm thick and a bar 12mm in the diameter. The bar, sheet and plates were heat treated under the standard conditions, namely, normalizing and tempering. The heat treated metal was used to fabricate cylindrical samples with the effective part size Ø5x25 mm to be tested for long-term strength and creep in compliance with GOST(ΓOCT) 10145-81 and GOST(ΓOCT) 3248-81. Tensile properties also after irradiation were determined using standard samples in tensile tests according to GOST (ΓOCT) 10446-80. The indicated samples had to simulate the condition of the metal in the high temperature part of a fuel cladding at the operating temperature not lower than 600°C.
- Simultaneously similar small-size gagarin samples were prepared that were to simulate the condition of the metal in the low temperature part of a fuel cladding operating at a temperature not higher than 400°C, i.e., they were used to test their propensity for LTIE.
- To create in the metal of those samples a structure having a higher resistance to LTIE the samples were subjected to cycling, i.e., heating to the temperature AC1+20°C, 10 min holding and cooling to room temperature at a rate of not less than 50°C/min within 600 to 20°C. Altogether 10 cycles were carried out. After the cyclic treatment the samples were subjected to tempering at 720°C for 2 h followed by accelerated cooling (not less than 50°C/min) to room temperature.
- The claimed steel was neutron irradiated in research fast neutron reactor BOR-60 at a temperature of 345-365°C to the fluence of (1.14-2.0) 1022 n/cm2 (E>0.1MeV) at the damage dose of 5.8-8.0 dpa. Tensile tests were conducted using remotely operated breaking machine 1794-Y5 in air at a strain rate of ~1 mm/min. Under the indicated conditions samples were irradiated that had been heat treated under the standard conditions as well as samples that had been subjected to the cyclic heat treatment.
- The chemical compositions of the steels for use as claddings of the claimed fuel element and the known steel are tabulated in table 1, the results of calculating the decay kinetics of the induced activity of those steels are summarized in table 2 and the results of tensile testing are presented in tables 3 and 4.
- The data on the calculated kinetics of the induced activity decay (i.e., the γ-irradiation dose rate) of steels after the assumed irradiation in fast neutron reactors BN-600 for 560 h and subsequent holding up to 500 years evidence the advantages of the claimed steel, that are particularly noticeable after holding for more than 10 years (see table 2). After holding for 50 years the claimed steel might be managed without special protection and might be remelted for re-use.
- Similar calculations carried out for the neutron spectrum of the fusion reactor DEMO demonstrate that the prompt decay of induced activity makes it safe after 50 years holding.
- The results of testing tensile properties (see table 3) corroborate that the steel for the claimed fuel cladding has a substantially higher margin of the LTIE resistance after cycling treatment. So, the values of the per cent elongation of the claimed steel samples as BN-600 reactor irradiated at temperatures of 345-365°C at which LTIE is revealed have lower values at both 20°C (2.6-6.1%) and at the irradiation temperature (1.3-1.7%) while after cycling treatment these values are 1.5-2 times higher.
- The results of long-term strength and creep tests carried out according to GOST (ΓOCT)10145-81 and GOST (ΓOCT) 3248-81 demonstrated (see table4) that the steel for claddings of the claimed fuel element after heat treatments under the chosen conditions is heat resistant at temperatures of 650-750°C and even in its modifications having a lower nitrogen content. For instance, the creep rate of the claimed steel at 650°C at a stress of 8kgf/mm2 makes up (0.9-7)x10-4 %/h. Similar results are also observable at stresses of 10 and 12 kgf/mm2.
- Thus the claimed fuel element cladding is usable in cores of fast neutron reactors. The use of a fuel element with a cladding having the claimed properties shall provide for high cost-effectiveness due to a more prompt decay of induced activity and have high properties of heat resistance and resistance to low temperature irradiation embrittlement. This cost-effectiveness effect will manifest in lower contamination of environment effected by operating nuclear power facilities of novel generation and in feasibility of re-using structural materials.
Table 2. Kinetics of Decay of Absorbed γ-Radiation Dose Rate (Sv/h) in Claimed Steel as Fusion Reactor DEMO Irradiated (neutron burden on first wall is 12,5 MW·year/m2, irradiation time - 10 years, E=14 MeV) Nominal N Of ingot γ - irradiation dose after end of irradiation (Sv/h) 1 hour 1 month 1 year 10 years 50 years 100 years 500 years 1 5·102 2.9·102 16 1 1·1O-2** 1·1O-3 5·1O-4 2 4·102 1.5·102 20 1 1·1O-2** 1·1O-3 5·1O-4 3 6·102 2.5·102 17 1 1·1O-2** 1·1O-3 5·1O-4 4 1·102 4·102 30 1 1·1O-2** 1·1O-3 5·1O-4 Notes: * Transmutation of elements and induced activity were computed using program FISPACT-30 (R.A. Forrest, J.-CH. Sublet. "FISPACT-3 User Manual", report AEA/FUS/227, 1993). γ - radiation dose rate that attends radioactive decay of ** 1·1O-2 Sv/h - is safe level of γ - radiation at which according to IAEA rules material might be re-used.
Claims (6)
- A fuel element for fast neutron reactor fuel element that consists of tubular cladding sealed with top and bottom plugs at its ends, pelletized nuclear fuel sited within cladding as well as needed structural elements, CHARACTERIZED in that its cladding is fabricated from ferritic-martensitic steel the structure of which along cladding length contains at least two zones; steel structure in the top zone of cladding providing higher heat resistance while in the bottom zone providing higher resistance to low temperature irradiation embrittlement.
- A fuel element as claimed in claim 1, CHARACTERIZED in that the structure of steel along cladding length has three zones with the steel structure in the middle zone having intermediate values of characteristics of heat resistance and resistance to low temperature irradiation embrittlement in comparison to those in the top and bottom zones.
- A fuel element for fast neutron reactor comprising a tubular cladding sealed with top and bottom plugs at its ends, pelletized nuclear fuel sited within cladding as well as needed structural elements, CHARACTERIZED in that its cladding is fabricated from low activation steel containing carbon, silicon, manganese, chromium, vanadium, tungsten, boron, cerium and/or yttrium, titanium, tantalum, zirconium, nitrogen, iron and unavoidable impurities at the following ratio between components, percent by weight:carbon - 0.10-0.21;silicon - 0.1-0.8;manganese - 0.5-2.0;chromium - 10.0-13.5;tungsten - 0.8-2.5;vanadium - 0.05-0.4;titanium - 0.03-0.3;boron - 0.001-0.008;cerium and/or yttrium in total - 0.001-0.10;zirconium - 0.05-0.2;tantalum - 0.05-0.2;nitrogen - 0.02-0.15;iron - the balanceat the ratio of the total content of vanadium, titanium, zirconium and tantalum to the total content of carbon and nitrogen equal to 2 to 9, with the steel structure along the cladding length having at least two zones; the steel structure in the top zone of a fuel cladding provides higher heat resistance and contains α-ferrite, δ-ferrite, sorbite, chromium carbides M23C6 and M6C, carbides and carbonitrides of steel components (V, Ta, Ti, Zr, W and others), intermetallics of Fe2(W) type while the structure in the bottom zone provides higher resistance to low temperature irradiation embattlement and consists of sorbite, δ-ferrite, α-ferrite, residual austenite, carbides and carbonitrides of steel components (Cr, V, Ta, W and others); with large angle boundaries of grains being occupied by carbides M23C6 and M6C while grains of both sorbite and δ -ferrite having only individual precipitates of carbides and carbonitrides VC, V(CN), Ti(CN) and Ta(CN) while the other elements (Fe, Mn, Mo, W, Si and others) entering into the compositions of either complex carbides M23C6 and M6C or solid solution FeCr.
- A Fuel cladding for fast neutron reactor that is fabricated from low activation steel containing carbon, silicon, manganese, chromium, vanadium, tungsten, boron, cerium and/or yttrium, titanium, tantalum, zirconium, nitrogen, iron and unavoidable impurities at the following ratio between components, percent by weight:carbon - 0.10-0.21;silicon - 0.1-0.8;manganese - 0.5-2.0;chromium - 10.0-13.5;tungsten - 0.8-2.5;vanadium - 0.05-0.4;titanium - 0.03-0.3;boron - 0.001-0.008;cerium and/or yttrium in total - 0.001-0.10;zirconium - 0.05-0.2;tantalum - 0.05-0.2;nitrogen - 0.02-0.15;iron - the balanceat the ratio of the total content of vanadium, titanium, zirconium and tantalum to the total content of carbon and nitrogen equal to 2 up to 9, with the steel structure along the cladding length having at least two zones; the steel structure in the top zone of a fuel element provides its higher heat resistance and contains α -ferrite, δ -ferrite, sorbite, chromium carbides M23C6 and M6C, carbides and carbonitrides of steel components (V, Ta, Ti, Zr, W and others), intermetallics of Fe2(W) type while the structure in the bottom zone provides higher resistance to low temperature irradiation embrittlement and consists of sorbite, δ- ferrite, α-ferrite, residual austenite, carbides and carbonitrides of steel components (Cr, V, Ta, W and others); with large angle grain boundaries being occupied by carbides M23C6 and M6C while grains of both sorbite and δ-ferrite having only individual precipitates of carbides and carbonitredes VC, V(CN), Ti(CN), Ta(CN) and the other elements entering into the compositions of either complex carbides M23C6 and M6C or solid solution FeCr.
- A fuel cladding as claimed in claim 4, CHARACTERIZED in that the content of unavoidable impurities in steel is restricted by the concentrations:nickel - not more than 0.1;niobium - not more than 0.01;molybdenum - not more than 0.01;copper - not more than 0.1;cobalt - not more than 0.01;sulphur - not more than 0.008;phosphorus - not more than 0.008;oxygen - not more than 0.005.at the total content of impurities of high activation metals, namely, molybdenum, niobium nickel, copper and cobalt not exceeding 0.10 percent by weight.
- A fuel cladding as claimed in claim 4, CHARACTERIZED in that the total content of impurities of low melting metals, namely, lead, bithmuth, tin, antimony and arsenic, does not exceed 0.05 percent by weight.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2003129679/02A RU2262753C2 (en) | 2003-10-06 | 2003-10-06 | Fast reactor fuel element (versions) and the can for its fabrication |
PCT/RU2004/000384 WO2005034139A2 (en) | 2003-10-06 | 2004-10-04 | Fuel element for a fast neutron reactor (variants) and a cladding for the production thereof |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1693855A2 true EP1693855A2 (en) | 2006-08-23 |
EP1693855A4 EP1693855A4 (en) | 2013-01-02 |
EP1693855B1 EP1693855B1 (en) | 2014-12-17 |
Family
ID=34420871
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04793751.1A Active EP1693855B1 (en) | 2003-10-06 | 2004-10-04 | Fuel element for a fast neutron reactor (variants) and a cladding for the production thereof |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1693855B1 (en) |
CN (1) | CN1890758B (en) |
RU (1) | RU2262753C2 (en) |
WO (1) | WO2005034139A2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102194531A (en) * | 2010-03-11 | 2011-09-21 | 中国核动力研究设计院 | Dual travelling wave partition burning method for fast reactor fuels |
US20160225468A1 (en) * | 2013-11-19 | 2016-08-04 | Joint Stock Company "Akme-Engineering" | Fuel rod cladding, fuel rod and fuel assembly |
WO2017180647A1 (en) * | 2016-04-11 | 2017-10-19 | Terrapower, Llc | High temperature, radiation-resistant, ferritic-martensitic steels |
RU2634867C1 (en) * | 2016-12-28 | 2017-11-07 | Акционерное общество "Научно-производственное объединение "Центральный научно-исследовательский институт технологии машиностроения", АО "НПО "ЦНИИТМАШ" | Heat-resistant and radiation-resistant steel |
EP2938751B1 (en) * | 2012-12-28 | 2022-07-27 | TerraPower LLC | Iron-based composition for fuel element |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2515716C1 (en) * | 2013-04-26 | 2014-05-20 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Low-activated fire-resistant radiation-resistant steel |
KR101676243B1 (en) * | 2014-12-02 | 2016-11-30 | 현대자동차주식회사 | Heat resistant cast steel having superior high temperature strength and oxidation resistant |
RU2615961C1 (en) * | 2015-11-26 | 2017-04-11 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Assembly of welded joint of fuel element jacket with plug made of high-chromium steel (versions) |
RU2603355C1 (en) * | 2015-11-26 | 2016-11-27 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Sealing method of nuclear reactor fuel elements with high-chromium steel shell |
CN108356263B (en) * | 2018-04-28 | 2019-09-24 | 苏州大学 | Laser gain material manufacture heat-resisting steel alloy powder of novel martensitic and preparation method thereof |
RU2683168C1 (en) * | 2018-05-15 | 2019-03-26 | Акционерное общество "Научно-производственное объединение "Центральный научно-исследовательский институт технологии машиностроения", АО "НПО "ЦНИИТМАШ" | Neutron-irrigate steel |
CN112695256A (en) * | 2020-11-27 | 2021-04-23 | 中国核动力研究设计院 | Ferrite martensite steel ladle shell material and preparation method thereof |
CN112695255B (en) * | 2020-11-27 | 2021-09-17 | 中国核动力研究设计院 | Preparation method of ferrite martensite steel clad tube |
CN113355497B (en) * | 2021-06-04 | 2022-05-31 | 西安建筑科技大学 | Low-activation steel plate and preparation process thereof |
CN114959484B (en) * | 2022-06-06 | 2023-04-25 | 武汉钢铁有限公司 | Hot-rolled wire rod for 80-grade bead wire, preparation method of hot-rolled wire rod and automobile tire |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4960562A (en) * | 1988-11-19 | 1990-10-02 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Dispersion strengthened ferritic steel cladding tube for nuclear reactor and its production method |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU749914A1 (en) * | 1977-07-04 | 1980-07-23 | Предприятие П/Я А-3700 | Method of thermal treatment of high-streength corrosion-resistant martensite steels |
US4927468A (en) * | 1988-11-30 | 1990-05-22 | The United States Of America As Represented By The United States Department Of Energy | Process for making a martensitic steel alloy fuel cladding product |
FR2642215B1 (en) * | 1989-01-23 | 1992-10-02 | Framatome Sa | PENCIL FOR FUEL ASSEMBLY OF A CORROSION AND WEAR RESISTANT NUCLEAR REACTOR |
RU2033461C1 (en) * | 1991-06-28 | 1995-04-20 | Институт металлургии им.А.А.Байкова РАН | Low-activated heat-resistant steel |
FR2686445B1 (en) * | 1992-01-17 | 1994-04-08 | Framatome Sa | NUCLEAR FUEL PENCIL AND METHOD FOR MANUFACTURING THE SHEATH OF SUCH A PENCIL. |
RU2072572C1 (en) * | 1994-08-05 | 1997-01-27 | Научно-исследовательский институт атомных реакторов | Method for detection of gas permeability of fuel column of heat elements and for detection of position of gas-tight lock |
RU2211878C2 (en) * | 2001-07-06 | 2003-09-10 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт неорганических материалов им. акад. А.А.Бочвара" | Low-active high-temperature radiation steel |
-
2003
- 2003-10-06 RU RU2003129679/02A patent/RU2262753C2/en active
-
2004
- 2004-10-04 EP EP04793751.1A patent/EP1693855B1/en active Active
- 2004-10-04 CN CN2004800361451A patent/CN1890758B/en active Active
- 2004-10-04 WO PCT/RU2004/000384 patent/WO2005034139A2/en active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4960562A (en) * | 1988-11-19 | 1990-10-02 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Dispersion strengthened ferritic steel cladding tube for nuclear reactor and its production method |
Non-Patent Citations (2)
Title |
---|
IOLTUKHOVSKIY A G ET AL: "Heat resistant reduced activation 12% Cr steel of 16Cr12W2VTaB type-advanced structural material for fusion and fast breeder power reactors", JOURNAL OF NUCLEAR MATERIALS, ELSEVIER BV, NL, vol. 307-311, 1 December 2002 (2002-12-01) , pages 532-535, XP004400748, ISSN: 0022-3115, DOI: 10.1016/S0022-3115(02)01087-5 * |
See also references of WO2005034139A2 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102194531A (en) * | 2010-03-11 | 2011-09-21 | 中国核动力研究设计院 | Dual travelling wave partition burning method for fast reactor fuels |
EP2938751B1 (en) * | 2012-12-28 | 2022-07-27 | TerraPower LLC | Iron-based composition for fuel element |
US20160225468A1 (en) * | 2013-11-19 | 2016-08-04 | Joint Stock Company "Akme-Engineering" | Fuel rod cladding, fuel rod and fuel assembly |
US10720244B2 (en) * | 2013-11-19 | 2020-07-21 | Joint Stock Company “Akme-Engineering” | Fuel rod cladding, fuel rod and fuel assembly |
WO2017180647A1 (en) * | 2016-04-11 | 2017-10-19 | Terrapower, Llc | High temperature, radiation-resistant, ferritic-martensitic steels |
RU2634867C1 (en) * | 2016-12-28 | 2017-11-07 | Акционерное общество "Научно-производственное объединение "Центральный научно-исследовательский институт технологии машиностроения", АО "НПО "ЦНИИТМАШ" | Heat-resistant and radiation-resistant steel |
Also Published As
Publication number | Publication date |
---|---|
WO2005034139A3 (en) | 2005-07-28 |
EP1693855A4 (en) | 2013-01-02 |
EP1693855B1 (en) | 2014-12-17 |
RU2262753C2 (en) | 2005-10-20 |
RU2003129679A (en) | 2005-04-10 |
CN1890758A (en) | 2007-01-03 |
CN1890758B (en) | 2010-07-21 |
WO2005034139A2 (en) | 2005-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1693855B1 (en) | Fuel element for a fast neutron reactor (variants) and a cladding for the production thereof | |
EP2647732B1 (en) | Precipitation-strengthened ni-based heat-resistant alloy and method for producing the same | |
Diercks et al. | Alloying and impurity effects in vanadium-base alloys | |
HAWTHORNE | Irradiation embrittlement | |
Klueh | Heat treatment behavior and tensile properties of Cr− W steels | |
Salama et al. | Distinct properties of tungsten austenitic stainless alloy as a potential nuclear engineering material | |
US5292384A (en) | Cr-W-V bainitic/ferritic steel with improved strength and toughness and method of making | |
Klueh et al. | Development of low-chromium, chromium-tungsten steels for fusion | |
US4818485A (en) | Radiation resistant austenitic stainless steel alloys | |
Chaouadi et al. | Neutron irradiation hardening of chemically-tailored RPV steels with respect to Cu/P and Ni/Mn elements | |
RU2360992C1 (en) | Low-activated heat-resistant radiation-resistant steel | |
EP3369833B1 (en) | Dispersion strengthened austenitic stainless steel, method for manufacturing stainless steel and product made from stainless steel | |
CN106148845B (en) | Low-activation bainitic steel applicable to neutron-irradiated environment and preparation method thereof | |
EP0076110B1 (en) | Maraging superalloys and heat treatment processes | |
RU2325459C2 (en) | Chromium low-doped corrosion-resistant and radiation-resistant steel | |
RU2211878C2 (en) | Low-active high-temperature radiation steel | |
Materna-Morris et al. | The influence of boron on structural properties of martensitic 8-10% Cr-steels | |
Rao | Materials development for indian nuclear power programme: an industry perspective | |
KR100896988B1 (en) | High-Cr Ferritic/Martensitic Steels having improved neutron irradiation stability containing an enriched boron-11 for the in-core component materials in the Gen-? fission reactor and the fusion reactor | |
EP3778972B1 (en) | Low alloy heat-resistant steel and steel pipe | |
RU2267173C1 (en) | Breeding element for a thermonuclear reactor of synthesis | |
RU2515716C1 (en) | Low-activated fire-resistant radiation-resistant steel | |
JP2546549B2 (en) | Method for producing B-containing austenitic stainless steel | |
Ioltukhovskiy et al. | Heat resistant reduced activation 12% Cr steel of 16Cr12W2VTaB type-advanced structural material for fusion and fast breeder power reactors | |
Shibahara | Development of in-core materials for fast breeder reactors |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20060508 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20121129 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C22C 38/22 20060101ALI20121123BHEP Ipc: C21D 9/00 20060101ALI20121123BHEP Ipc: C22C 38/24 20060101ALI20121123BHEP Ipc: C21D 6/00 20060101ALI20121123BHEP Ipc: G21D 1/00 20060101AFI20121123BHEP |
|
17Q | First examination report despatched |
Effective date: 20130626 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20140422 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 702402 Country of ref document: AT Kind code of ref document: T Effective date: 20150115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602004046356 Country of ref document: DE Effective date: 20150129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20150318 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 702402 Country of ref document: AT Kind code of ref document: T Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602004046356 Country of ref document: DE |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
26N | No opposition filed |
Effective date: 20150918 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20151004 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151031 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151031 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151004 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20041004 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141217 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20220802 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20220706 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20220812 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602004046356 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20231004 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20231004 |