EP2432905B1 - Alliage ferrito-martensitique à base de fer, un élément de construction et un procédé - Google Patents
Alliage ferrito-martensitique à base de fer, un élément de construction et un procédé Download PDFInfo
- Publication number
- EP2432905B1 EP2432905B1 EP09776639.8A EP09776639A EP2432905B1 EP 2432905 B1 EP2432905 B1 EP 2432905B1 EP 09776639 A EP09776639 A EP 09776639A EP 2432905 B1 EP2432905 B1 EP 2432905B1
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- European Patent Office
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- pressure turbine
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- 229910045601 alloy Inorganic materials 0.000 title claims description 21
- 239000000956 alloy Substances 0.000 title claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 5
- 229910052742 iron Inorganic materials 0.000 title claims description 4
- 229910000734 martensite Inorganic materials 0.000 title description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- 230000007774 longterm Effects 0.000 description 7
- 229910001566 austenite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001068 laves phase Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- 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
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
-
- 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
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
Definitions
- the invention relates to a ferritic martensitic alloy, a component and a method.
- Iron-base alloys are inexpensive alloys compared to nickel-base superalloys, but the strengths and tougures are lower compared to the nickel-base superalloys.
- the object is achieved by an alloy according to claim 1, by a component according to claim 10 and a method according to claim 11.
- the new ferritic martensitic alloy preferably dispenses with the addition of tungsten (W) except for the commercial impurities which are significantly below 0.1 wt%, in particular below 0.01 wt%.
- FIGS. 1 to 3 show some embodiments of the invention.
- the boron content gives a very good long-term stability at elevated temperatures.
- the boron content with the required nitrogen content is optimized to prevent the formation of Boron nitrides to avoid. This results in a good balance of skill and tenacity. Boron stabilizes the microstructure by incorporation into chromium-based M23C6 carbides and reduces the growth of the M23C6 carbides, thereby achieving high microstructure stabilization and, thus, creep rupture strength.
- tungsten it has been found that no tungsten must be used to achieve high long term crafting with good long term pot life.
- the tenacities do not change as a function of temperature and time.
- Tungsten is preferably not added, since tungsten acts as a solid-solution hardener, but tungsten is long-term precipitated as Laves phase and then coarsened faster than other particles and thus no longer participates in the particle stabilization of the structure.
- temperatures ⁇ 550 ° C the long-term ability of tungsten may be degraded.
- the nickel content gives good forgeability.
- the content of nickel is lowered because of the improvement of the creep strength by reducing the diffusion coefficients in the microstructure.
- a compensation of the changed through temperability takes place by adding carbon (C) and cobalt (Co).
- the content of carbon (C) is lowered because of balance with other elements to obtain a martensite structure with high toughness. Due to the lowered carbon content, a complete transformation of the austenite on cooling to room temperature can take place (no retained austenite) whereby a high structural homogeneity, good martensite lath structure, high toughness, fine carbide formation of M23C6 is achieved in order to achieve a good creep rupture strength. Carbon is required to form M23C6.
- carbon contents> 0.13wt% are used.
- Nitrogen forms MX particles (VN, VCC, N) Nb (C, N) for particle hardening of the martensite microstructure based on (V, Nb) N, thereby increasing the creep rupture strength (MX stands for precipitates of the form VN, V (C, N ) Nb (C, N).
- nitrogen contents > 150 ppm are used.
- the content of silicon is lowered because of the thereby improved long-term ability and reduction of nucleation for Laves phase precipitation (see under tungsten).
- the levels of phosphorus, sulfur, copper are lowered to improve the initial toughness of the structure and ensure high long-term capability.
- Titanium is preferably not used because otherwise nitrogen would be bound as TiN and thus would miss the MX particles of the form (V, Nb) N required for creep rupture.
- FIG. 2 a steam turbine 300, 303 is shown with a turbine shaft 309 extending along a rotation axis 306.
- the steam turbine has a high-pressure turbine section 300 and a medium-pressure turbine section 303, each having an inner housing 312 and an outer housing 315 enclosing this.
- the high-pressure turbine part 300 is designed, for example, in Topfbauart.
- the medium-pressure turbine part 303 is designed, for example, double-flow. It is also possible for the medium-pressure turbine section 303 to be single-flow.
- a bearing 318 is arranged between the high-pressure turbine section 300 and the medium-pressure turbine section 303, the turbine shaft 309 having a bearing region 321 in the bearing 318.
- the turbine shaft 309 is supported on another bearing 324 adjacent to the high pressure turbine sub 300.
- the high-pressure turbine section 300 has a shaft seal 345.
- the turbine shaft 309 is sealed off from the outer housing 315 of the medium-pressure turbine section 303 by two further shaft seals 345.
- the turbine shaft 309 in the high-pressure turbine section 300 has the high-pressure impeller blade 357. This high pressure blading 357 represents with the associated, not shown blades a first blading area 360.
- the medium-pressure turbine part 303 has a central steam inflow region 333.
- the turbine shaft 309 has a radially symmetrical shaft shield 363, a cover plate, on the one hand for dividing the steam flow into the two flows of the medium-pressure turbine section 303 and for preventing direct contact of the hot steam with the turbine shaft 309.
- the turbine shaft 309 has a second blading area 366 with the medium-pressure rotor blades 354 in the medium-pressure turbine section 303. The hot steam flowing through the second blading area 366 flows out of the medium-pressure turbine section 303 from a discharge connection 369 to a downstream low-pressure turbine, not shown.
- the turbine shaft 309 is composed for example of two partial turbine shafts 309a and 309b, which are fixedly connected to one another in the region of the bearing 318.
- Each turbine shaft 309a, 309b has a cooling line 372 formed as a central bore 372a along the axis of rotation 306.
- the cooling line 372 is connected to the steam outlet region 351 via an inflow line 375 having a radial bore 375a.
- the coolant line 372 is connected to a cavity not shown below the shaft shield.
- the feed lines 375 are configured as a radial bore 375a, allowing "cold" steam from the high pressure turbine section 300 to flow into the central bore 372a.
- the vapor passes through the storage area 321 into the medium-pressure turbine section 303 and there to the mantle surface 330 of the turbine shaft 309 in the steam inflow area 333.
- the steam flowing through the cooling line has a significantly lower temperature as the reheated steam flowing into the steam inflow region 333, see FIG that an effective cooling of the first rotor blade rows 342 of the medium-pressure turbine section 303 and of the jacket surface 330 in the region of these rotor blade rows 342 is ensured.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Claims (11)
- Alliage à base de fer,
qui est constitué de (en pourcentage en poids) :carbone (C) : de 0,13 % à 0,22 %,chrome (Cr) : de 9,0 % à 9,8 %molybdène (Mo) : de 1,0 % à 2,0 %, notamment de 1,4 % à 1,6 %,nickel (Ni) : de 0,3 % à 0,8 %, notamment de 0,3 % à 0,7 %,vanadium (V) : de 0,25 % à 0,35 %, notamment de 0,25 % à 0,3 %,aluminium (Al) : de 0,005 % à 0,01 %,niobium (Nb) : de 0,04 % à 0,06 %,bore (B) : de 20ppm à 70 ppm, notamment de 35 ppm à 55 ppm,azote (N) : de 150 ppm à 500 ppm,notamment au maximum 350 ppm,d'une manière tout à fait particulière au maximum 300ppm,cobalt (Co) : de 0,8 % à 1,5 %, notamment jusqu'à 1,3 %,manganèse (Mn) : de 0 % à 0,15 %,notamment au moins à 0,05 %,silicium (Si) : de 0 % à 0,1 %,notamment au moins 0,01 %,phospore (P) : de 0 % à 0,005 %,soufre (S) : de 0 % à 0,003 %,notamment au moins 0, 001 %,arsenic (As) : au maximum 0,015 %,étain (Sn) : au maximum 0,015 %,antimoine (Sb) : au maximum 0,015 %,cuivre (Cu) : au maximum 0,1 %,notamment au moins 0,01 %,d'une manière tout à fait particulière au moins 0,05 %,fer (Fe). - Alliage suivant la revendication 1,
qui contient au maximum 0,18 % de carbone (C),
qui contient notamment au maximum 0,15 % en poids de carbone (C). - Alliage suivant la revendication 1,
qui contient au moins 0,15 % en poids de carbone,
qui contient notamment au moins 0,18 % en poids de carbone, - Alliage suivant la revendication 1, 2 ou 3,
qui a au moins 9,3 % en poids de chrome (Cr). - Alliage suivant la revendication 1, 2, 3 ou 4,
qui a au maximum 9,4 % en poids de chrome (Cr). - Alliage suivant la revendication 1, 2, 3, 4 ou 5,
qui a au moins 0,5 % en poids de nickel (Ni). - Alliage suivant la revendication 1, 2, 3, 4 ou 5,
qui a au maximum 0,4 % en poids de nickel (Ni). - Alliage suivant la revendication 1, 2, 3, 4, 5, 6 ou 7,
qui a au moins 0,9 % en poids de cobalt (Co). - Alliage suivant l'une ou plusieurs des revendications précédentes 1 à 8,
qui contient du phosphore (P),
notamment au moins 0,001 % en poids. - Pièce en un alliage suivant l'une ou plusieurs des revendications 1 à 9.
- Procédé de fabrication d'une pièce par coulée, dans lequel on coule un alliage suivant l'une ou plusieurs des revendications 1 à 9.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2009/003640 WO2010133244A1 (fr) | 2009-05-22 | 2009-05-22 | Alliage ferrito-martensitique à base de fer, un élément de construction et un procédé |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2432905A1 EP2432905A1 (fr) | 2012-03-28 |
EP2432905B1 true EP2432905B1 (fr) | 2016-04-13 |
Family
ID=42173351
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09776639.8A Active EP2432905B1 (fr) | 2009-05-22 | 2009-05-22 | Alliage ferrito-martensitique à base de fer, un élément de construction et un procédé |
Country Status (4)
Country | Link |
---|---|
US (1) | US20120070329A1 (fr) |
EP (1) | EP2432905B1 (fr) |
CN (1) | CN102428197B (fr) |
WO (1) | WO2010133244A1 (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9039365B2 (en) * | 2012-01-06 | 2015-05-26 | General Electric Company | Rotor, a steam turbine and a method for producing a rotor |
JP6317542B2 (ja) * | 2012-02-27 | 2018-04-25 | 三菱日立パワーシステムズ株式会社 | 蒸気タービンロータ |
EP2653587A1 (fr) * | 2012-04-16 | 2013-10-23 | Siemens Aktiengesellschaft | Composants de turbomachine avec un revêtement de fonction |
WO2015039005A2 (fr) * | 2013-09-13 | 2015-03-19 | Federal-Mogul Corporation | Joint chaud en acier inoxydable |
CN104372262B (zh) * | 2014-11-10 | 2016-05-04 | 苏州蔻美新材料有限公司 | 一种医疗器械用不锈钢及其制备方法 |
CN105438637A (zh) * | 2015-12-24 | 2016-03-30 | 常熟市新冶机械制造有限公司 | 摩根线材打捆机 |
US20200165709A1 (en) * | 2017-09-21 | 2020-05-28 | Mitsubishi Hitachi Power Systems, Ltd. | Gas turbine disk material and heat treatment method therefor |
CN108342661A (zh) * | 2018-01-22 | 2018-07-31 | 江苏理工学院 | 一种火电机组用耐热钢合金材料及其制造工艺 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3387145B2 (ja) * | 1993-04-08 | 2003-03-17 | 住友金属工業株式会社 | 高温延性および高温強度に優れた高Crフェライト鋼 |
DE19607736A1 (de) * | 1996-02-29 | 1997-09-04 | Siemens Ag | Turbinenwelle |
JPH09296258A (ja) * | 1996-05-07 | 1997-11-18 | Hitachi Ltd | 耐熱鋼及び蒸気タービン用ロータシャフト |
DE60220191T2 (de) * | 2001-06-06 | 2008-01-17 | Nippon Steel Corp. | Hochfestes feuerverzinktes galvanisiertes stahlblech und feuerverzinktes geglühtes stahlblech mit ermüdungsfestigkeit,korrosionsbeständigkeit,duktilität und plattierungshaftung,nach starker verformung und verfahren zu dessen herstellung |
US7491910B2 (en) * | 2005-01-24 | 2009-02-17 | Lincoln Global, Inc. | Hardfacing electrode |
-
2009
- 2009-05-22 CN CN2009801593641A patent/CN102428197B/zh active Active
- 2009-05-22 EP EP09776639.8A patent/EP2432905B1/fr active Active
- 2009-05-22 US US13/321,196 patent/US20120070329A1/en not_active Abandoned
- 2009-05-22 WO PCT/EP2009/003640 patent/WO2010133244A1/fr active Application Filing
Non-Patent Citations (2)
Title |
---|
ASHLEY G: "Patentability of alloys at the European Patent Office", INTELLECTUAL PROPERTY, BIRMINGHAM, GB, vol. 2, no. 3, 1 May 1997 (1997-05-01), pages 3 - 6, XP007922941, ISSN: 1361-5793 * |
SPIEKERMANN P: "Alloys - a special problem of patent law", NONPUBLISHED ENGLISH TRANSLATION OF DOCUMENT, pages 1 - 20, XP002184689 * |
Also Published As
Publication number | Publication date |
---|---|
WO2010133244A1 (fr) | 2010-11-25 |
CN102428197B (zh) | 2013-12-11 |
EP2432905A1 (fr) | 2012-03-28 |
US20120070329A1 (en) | 2012-03-22 |
CN102428197A (zh) | 2012-04-25 |
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