EP2728028B1 - Edelstahllegierung ohne Nickel - Google Patents
Edelstahllegierung ohne Nickel Download PDFInfo
- Publication number
- EP2728028B1 EP2728028B1 EP12191101.0A EP12191101A EP2728028B1 EP 2728028 B1 EP2728028 B1 EP 2728028B1 EP 12191101 A EP12191101 A EP 12191101A EP 2728028 B1 EP2728028 B1 EP 2728028B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- maximum value
- valeur
- minimum value
- value
- nickel
- 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.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 88
- 229910052759 nickel Inorganic materials 0.000 title claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 229910045601 alloy Inorganic materials 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 23
- 229910052804 chromium Inorganic materials 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 15
- 239000010959 steel Substances 0.000 description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910001566 austenite Inorganic materials 0.000 description 6
- 229910000734 martensite Inorganic materials 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 206010011416 Croup infectious Diseases 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001353 gamma loop Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 101150034785 gamma gene Proteins 0.000 description 1
- 238000011194 good manufacturing practice Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000003466 welding Methods 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
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- 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
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- 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
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
-
- 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
- C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
-
- 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
- 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
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium 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
- C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
-
- G—PHYSICS
- G04—HOROLOGY
- G04G—ELECTRONIC TIME-PIECES
- G04G17/00—Structural details; Housings
- G04G17/02—Component assemblies
-
- G—PHYSICS
- G04—HOROLOGY
- G04G—ELECTRONIC TIME-PIECES
- G04G17/00—Structural details; Housings
- G04G17/08—Housings
Definitions
- the invention relates to a stainless steel alloy having a base of iron and chromium.
- the invention also relates to a watch component made of such an alloy.
- the invention relates to the fields of watchmaking, jewelery, and jewelery, in particular for structures: watch cases, squares, turntables, bracelets, rings, earrings and others.
- Stainless steels are commonly used in the fields of watchmaking, jewelery, and jewelery, especially for structures: watch cases, casebacks, turntables, bracelets, and others.
- Nickel is, however, a basic component of most common stainless steels because it improves mechanical properties and ductility, malleability and resilience. By cons nickel is harmful in the field of friction surfaces. Nickel improves the properties of the passive layer, and integrates with the surface layer of oxide.
- alloy X2CrNiMo17-12 EN (or 316L AISI) comprises between 10.5 and 13% of nickel. Nickel is a metal whose cost is growing continuously, and which, in 2012, is close to 20'000 USD per ton, which increases the cost of alloys containing it.
- Nickel-free stainless steel alloys are known which are ferritic steels with a cubic centered structure. However, these ferritic steels are not hardenable by heat treatment, but only by hardening. Their structure is not very fine, and this family of alloys is not very suitable for polishing.
- Austenitic steels of face-centered cubic structure, generally have very good forming properties, which is particularly advantageous for watchmaker or jeweler-type components. They have a very high chemical resistance. They are also non-magnetic because of their face-centered cubic structure. They are also the most suitable for welding. But conventional austenitic stainless steels still contain from 3.5 to 32% of nickel, and more commonly from 8.0 to 15.0% of nickel. Indeed, nickel is a gammagene element which makes it possible to obtain the austenitic structure, and in particular to obtain sheets capable of forming deformations. Some documents, such as FR 2,534,931 on behalf of CABOT CORPORATION go so far as to say that nickel must be present to favor an austenitic structure in the alloy.
- the gamma loop of the iron-chromium system specific to stainless steels defines an austenitic domain, even with a low or zero nickel content, but the loop is of very limited magnitude compared to that of alloys containing nickel. in higher proportion. In addition, this austenitic domain exists at temperatures much higher than ambient. The effect of the gammagenic alloy elements is twofold since it also makes it possible to widen the austenitic loop in chemical composition (relative to chromium) and to widen the temperature range on which this structure is stable.
- Austeno-ferritic steels also called duplex, are weak magnetic, and generally comprise between 3.5% and 8% nickel.
- the nickel-free stainless steels are mainly ferritic steels
- the advantages of the austenitic steels, which are generally cataloged as nickel steels, should be available.
- gammagens such as nickel, manganese or nitrogen are generally used (these are called super-austenitic steels for the last two mentioned), which increase the range of stability of austenite. Theoretically it would therefore be possible to use a super-austenitic steel with manganese or nitrogen in place of nickel.
- the patent EP 1 025 273 B1 on behalf of SIMA describes such a nickel-free austenitic stainless steel, comprising 15 to 24% manganese, 15 to 20% chromium, 2.5 to 4% molybdenum, 0.6 to 0.85% d nitrogen, 0.1 to 0.5% vanadium, less than 0.5% copper, less than 0.5% cobalt, less than 0.5% for total niobium and tantalum, less than 0.06% of carbon, other elements each limited to 0.020% by weight, the balance being iron, and the compositions of certain metals being limited to each other by means of a system of equations and inequalities, which regulate the contents of chromium, molybdenum, nitrogen, vanadium, niobium, and manganese.
- the invention also relates to a watch or jewelery component made of such an alloy.
- the invention proposes to produce stainless steels without nickel, which have properties similar to those of austenitic stainless steels with nickel.
- nickel-free alloy will be referred to below as an alloy comprising less than 0.5% by weight of nickel.
- the alloy comprises, in addition to a base consisting of iron and chromium, at least one filler metal selected from a first group consisting of copper, ruthenium, rhodium, palladium and rhenium. , osmium, iridium, platinum, and gold.
- the alloy comprises, in addition to a base consisting of iron, carbon and chromium, at least one filler metal chosen from a subset of the first set consisting of ruthenium, rhodium, palladium, rhenium, osmium, iridium, and platinum.
- these metals are part of PGM (platinum group metals) or platinoids, that is to say that they are characterized by common and unusual properties for metals.
- PGM platinum group metals
- platinoids that is to say that they are characterized by common and unusual properties for metals.
- These PGM group metals are also more soluble in iron than copper and gold.
- a suitable (mass) composition is 18% chromium, 35% palladium, and 46 to 47% iron. Like all stainless steel, this alloy can contain up to 0.03% carbon.
- its mass composition is 18% chromium, 35% palladium, 0% to 0.03% carbon, and the iron supplement. More particularly, its mass composition is 18% chromium, 35% palladium, and 46.97 to 47% iron, and 0 to 0.03% carbon.
- the figure 2 is a Schaeffler diagram, which has on the abscissa an equivalent chromium, and on the ordinate a nickel equivalent, both in percentage by mass.
- This Schaeffler diagram delimits the ferritic, martensitic and austenitic domains, the latter limited by the curve corresponding to the zero ferrite content.
- So-called stainless steels are, according to current standards, those containing more than 10.5% of chromium.
- the curves C1 and C2 delimit the possible presence of austenite A: above C1 and C2 we have austenite A, underneath there is none.
- the curve C3 delimits the possible presence of ferrite F: below C3 there is ferrite F, above there is none.
- the curve C4 delimits the possible presence of martensite M: below C4 there is martensite M, above there is none.
- the composition must be such that one is both above the C3 and C4 curves, so as to have only austenite A.
- a first variant of the invention consists in incorporating into the alloy, in the limit of 0.5% by weight of the total, at least one carburigenic element taken from a second group consisting of tungsten, vanadium, niobium and zirconium. , and titanium, replacing an equivalent mass of iron in the alloy.
- This incorporation of one or more carburigenic elements has the effect of forcing the precipitation of specific carbides less harmful to the corrosion resistance than chromium carbides.
- the invention also relates to a watch or jewelery component made of such an alloy.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Adornments (AREA)
- Heat Treatment Of Steel (AREA)
- Soft Magnetic Materials (AREA)
Description
L'invention concerne un alliage d'acier inoxydable comportant une base constituée de fer et de chrome.The invention relates to a stainless steel alloy having a base of iron and chromium.
L'invention concerne encore un composant d'horlogerie réalisé en un tel alliage.The invention also relates to a watch component made of such an alloy.
L'invention concerne les domaines de l'horlogerie, de la bijouterie, et de la joaillerie, en particulier pour les structures : boîtes de montres, carrures, platines, bracelets, bagues, boucles d'oreilles et autres.The invention relates to the fields of watchmaking, jewelery, and jewelery, in particular for structures: watch cases, squares, turntables, bracelets, rings, earrings and others.
Les aciers inoxydables sont couramment utilisés dans les domaines de l'horlogerie, de la bijouterie, et de la joaillerie, en particulier pour les structures : boîtes de montres, carrures, platines, bracelets, et autres.Stainless steels are commonly used in the fields of watchmaking, jewelery, and jewelery, especially for structures: watch cases, casebacks, turntables, bracelets, and others.
Les composants à usage externe, destinés à être en contact avec la peau de l'utilisateur, doivent obéir à certaines contraintes, en particulier en raison des effets allergènes de certains métaux, notamment le nickel. Malgré les qualités de protection et d'éclat du nickel une fois poli, on s'attache de plus en plus à mettre sur le marché des alliages comportant peu voire pas de nickel.The components for external use, intended to be in contact with the skin of the user, must obey certain constraints, in particular because of the allergenic effects of certain metals, especially nickel. Despite the protective and polished qualities of nickel once polished, there is an increasing focus on placing on the market alloys with little or no nickel.
Le nickel est toutefois un composant de base de la plupart des aciers inoxydables usuels, car il améliore les propriétés mécaniques et la ductilité, la malléabilité et la résilience. Par contre le nickel est néfaste dans le domaine des surfaces de frottement. Le nickel améliore les propriétés de la couche passive, et s'intègre à la couche superficielle d'oxyde. En particulier l'alliage X2CrNiMo17-12 EN (ou 316L AISI) comporte entre 10,5 et 13% de nickel. Le nickel est un métal dont le coût est en croissance continue, et qui, en 2012, est voisin de 20'000 USD par tonne, ce qui renchérit le coût des alliages qui en contiennent.Nickel is, however, a basic component of most common stainless steels because it improves mechanical properties and ductility, malleability and resilience. By cons nickel is harmful in the field of friction surfaces. Nickel improves the properties of the passive layer, and integrates with the surface layer of oxide. In particular alloy X2CrNiMo17-12 EN (or 316L AISI) comprises between 10.5 and 13% of nickel. Nickel is a metal whose cost is growing continuously, and which, in 2012, is close to 20'000 USD per ton, which increases the cost of alloys containing it.
On connaît des alliages d'acier inoxydable sans nickel qui sont des aciers ferritiques, de structure cubique centrée. Toutefois ces aciers ferritiques ne sont pas durcissables par traitement thermique, mais seulement par écrouissage. Leur structure est peu fine, et cette famille d'alliages est peu apte au polissage.Nickel-free stainless steel alloys are known which are ferritic steels with a cubic centered structure. However, these ferritic steels are not hardenable by heat treatment, but only by hardening. Their structure is not very fine, and this family of alloys is not very suitable for polishing.
Le document
On connaît encore d'autres alliages d'acier inoxydable sans nickel qui sont des aciers martensitiques, qui sont durcissables par traitement thermique, ils sont en revanche difficiles à usiner, particulièrement les nuances de type « maraging » qui comportent des précipités de composants durcissant, et ne peuvent être envisagés pour les applications horlogères.Other nickel-free stainless steel alloys are known that are martensitic steels, which are hardenable by heat treatment, but are difficult on the other hand. to be machined, particularly the "maraging" grades which comprise precipitates of hardening components, and can not be envisaged for horological applications.
Le brevet
Les aciers austénitiques, de structure cubique faces centrées, ont généralement de très bonnes propriétés de formage, ce qui est particulièrement intéressant pour des composants de type horloger ou bijoutier. Ils ont une résistance chimique très élevée. Ils sont aussi amagnétiques en raison de leur structure cubique faces centrées. Ce sont aussi les plus aptes au soudage. Mais les aciers inoxydables austénitiques usuels comportent toujours de 3,5 à 32% de nickel, et plus couramment de 8,0 à 15,0 % de nickel. En effet, le nickel est un élément gammagène qui permet l'obtention de la structure austénitique, et d'obtenir notamment des tôles aptes aux déformations de mise en forme. Certains documents, comme
Dans la théorie, la boucle gamma du système fer-chrome propre aux aciers inoxydables, définit un domaine austénitique, même avec un taux de nickel bas ou nul, mais la boucle est d'ampleur très restreinte par rapport à celle des alliages comportant du nickel en proportion supérieure. De plus, ce domaine austénitique existe à des températures beaucoup plus élevées que l'ambiante. L'effet des éléments d'alliages gammagènes est double puisqu'il permet également d'élargir la boucle austénitique en composition chimique (par rapport au chrome) et d'élargir la gamme de température sur laquelle cette structure est stable.In theory, the gamma loop of the iron-chromium system specific to stainless steels defines an austenitic domain, even with a low or zero nickel content, but the loop is of very limited magnitude compared to that of alloys containing nickel. in higher proportion. In addition, this austenitic domain exists at temperatures much higher than ambient. The effect of the gammagenic alloy elements is twofold since it also makes it possible to widen the austenitic loop in chemical composition (relative to chromium) and to widen the temperature range on which this structure is stable.
Les aciers austéno-ferritiques, encore dits duplex, sont quant à eux faiblement magnétiques, et comportent généralement entre 3,5% et 8% de nickel.Austeno-ferritic steels, also called duplex, are weak magnetic, and generally comprise between 3.5% and 8% nickel.
En somme, si, dans l'acception générale, les aciers inoxydables sans nickel sont principalement des aciers ferritiques, il faudrait pouvoir disposer des avantages des aciers austénitiques, qui sont généralement catalogués comme aciers au nickel.In sum, if, in the general sense, the nickel-free stainless steels are mainly ferritic steels, the advantages of the austenitic steels, which are generally cataloged as nickel steels, should be available.
Pour l'obtention d'un acier inoxydable austénitique, on utilise généralement des éléments gammagènes tels que le nickel, le manganèse ou l'azote (on parle alors d'aciers super-austénitiques pour les deux derniers mentionnés), qui augmentent la plage de stabilité de l'austénite. Théoriquement il serait donc possible d'utiliser un acier super-austénitique avec manganèse ou azote en lieu et place du nickel.In order to obtain austenitic stainless steel, gammagens such as nickel, manganese or nitrogen are generally used (these are called super-austenitic steels for the last two mentioned), which increase the range of stability of austenite. Theoretically it would therefore be possible to use a super-austenitic steel with manganese or nitrogen in place of nickel.
Le brevet
Mais, si ces alliages super-austénitiques ont des propriétés mécaniques élevées, leur mise en forme est très difficile, notamment l'usinage est difficile, le matriçage n'est pas possible, et leur utilisation est de ce fait malcommode.But, if these super-austenitic alloys have high mechanical properties, their shaping is very difficult, especially the machining is difficult, the stamping is not possible, and their use is therefore inconvenient.
Des alliages inoxydables austénitiques sont connus des documents :
-
EP 1 783 240 A1 -
EP 1 025 273 B1 -
EP 1 626 101 A1 -
EP 0 896 072 A1 -
US 2009/060 775 A1 -
DE 197 16 795 A1 -
US 3 904 401 A
-
EP 1 783 240 A1 -
EP 1 025 273 B1 -
EP 1 626 101 A1 -
EP 0 896 072 A1 -
US 2009/060775 A1 -
DE 197 16 795 A1 -
US 3,904,401A
A cet effet, l'invention concerne un alliage d'acier inoxydable sur une base constituée de fer et de chrome, caractérisé en ce qu'il comporte moins de 0,5% en masse de nickel, et est arrangé selon une structure austénitique cubique à faces centrées, et qu'il consiste, en valeurs en masse, en :
- chrome : valeur mini 16%, valeur maxi 20 % ;
- au moins un métal d'apport, la valeur du total dudit au moins un métal d'apport ou desdits métaux d'apport étant comprise entre : valeur mini 30%, valeur maxi 40%, ledit au moins un métal d'apport étant choisi parmi un premier ensemble constitué du cuivre, du ruthénium, du rhodium, du palladium, du rhénium, de l'osmium, de l'iridium, du platine, et de l'or :
- la valeur du cuivre étant comprise entre : valeur mini 0%, valeur maxi 2 % ;
- la valeur de l'or étant comprise entre : valeur mini 0%, valeur maxi 2 % ;
- carbone : valeur mini 0%, valeur maxi 0,03 % ;
- molybdène : valeur mini 0%, valeur maxi 2 % ;
- manganèse : valeur mini 0%, valeur maxi 2 % ;
- silicium : valeur mini 0%, valeur maxi 1 % ;
- azote: valeur mini 0%, valeur maxi 0,1% ;
- dans la limite de 0,5% en masse du total, au moins un élément carburigène pris parmi un deuxième ensemble constitué du tungstène, du vanadium, du niobium, du zirconium, et du titane, en remplacement d'une masse équivalent de fer dans l'alliage ;
- fer et impuretés inévitables: le complément à 100 %.
- chrome: min.
value 16%, max.value 20%; - at least one filler metal, the value of the total of said at least one filler metal or said filler metals being between: minimum value 30%, maximum value 40%, said at least one filler metal being chosen among a first set consisting of copper, ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum, and gold:
- the copper value being between:
minimum value 0%, maximum value 2%; - the value of the gold being between:
minimum value 0%, maximum value 2%;
- the copper value being between:
- carbon:
minimum value 0%, maximum value 0.03%; - molybdenum:
minimum value 0%, maximum value 2%; - manganese:
minimum value 0%, maximum value 2%; - silicon:
minimum value 0%,maximum value 1%; - nitrogen:
minimum value 0%, maximum value 0.1%; - in the limit of 0.5% by mass of the total, at least one carburigenic element taken from a second group consisting of tungsten, vanadium, niobium, zirconium and titanium, replacing an equivalent mass of iron in the alloy;
- iron and unavoidable impurities: the complement to 100%.
L'invention concerne encore un composant d'horlogerie ou de joaillerie réalisé en un tel alliage.The invention also relates to a watch or jewelery component made of such an alloy.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description détaillée qui va suivre, en référence aux dessins annexés, où :
- la
figure 1 représente, de façon schématisée, la boucle gamma d'un système fer-chrome, en fonction du taux de nickel dans l'alliage ; - la
figure 2 représente, de façon schématisée, un diagramme de Schaeffler, avec en abscisse un chrome équivalent, et en ordonnée un nickel équivalent. Ce diagramme délimite les domaines ferritique, martensitique et austénitique, ce dernier limité par la courbe correspondant au taux nul de ferrite.
- the
figure 1 represents schematically the gamma loop of an iron-chromium system, as a function of the nickel content in the alloy; - the
figure 2 schematically represents a Schaeffler diagram, with an equivalent chromium on the abscissa and an equivalent nickel on the ordinate. This diagram delimits the ferritic, martensitic and austenitic domains, the latter limited by the curve corresponding to the zero ferrite content.
L'invention se propose de produire des aciers inoxydables sans nickel, qui possèdent des propriétés analogues à celles des aciers inoxydables austénitiques avec nickel.The invention proposes to produce stainless steels without nickel, which have properties similar to those of austenitic stainless steels with nickel.
On appellera ci-après « alliage sans nickel » un alliage comportant moins de 0,5% en masse de nickel.The term "nickel-free alloy" will be referred to below as an alloy comprising less than 0.5% by weight of nickel.
Il s'agit donc de rechercher la fabrication d'alliages, qui, comme les super-austénitiques, comportent des éléments de substitution au nickel, mais qui durcissent moins l'acier que le couple manganèse-azote.It is therefore a question of looking for the production of alloys, which, like the super-austenitics, contain elements of substitution for nickel, but which harden the steel less than the manganese-nitrogen pair.
Ces éléments de substitution doivent être solubles dans le fer, de façon à permettre la construction d'une structure austénitique cubique à faces centrées. Selon l'invention, l'alliage comporte, en complément d'une base constituée de fer et de chrome, au moins un métal d'apport choisi parmi un premier ensemble constitué du cuivre, du ruthénium, du rhodium, du palladium, du rhénium, de l'osmium, de l'iridium, du platine, et de l'or.These substitution elements must be soluble in iron, so as to allow the construction of a cubic austenitic structure with centered faces. According to the invention, the alloy comprises, in addition to a base consisting of iron and chromium, at least one filler metal selected from a first group consisting of copper, ruthenium, rhodium, palladium and rhenium. , osmium, iridium, platinum, and gold.
Dans une application préférée, l'alliage comporte, en complément d'une base constituée de fer, de carbone et de chrome, au moins un métal d'apport choisi parmi un sous-ensemble du premier ensemble constitué du ruthénium, du rhodium, du palladium, du rhénium, de l'osmium, de l'iridium, et du platine. En effet, ces métaux font partie du groupe dit PGM (platinum group metals) ou platinoïdes, c'est-à-dire qu'ils sont caractérisés par des propriétés communes et inhabituelles pour les métaux. Ces métaux du groupe PGM sont également plus solubles dans le fer que le cuivre et l'or.In a preferred application, the alloy comprises, in addition to a base consisting of iron, carbon and chromium, at least one filler metal chosen from a subset of the first set consisting of ruthenium, rhodium, palladium, rhenium, osmium, iridium, and platinum. Indeed, these metals are part of PGM (platinum group metals) or platinoids, that is to say that they are characterized by common and unusual properties for metals. These PGM group metals are also more soluble in iron than copper and gold.
Le choix du palladium comme métal d'apport permet, plus particulièrement, d'atteindre les propriétés recherchées.The choice of palladium as filler metal allows, more particularly, to achieve the desired properties.
Une composition (en masse) convenable est de 18 % de chrome, de 35 % de palladium, et de 46 à 47 % de fer. Comme tout acier inoxydable, cet alliage peut contenir jusqu'à 0,03% de carbone.A suitable (mass) composition is 18% chromium, 35% palladium, and 46 to 47% iron. Like all stainless steel, this alloy can contain up to 0.03% carbon.
De façon préférée, sa composition en masse est de 18 % de chrome, de 35 % de palladium, de 0% à 0,03% de carbone, et le complément en fer. Plus particulièrement, sa composition en masse est de 18 % de chrome, de 35 % de palladium, et de 46,97 à 47 % de fer, et de 0 à 0,03% de carbone.Preferably, its mass composition is 18% chromium, 35% palladium, 0% to 0.03% carbon, and the iron supplement. More particularly, its mass composition is 18% chromium, 35% palladium, and 46.97 to 47% iron, and 0 to 0.03% carbon.
La
Le chrome équivalent Créq répond ici à la définition suivante :
Ce modèle est voisin du modèle de Schaeffler ou celui de Delong :
Le point important est la détermination du taux de métal d'apport, en remplacement du nickel qui est proscrit. La notion de nickel équivalent qualifie la proportion en masse du métal d'apport, ou des métaux d'apport s'il y en a plusieurs.The important point is the determination of the filler metal content, replacing the nickel that is outlawed. The notion of equivalent nickel qualifies the proportion by weight of the filler metal, or filler metals if there are several.
Dans le cas particulier de l'emploi du palladium pour remplacer le nickel, le nickel équivalent Niéq répond à la définition suivante :
Ce modèle est adapté à la présence de palladium, et dérive des modèles connus de Schaeffler (pour un alliage base manganèse):
Dans une généralisation à l'ensemble capable de métaux d'apport, la formule de nickel équivalent peut encore s'écrire :
Ce diagramme de Schaeffler délimite les domaines ferritique, martensitique et austénitique, ce dernier limité par la courbe correspondant au taux nul de ferrite.This Schaeffler diagram delimits the ferritic, martensitic and austenitic domains, the latter limited by the curve corresponding to the zero ferrite content.
Les aciers dits inoxydables sont, selon les normes en vigueur, ceux qui contiennent plus de 10,5% de chrome.So-called stainless steels are, according to current standards, those containing more than 10.5% of chromium.
Les courbes C1 et C2 délimitent la présence possible d'austénite A : au-dessus de C1 et de C2 on a de l'austénite A, en-dessous il n'y en a pas.The curves C1 and C2 delimit the possible presence of austenite A: above C1 and C2 we have austenite A, underneath there is none.
La courbe C3 délimite la présence possible de ferrite F : en-dessous de C3 il y a de la ferrite F, au-dessus il n'y en a pas.The curve C3 delimits the possible presence of ferrite F: below C3 there is ferrite F, above there is none.
La courbe C4 délimite la présence possible de martensite M : en-dessous de C4 il y a de la martensite M, au-dessus il n'y en a pas.The curve C4 delimits the possible presence of martensite M: below C4 there is martensite M, above there is none.
Pour bénéficier au mieux des propriétés de l'austénite, la composition doit être telle que l'on soit à la fois au-dessus des courbes C3 et C4, de façon à n'avoir que de l'austénite A.To best benefit from the properties of austenite, the composition must be such that one is both above the C3 and C4 curves, so as to have only austenite A.
Pour bénéficier des propriétés propres aux aciers inoxydables, il faut respecter le taux minimal de chrome figuré par la courbe C5, et le domaine est alors celui situé à droite de la courbe C5. Le domaine D1 hachuré sur la
Selon une approximation, les courbes sont des droites, d'équations :
- C1 :
- C2 :
- C3 :
- C4 :
- C1:
- C2:
- C3:
- C4:
Le domaine D1 obéit aux trois conditions suivantes :
Bien sûr, on peut tolérer la présence d'un peu de ferrite ou de martensite avec l'austénite, et le domaine réel d'application peut être un peu plus large que le domaine D1, et en particulier pour abaisser le plus possible le niveau du nickel équivalent, en raison du coût souvent très élevé des métaux choisis en substitution au nickel ; rappelons par exemple que, en 2012 le coût du palladium est d'environ la moitié de celui de l'or, et compris entre le quart et la moitié de celui du platine.Of course, we can tolerate the presence of a little ferrite or martensite with austenite, and the real area of application can be a little wider than the D1 domain, and in particular to lower the level as much as possible. equivalent nickel, because of the often very high cost of metals chosen as substitutes for nickel; remember that in 2012 the cost of palladium is about half that of gold, and between one quarter and one half that of platinum.
Le domaine rectangulaire D2, défini par les deux inégalités suivantes :
- palladium : valeur mini 30%, valeur maxi 40 %
- chrome : valeur mini 16%, valeur
maxi 20 % - molybdène : valeur mini 0%, valeur maxi 2 %
- manganèse : valeur mini 0%, valeur maxi 2 %
- cuivre : valeur mini 0%, valeur maxi 2 %
- or : valeur mini 0%, valeur maxi 2 %
- silicium : valeur mini 0%, valeur
maxi 1 % - azote: valeur mini 0%, valeur
0,1%maxi - carbone : valeur mini 0%, valeur
maxi 0,03 % - fer: le complément à 100 %.
- palladium: minimum value 30%, maximum value 40%
- chrome:
minimum value 16%,maximum value 20% - molybdenum:
minimum value 0%, maximum value 2%- manganese:
minimum value 0%, maximum value 2%
- manganese:
- copper:
minimum value 0%, maximum value 2% - gold:
minimum value 0%, maximum value 2% - silicon:
minimum value 0%,maximum value 1% - nitrogen:
minimum value 0%, maximum value 0.1% - carbon:
minimum value 0%, maximum value 0.03% - iron: the 100% supplement.
Dans la généralisation à au moins un métal d'apport pris parmi le premier ensemble ou son sous-ensemble limité aux PGM, la composition en masse selon la revendication 1 devient :
- total du ou des métaux d'apport du premier ensemble ou de son sous-ensemble des PGM : valeur mini 30%, valeur maxi 40 %
- chrome : valeur mini 16%, valeur
maxi 20 % - molybdène : valeur mini 0%, valeur maxi 2 %
- manganèse : valeur mini 0%, valeur maxi 2 %
- cuivre : valeur mini 0%, valeur maxi 2 %
- or : valeur mini 0%, valeur maxi 2 %
- silicium : valeur mini 0%, valeur
maxi 1 % - azote: valeur mini 0%, valeur
0,1%maxi - carbone : valeur mini 0%, valeur
maxi 0,03 % - fer: le complément à 100 %.
- total filler metal (s) of the first set or its subset of PGMs: minimum value 30%, maximum value 40%
- chrome:
minimum value 16%,maximum value 20% - molybdenum:
minimum value 0%, maximum value 2% - manganese:
minimum value 0%, maximum value 2% - copper:
minimum value 0%, maximum value 2% - gold:
minimum value 0%, maximum value 2% - silicon:
minimum value 0%,maximum value 1% - nitrogen:
minimum value 0%, maximum value 0.1% - carbon:
minimum value 0%, maximum value 0.03% - iron: the 100% supplement.
Une première variante de l'invention consiste à incorporer dans l'alliage, dans la limite de 0,5% en masse du total, au moins un élément carburigène pris parmi un deuxième ensemble constitué du tungstène, du vanadium, du niobium, du zirconium, et du titane, en remplacement d'une masse équivalent de fer dans l'alliage.A first variant of the invention consists in incorporating into the alloy, in the limit of 0.5% by weight of the total, at least one carburigenic element taken from a second group consisting of tungsten, vanadium, niobium and zirconium. , and titanium, replacing an equivalent mass of iron in the alloy.
Cette incorporation d'un ou plusieurs éléments carburigènes a pour effet de forcer la précipitation de carbures spécifiques moins néfastes pour la résistance à la corrosion que les carbures de chrome.This incorporation of one or more carburigenic elements has the effect of forcing the precipitation of specific carbides less harmful to the corrosion resistance than chromium carbides.
Une deuxième variante de l'invention consiste à incorporer dans l'alliage, à la fois d'une part au moins un tel métal d'apport, et d'autre part du manganèse et de l'azote, pour ajuster les propriétés mécaniques de l'alliage. De préférence, dans cette deuxième variante, la composition en masse selon la revendication 1devient :
- total de, d'une part le ou les métaux d'apport du premier ensemble ou de son sous-ensemble des PGM, et d'autre part le manganèse et l'azote : valeur mini 30%, valeur maxi 40 %
- chrome : valeur mini 16%, valeur
maxi 20 % - molybdène : valeur mini 0%, valeur maxi 2 %
- cuivre : valeur mini 0%, valeur maxi 2 %
- or : valeur mini 0%, valeur maxi 2 %
- silicium : valeur mini 0%, valeur
maxi 1 % - carbone : valeur mini 0%, valeur
maxi 0,03 % - fer : le complément à 100 %.
- total of, on the one hand, the filler metal (s) of the first set or its subset of GMPs, and on the other hand manganese and nitrogen: minimum value 30%, maximum value 40%
- chrome:
minimum value 16%,maximum value 20% - molybdenum:
minimum value 0%, maximum value 2% - copper:
minimum value 0%, maximum value 2% - gold:
minimum value 0%, maximum value 2% - silicon:
minimum value 0%,maximum value 1% - carbon:
minimum value 0%, maximum value 0.03% - iron: the 100% supplement.
L'invention concerne encore un composant d'horlogerie ou de joaillerie réalisé en un tel alliage.The invention also relates to a watch or jewelery component made of such an alloy.
Claims (5)
- Stainless steel alloy with a base formed of iron and chromium, characterized in that the alloy includes less than 0.5% by mass of nickel and is arranged in an austenitic face-centred cubic structure and consists, in values by mass, of:- chromium: minimum value 16%, maximum value 20%;- at least one additional metal, the value of the total of said at least one additional metal or said additional metals being comprised between: minimum value 30% and maximum value 40%, said at least one additional metal being selected from among a first group comprising copper, ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum and gold:- the copper value being comprised between: minimum value 0% and maximum value 2%;- the gold value being comprised between: minimum value 0% and maximum value 2%;- carbon: minimum value 0%, maximum value 0.03%;- molybdenum: minimum value 0%, maximum value 2%;- manganese: minimum value 0%, maximum value 2%;- silicon: minimum value 0%, maximum value 1 %;- nitrogen: minimum value 0%, maximum value 0.1%;- within the limit of 0.5% in mass of the total, at least one carburigen element taken from among a second group including tungsten, vanadium, niobium, zirconium and titanium, to replace an equivalent mass of iron in the alloy;- iron and inevitable impurities: the complement to 100%.
- Alloy according to claim 1, characterized in that at least one said additional metal is selected from among a sub-group, called the platinoid group, of said first group, said platinoid sub-group including ruthenium, rhodium, palladium, rhenium, osmium, iridium and platinum.
- Alloy according to claim 2, characterized in that said at least one additional metal is exclusively selected from among said platinoid sub-group.
- Alloy according to any of claims 1 to 3, characterized in that the alloy consists, in values by mass, of:- chromium: 18%;- palladium: 35%;- carbon: 0% to 0.03%;- iron and inevitable impurities: the complement to 100%.
- Timepiece or jewellery component including made of an alloy according to any of the preceding claims.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12191101.0A EP2728028B1 (en) | 2012-11-02 | 2012-11-02 | Edelstahllegierung ohne Nickel |
US14/425,455 US20150225820A1 (en) | 2012-11-02 | 2013-10-17 | Nickel free stainless steel alloy |
PCT/EP2013/071770 WO2014067795A1 (en) | 2012-11-02 | 2013-10-17 | Nickel-free stainless steel alloy |
RU2015120760A RU2625363C2 (en) | 2012-11-02 | 2013-10-17 | Stainless steel free of nickel |
EP13785379.2A EP2914759B1 (en) | 2012-11-02 | 2013-10-17 | Edelstahllegierung ohne nickel |
JP2015533640A JP5976945B2 (en) | 2012-11-02 | 2013-10-17 | Nickel free stainless steel alloy |
CN201380057112.4A CN104769145B (en) | 2012-11-02 | 2013-10-17 | Stainless steel alloy without nickel |
TW102138458A TWI586816B (en) | 2012-11-02 | 2013-10-24 | Nickel free stainless steel alloy |
HK15112788.4A HK1211992A1 (en) | 2012-11-02 | 2015-12-29 | Nickel-free stainless steel alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12191101.0A EP2728028B1 (en) | 2012-11-02 | 2012-11-02 | Edelstahllegierung ohne Nickel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2728028A1 EP2728028A1 (en) | 2014-05-07 |
EP2728028B1 true EP2728028B1 (en) | 2018-04-04 |
Family
ID=47115583
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12191101.0A Active EP2728028B1 (en) | 2012-11-02 | 2012-11-02 | Edelstahllegierung ohne Nickel |
EP13785379.2A Active EP2914759B1 (en) | 2012-11-02 | 2013-10-17 | Edelstahllegierung ohne nickel |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP13785379.2A Active EP2914759B1 (en) | 2012-11-02 | 2013-10-17 | Edelstahllegierung ohne nickel |
Country Status (8)
Country | Link |
---|---|
US (1) | US20150225820A1 (en) |
EP (2) | EP2728028B1 (en) |
JP (1) | JP5976945B2 (en) |
CN (1) | CN104769145B (en) |
HK (1) | HK1211992A1 (en) |
RU (1) | RU2625363C2 (en) |
TW (1) | TWI586816B (en) |
WO (1) | WO2014067795A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3147378A1 (en) * | 2015-09-25 | 2017-03-29 | The Swatch Group Research and Development Ltd. | Nickel-free austenitic stainless steel |
CN106636947A (en) * | 2016-12-16 | 2017-05-10 | 安徽宝恒新材料科技有限公司 | Seawater-corrosion-resistant stainless steel and production method thereof |
EP3486009B1 (en) * | 2017-11-17 | 2024-01-17 | The Swatch Group Research and Development Ltd | Method for sintering an austenitic stainless steel |
RU2650947C1 (en) * | 2017-11-27 | 2018-04-18 | Юлия Алексеевна Щепочкина | Steel for manufacturing items of jewelry |
RU2650949C1 (en) * | 2017-11-27 | 2018-04-18 | Юлия Алексеевна Щепочкина | Steel for manufacturing jewelry |
RU2663501C1 (en) * | 2018-01-09 | 2018-08-07 | Юлия Алексеевна Щепочкина | Iron-based alloy |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3904401A (en) * | 1974-03-21 | 1975-09-09 | Carpenter Technology Corp | Corrosion resistant austenitic stainless steel |
SU1049560A1 (en) * | 1982-04-05 | 1983-10-23 | Институт Металлургии Им.50-Летия Ссср | Steel |
US4487630A (en) | 1982-10-25 | 1984-12-11 | Cabot Corporation | Wear-resistant stainless steel |
JP2634299B2 (en) * | 1990-05-23 | 1997-07-23 | 三菱重工業株式会社 | Pd-added stainless steel for high temperature, high concentration sulfuric acid |
FR2706489B1 (en) | 1993-06-14 | 1995-09-01 | Ugine Savoie Sa | Martensitic stainless steel with improved machinability. |
CH688862A5 (en) * | 1995-01-03 | 1998-04-30 | Basf Ag | Nickel-free austenitic chromium steel |
DE19513407C1 (en) * | 1995-04-08 | 1996-10-10 | Vsg En & Schmiedetechnik Gmbh | Steel alloy used for jewellery implants and dental applications |
DE19716795C2 (en) * | 1997-04-22 | 2001-02-22 | Krupp Vdm Gmbh | Use of a high-strength and corrosion-resistant iron-manganese-chrome alloy |
FR2764307B1 (en) | 1997-06-04 | 1999-08-27 | Metallurg Avancee Soc Ind De | NICKEL FREE STAINLESS STEEL FOR BIOMEDICAL APPLICATIONS |
FR2766843B1 (en) * | 1997-07-29 | 1999-09-03 | Usinor | AUSTENITIC STAINLESS STEEL WITH A VERY LOW NICKEL CONTENT |
EP0964071A1 (en) | 1998-06-12 | 1999-12-15 | Asulab S.A. | Ferritic stainless steel and exterior cover part for a watch made with such a steel |
CH694401A5 (en) * | 1999-05-26 | 2004-12-31 | Basf Ag | Low-nickel, low-molybdenum, biocompatible, non-allergenic, corrosion-resistant austenitic steel. |
WO2001055465A1 (en) * | 2000-01-26 | 2001-08-02 | Jeneric/Pentron Incorporated | Dental alloys |
US7294214B2 (en) * | 2003-01-08 | 2007-11-13 | Scimed Life Systems, Inc. | Medical devices |
JP4379804B2 (en) * | 2004-08-13 | 2009-12-09 | 大同特殊鋼株式会社 | High nitrogen austenitic stainless steel |
US7794652B2 (en) * | 2004-12-27 | 2010-09-14 | The Argen Corporation | Noble dental alloy |
JP4915202B2 (en) * | 2005-11-03 | 2012-04-11 | 大同特殊鋼株式会社 | High nitrogen austenitic stainless steel |
JP2007247035A (en) * | 2006-03-17 | 2007-09-27 | Seiko Epson Corp | Ornament and watch |
TW200909593A (en) * | 2007-08-29 | 2009-03-01 | Advanced Int Multitech Co Ltd | Chromium-manganese-nitrogen austenite series stainless steel |
-
2012
- 2012-11-02 EP EP12191101.0A patent/EP2728028B1/en active Active
-
2013
- 2013-10-17 CN CN201380057112.4A patent/CN104769145B/en active Active
- 2013-10-17 JP JP2015533640A patent/JP5976945B2/en active Active
- 2013-10-17 RU RU2015120760A patent/RU2625363C2/en not_active IP Right Cessation
- 2013-10-17 US US14/425,455 patent/US20150225820A1/en not_active Abandoned
- 2013-10-17 EP EP13785379.2A patent/EP2914759B1/en active Active
- 2013-10-17 WO PCT/EP2013/071770 patent/WO2014067795A1/en active Application Filing
- 2013-10-24 TW TW102138458A patent/TWI586816B/en not_active IP Right Cessation
-
2015
- 2015-12-29 HK HK15112788.4A patent/HK1211992A1/en unknown
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
WO2014067795A1 (en) | 2014-05-08 |
CN104769145B (en) | 2016-10-19 |
HK1211992A1 (en) | 2016-06-03 |
JP5976945B2 (en) | 2016-08-24 |
US20150225820A1 (en) | 2015-08-13 |
TW201432064A (en) | 2014-08-16 |
TWI586816B (en) | 2017-06-11 |
EP2914759A1 (en) | 2015-09-09 |
CN104769145A (en) | 2015-07-08 |
JP2015535888A (en) | 2015-12-17 |
EP2728028A1 (en) | 2014-05-07 |
RU2015120760A (en) | 2016-12-27 |
EP2914759B1 (en) | 2016-10-05 |
RU2625363C2 (en) | 2017-07-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2914759B1 (en) | Edelstahllegierung ohne nickel | |
EP3543368B1 (en) | High-entropy alloys for covering components | |
EP3147380B1 (en) | Nickel-free austenitic stainless steel | |
EP3240915B1 (en) | Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold | |
CA2565162A1 (en) | Steel with high mechanical strength and wear resistance | |
MA45131B1 (en) | Process for manufacturing cold rolled and tempered steel sheet | |
CA3001158C (en) | Steel, product created from said steel, and manufacturing method thereof | |
JP6602463B2 (en) | Cr-based two-phase alloy and product thereof | |
CH714802A2 (en) | High entropy alloys for dressing components. | |
EP3219823A1 (en) | Low cobalt hard facing alloy | |
CH708231B1 (en) | Clock spring made of austenitic stainless steel. | |
EP1025273B1 (en) | Nickel-free stainless steel for biomedical applications | |
EP1885900B1 (en) | Steel for submarine hulls with improved weldability | |
CH707203A2 (en) | Stainless steel alloy, useful in component of clockwork and jewelry, comprises base including iron and chromium, nickel, and filler metal of first assembly comprising copper, ruthenium, rhodium, palladium, rhenium and osmium | |
EP3249060B1 (en) | Method for thermal treatment of austenitic steels | |
EP1051533A1 (en) | Titanium alloy watch part | |
CH711568A2 (en) | Nickel-free austenitic stainless steel. | |
EP3800511B1 (en) | Pivoting shaft for a regulating organ | |
WO2023194522A1 (en) | Non-magnetic pivot pin | |
CH716664A2 (en) | Non-magnetic and hard watch component, in particular the pivot axis of a regulating organ. | |
CH710575B1 (en) | Precious alloy of titanium and gold and watchmaking or jewelery component made of a precious alloy of titanium and gold. | |
TW201215688A (en) | Fe-Cr-Ni casting alloy having high strength and toughness | |
CH703143B1 (en) | Palladium-based alloy, useful in jewelry article, comprises palladium, aluminum, and at least one additional metal or germanium |
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: 20121102 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
17P | Request for examination filed |
Effective date: 20141107 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
17Q | First examination report despatched |
Effective date: 20170428 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20171208 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C22C 38/28 20060101ALI20171124BHEP Ipc: C22C 38/38 20060101ALI20171124BHEP Ipc: C22C 38/26 20060101ALI20171124BHEP Ipc: C22C 38/02 20060101ALI20171124BHEP Ipc: G04B 37/22 20060101ALI20171124BHEP Ipc: C22C 38/18 20060101ALI20171124BHEP Ipc: C22C 38/04 20060101ALI20171124BHEP Ipc: C22C 30/00 20060101ALI20171124BHEP Ipc: C22C 38/00 20060101AFI20171124BHEP Ipc: C22C 38/22 20060101ALI20171124BHEP Ipc: C22C 38/24 20060101ALI20171124BHEP Ipc: C22C 38/20 20060101ALI20171124BHEP |
|
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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: CH Ref legal event code: NV Representative=s name: ICB INGENIEURS CONSEILS EN BREVETS SA, CH |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 985675 Country of ref document: AT Kind code of ref document: T Effective date: 20180415 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602012044672 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20180404 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
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: 20180404 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 7 |
|
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: 20180704 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: 20180404 Ref country code: NO 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: 20180704 Ref country code: LT 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: 20180404 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: 20180404 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: 20180404 Ref country code: AL 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: 20180404 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: 20180404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV 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: 20180404 Ref country code: RS 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: 20180404 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: 20180705 Ref country code: HR 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: 20180404 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 985675 Country of ref document: AT Kind code of ref document: T Effective date: 20180404 |
|
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: 20180806 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602012044672 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20180404 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: 20180404 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: 20180404 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: 20180404 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: 20180404 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: 20180404 |
|
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: 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: 20180404 Ref country code: SM 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: 20180404 |
|
26N | No opposition filed |
Effective date: 20190107 |
|
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: 20180404 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20181102 |
|
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: 20180404 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181102 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20181130 |
|
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: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20181130 |
|
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: 20181102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT 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: 20180404 |
|
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: 20180404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20121102 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: 20180404 Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS 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: 20180804 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230615 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20231019 Year of fee payment: 12 Ref country code: DE Payment date: 20231019 Year of fee payment: 12 Ref country code: CH Payment date: 20231201 Year of fee payment: 12 |