EP2960350A1 - Alliage de fonte au cuivre - Google Patents
Alliage de fonte au cuivre Download PDFInfo
- Publication number
- EP2960350A1 EP2960350A1 EP14002217.9A EP14002217A EP2960350A1 EP 2960350 A1 EP2960350 A1 EP 2960350A1 EP 14002217 A EP14002217 A EP 14002217A EP 2960350 A1 EP2960350 A1 EP 2960350A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mass
- alloy
- phase
- copper
- massenprozent
- 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
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 114
- 239000000956 alloy Substances 0.000 title claims abstract description 114
- 239000010949 copper Substances 0.000 title claims abstract description 93
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000005266 casting Methods 0.000 title claims abstract description 45
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 48
- 229910052718 tin Inorganic materials 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 25
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 239000003651 drinking water Substances 0.000 claims description 11
- 235000020188 drinking water Nutrition 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910017518 Cu Zn Inorganic materials 0.000 claims description 5
- 229910017752 Cu-Zn Inorganic materials 0.000 claims description 5
- 229910017943 Cu—Zn Inorganic materials 0.000 claims description 5
- 229910001278 Sr alloy Inorganic materials 0.000 claims description 5
- 229910000905 alloy phase Inorganic materials 0.000 claims description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011135 tin Substances 0.000 description 35
- 239000011701 zinc Substances 0.000 description 31
- 239000011133 lead Substances 0.000 description 26
- 229910052712 strontium Inorganic materials 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 15
- 238000007711 solidification Methods 0.000 description 12
- 230000008023 solidification Effects 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 9
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910000906 Bronze Inorganic materials 0.000 description 6
- 229910020994 Sn-Zn Inorganic materials 0.000 description 6
- 229910009069 Sn—Zn Inorganic materials 0.000 description 6
- 239000010974 bronze Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910001369 Brass Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000010951 brass Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910001339 C alloy Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000007528 sand casting Methods 0.000 description 4
- 101100078300 Caenorhabditis elegans mtm-9 gene Proteins 0.000 description 3
- 229910017755 Cu-Sn Inorganic materials 0.000 description 3
- 229910017927 Cu—Sn Inorganic materials 0.000 description 3
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- RZTAMFZIAATZDJ-UHFFFAOYSA-N felodipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC(Cl)=C1Cl RZTAMFZIAATZDJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 208000036829 Device dislocation Diseases 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910007610 Zn—Sn Inorganic materials 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000003462 vein Anatomy 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
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Definitions
- the present invention relates to a copper casting alloy, in particular for use in components for drinking water systems.
- Copper casting alloys in particular copper-tin-zinc casting alloys (multi-substance bronzes, in particular red brass) are today indispensable materials for water-bearing systems. Because these have bacteriostatic properties and also offer excellent corrosion resistance. Such copper casting alloys also show positive properties in shaping and can be cast well. Due to their high strength and toughness, the material is also highly valued in chipless, plastomechanical forming. However, this plastic deformability proves to be particularly disadvantageous in the case of machining by machining. In this case, copper casting alloys tend to form long chips, which inhibits the workflow during fully automated turning or drilling and leads to severe wear on the tool cutting edges.
- the modified CuSn5Zn5Pb2-C alloy (marking according to DIN EN 1982, 2008: CC499K) is usually used, which is a CuSn5Zn5Pb5-C alloy adapted to the requirements of the requirements.
- the CuSn5Zn5Pb2-C alloy contains 84 to 88 mass% Cu, 4.0 to 6.0 mass% Zn, 4.0 to 6.0 mass% Sn, up to 3.0 mass% Pb, up to 0.3 mass% Fe, up to 0.6 mass% Ni, up to 0.01 mass% Al, up to 0.04 mass% P, up to 0.04 mass% S, up to 0.01 mass% Si, up to 0.10 mass% Sb, up to 0.02 mass% Cd, up to 0.03 mass% As and up to 0.02 mass% Bi.
- the lead additive serves as a chip breaker. Because lead is practically insoluble in solid copper and fills in the casting due to the low melting point of the previously formed, solidification-related porosity. Thus, at the end of solidification, lead is present in the form of evenly distributed drops in the microstructure. These drops act as chip breakers and thus support economical, fully automatic mechanical processing.
- a copper casting alloy in which no lead is present and the chipbreaking property in the alloy is essentially achieved by Si.
- This alloy has the following composition: 70 to 80% by weight of Cu, 1.8 to 3.5% by weight of Si, 0.02 to 0.25% by mass of P, 0.3 to 3.5% by weight of Sn and the balance Zn and unavoidable impurities.
- the chipbreaker is a CuZnSi solid solution. While this alloy provides good machinability, the alloy is susceptible to wear during machining compared to the lead-containing copper alloys. In addition, relatively high Zn contents of often more than 10 percent by mass have a negative effect on the corrosion resistance of the alloy.
- Another copper alloy is from the WO2011 / 121799 A1 known.
- This alloy contains 19 to 22 mass% Zn, 1.0 to 2.0 mass% Si, 0.5 to 1.5 mass% Bi, and balance Cu and unavoidable impurities.
- the chipbreaker is a CuZnSi mixed crystal and bi-particles.
- bismuth wets the grain boundaries and thereby lowers the mechanical strength.
- bismuth is expensive to buy.
- the out of the WO2011 / 121799 A1 known alloy hard and leads to a wear-enhancing machinability.
- Another copper casting alloy is from the WO 97/00977 A1 known.
- the alloy contains 2 to 12 percent by weight of Zn and Bi and Se in the ratio of 1.8 to 5.
- Bismuth selenide is used here as chip breaker. The problem here is that bismuth selenide are first produced in an additional process step and the brass alloy melt must be added. Bismuth is also relatively expensive and selenium has a sharp limit in the Drinking Water Ordinance.
- a brass (Cu-Zn), bronze (Cu-Sn) or multi-metal bronze (Cu-Sn-Zn) alloy is added as a chip breaker instead of lead (Pb), strontium (Sr).
- Strontium is regarded as harmless to health, is not subject to any limit and is therefore able to design drinking water installations in the future in accordance with the law.
- the relatively non-noble strontium forms at least one Sr-containing phase (hereinafter the first Sr-containing phase) which is insoluble in a brass or bronze phase or multicomponent main phase (hereinafter copper alloy matrix phase).
- the first Sr-containing phase is present in the form of uniformly distributed aggregates in the microstructure.
- the copper casting alloy preferably contains a Sr-free copper alloy matrix phase and at least the first Sr-containing phase dispersed in the Sr-free copper alloy matrix phase.
- the first Sr-containing phase preferably has a Cu-Sr and / or Cu-Sn-Sr mixed phase, in particular having one of the empirical formulas Cu 5 Sr, Cu 9 Sn 4 Sr, Cu 4 Sn 2 Sr.
- the copper casting alloy contains a further Sr-containing phase (hereinafter second Sr-containing phase), which is dispersively distributed in the Sr-free copper alloy matrix phase and which has a deviating, in particular higher melting temperature than the first Sr-containing phase.
- second Sr-containing phase further Sr-containing phase
- the second Sr-containing phase is, as far as the alloy melt contains P, preferably a Cu-P-Sr mixed phase, in particular with the empirical formula Cu 9 P 4 Sr.
- the invention proposes a method for producing a copper casting alloy according to claim 5.
- a method for producing a copper casting alloy according to claim 5 By means of such a method, in particular the copper casting alloy according to the invention is produced.
- the invention furthermore relates to a shaped body, in particular for a drinking water system or a fitting or a component made of this shaped body.
- At least parts or regions of the fitting or of the component should contain the copper casting alloy according to the invention.
- fittings in the drinking water and sanitary engineering mainly functional elements are referred to, in particular valves or faucets.
- components within the meaning of the invention for example, a pipe connector, a piece of pipe or a functional assembly of a water pipe are considered.
- the present invention particularly drinking water systems in view, but this does not exclude that the claimed copper casting alloys also due to their excellent properties in components for other water-bearing systems, not provided for drinking water supply are use can find.
- the alloy according to the invention can also find application in other fields.
- An alloy melt which forms a copper casting alloy after cooling is preferably produced by fusing a Sn-Sr alloy, a Cu-Zn alloy, and crude copper (Cu).
- the so-called SnSr10 alloy is used as Sn-Sr alloy, which is available on the market prefabricated.
- This usually contains between 89 and 91 percent by weight, in particular 90 percent by weight Sn, between 9 and 10 percent by mass, in particular 9.5 percent by mass Sr and between 0.2 and 0.3, in particular 0.28 percent by mass Al.
- AI has an unfavorable effect on the properties of the casting alloy, it is present in the SnSr10 alloy for production reasons.
- strontium is bound as a stable intermetallic phase and therefore has no endangerment due to reactivity and, unlike elemental strontium, is not subject to any hazardous substances ordinance.
- a so-called CuZn32 master alloy is used as Cu-Zn alloy.
- copper is usually melted together with zinc above 1100 ° C, in particular at about 1210 ° C. This forms a homogeneous alloy melt, which is subsequently cooled to solidification.
- the alloy usually contains between 60 and 70 percent by mass copper, in particular about 68 percent by mass, and the remainder zinc, in particular 32 percent by mass (hence the name CuZn32 master alloy). Since elemental zinc has a high vapor pressure and a boiling point of 907 ° C, this would when in pure form at added higher temperatures of the alloy melt would leave the melt in the form of zinc vapor, unless special precautions were taken.
- the CuZn32 master alloy may in particular contain the following elements: lead, tin, phosphorus, silicon or aluminum and / or the elements described below for the copper casting alloy Amounts.
- the Sn-Sr alloy, the Cu-Zn alloy and crude copper (Cu) are preferably added together in solid form, in particular at 1200 ° C., preferably above or at 1100 ° C.
- further additives may be added to the alloy melt as an alloying ingredient or for other purposes such as deoxidation, or may be melted together with the base materials.
- phosphorus is advantageously added for deoxidation, for example in the form of "10% by mass of phosphorus copper” (so-called CuP10).
- the alloy melt is advantageously covered with coke so far as it operates under atmospheric oxygen conditions, so that it forms a reducing CO atmosphere.
- the alloy melt After the alloy melt has been produced, it is cooled in such a way that at least one 2-phase structure of the first Sr-containing mixed phase and a base phase, namely a copper alloy matrix phase, forms.
- This cooling is usually done after casting at about 1200 ° C in a mold.
- a casting mold can be any known casting mold, casting into a sand casting mold is particularly preferred here. With increasing pouring temperature and increasing contents of particularly oxygen-affinitive elements in the liquid metal, such as strontium in this case, the propensity to form reaction also increases.
- the copper casting alloy is present as a homogeneous melt. From a temperature of 1050 to 1000 ° C., in particular at 1020 ° C., first ⁇ -mixed crystals of a main phase which forms (copper alloy matrix phase) typically precipitate.
- This main phase is especially a brass or bronze, or multi-metal bronze phase, optionally with other alloying elements. Accordingly, the proportion of strontium increases in the residual alloy melt.
- the entire copper alloy matrix phase is solidified. In this solidified copper alloy matrix phase, at least one first Sr-containing phase uniformly distributed in the microstructure is present. This first Sr-containing phase is immiscible with the copper alloy matrix phase, the latter being essentially Sr-free.
- the first Sr-containing alloy phase forms an at least partially coherent network-like vein structure, wherein at high cooling rates, in particular of up to 5 ° C / s, a fine dispersive structure is formed, in which individual agglomerates of the first Sr-containing phase do not substantially touch.
- a copper- and / or tin-containing Sr phase having a different composition is formed during the cooling process.
- This first Sr-containing phase usually has one lower melting point than that of the copper alloy matrix phase and therefore falls only after the advanced solidification of the copper alloy matrix phase.
- this Sr-containing phase is formed from the residual melt as the last solidifying phase and is thus able to fill previously formed by solidification of the copper alloy matrix phase resulting voids in the casting and thus has a vein-like shape in Gussleg istöges divege.
- the first Sr-containing phase has the empirical formula Cu 4 Sn 2 Sr. lower Sr contents of less than 0.2 mass percent and the presence of phosphorus, the first Sr-containing phase has the empirical formula Cu 9 Sn 4 Sr.
- the first Sr-containing phase has in particular the empirical formula Cu 5 Sr, Cu 9 Sn 4 Sr , Cu 4 Sn 2 Sr.
- the first Sr-containing phase has the same empirical formula throughout the entire structure. However, it is also possible that a mixture of the aforementioned phases is present.
- the first Sr-containing phase is always common that this is essentially formed only after the beginning of the solidification of the copper alloy matrix phase from the residual melt and thus has a vein-shaped structure in the structure.
- the empirical formula of the alloy or the alloy phases this was determined by means of EDX or ICP.
- the first Sr-containing phase is a Cu 5 Sr compound, it is preferably formed in a temperature range of 850 ° C to 854 ° C.
- the first Sr-containing phase is the Cu 4 Sn 2 Sr mixed phase, it is preferably formed in a temperature range from 810 ° C. to 790 ° C., very particularly preferably in a temperature range from 810 ° to 797 ° C.
- the first Sr-containing phase is the Cu 9 Sn 4 Sr mixed phase, it is formed in particular in a temperature range from 720 ° C. to 700 ° C., preferably at approximately 710 ° C.
- phase During the cooling of the alloy melt, other phases may also form which are immiscible with the copper alloy matrix phase. These are then also distributed in the casting alloy. If, for example, further Sr-affine elements are present in the melt, preferably one or more further Sr-containing phases form (second Sr-containing mixed phase). If, for example, phosphorus is added to the melt as a deoxidizer, or is present in particular in amounts of more than 0.02% by mass in the melt, a phase with the following composition is formed, for example: Cu 9 P 4 Sr.
- This second Sr-containing phase is often not soluble in the alloy melt even at low temperatures and thus forms a dispersion with the second Sr-containing phase (liquid and / or partially or completely precipitated), the is dispersed in the at least partially molten copper alloy matrix phase.
- This second Sr-containing phase solidifies in particular above the temperature at which the first Sr-containing mixed phase solidifies, but below the temperature of the start of solidification of the copper alloy matrix phase.
- the second Sr-containing phase is the Cu 9 P 4 Sr phase
- the second phase has an oval or droplet-like structure, in contrast to the vein-shaped structure of the first Sr-containing phase.
- At least most of the aggregates of the first Sr-containing phase and the second Sr-containing phase do not contact each other within the microstructure.
- first Sr-containing alloy phase or second Sr-containing phase is used, this is to be understood as an individualization of the individual phases and not as an order in which individual phases crystallize out of the melt and are formed.
- the copper casting alloy contains at least two phases (first Sr-containing phase and copper alloy matrix phase), particularly three phases (first Sr-containing alloy phase, second Sr-containing phase, and copper alloy matrix phase). But there may also be other phases.
- the copper casting alloy contains at least 80 to 95% by mass, preferably 83 to 87% by mass, or alternatively preferably about 89 to 90% by mass Cu and at least one of the elements Sn or Zn.
- the proportion of the aforementioned elements (Sn / Zn) together is 5 to 20% by mass, preferably 9 to 10% by mass. Particularly preferably, both elements are present in the alloy.
- preferably 4 to 6% by mass of Sn, in particular 4 to 5% by mass of Sn and 4 to 6% by mass of Zn, in particular 5 to 6% by mass of Zn are provided.
- the Zn content is higher than that of the Sn to choose, in particular about 1 percentage point higher.
- the alloy contains strontium in an amount of greater than 0 percent by mass to 1.0 percent by mass.
- the strontium content is preferably between 0.01 and 0.7 percent by mass, very particularly preferably between 0.1 and 0.5 percent by mass, in particular about 0.4 percent by mass or alternatively about 0.14 percent by mass.
- the values in the rounding range of the unrecorded decimal places belong to the specified range.
- O may be incorporated in the alloy during the manufacturing process in oxidic form as an unavoidable impurity.
- Alloys were produced under the atmosphere of the protective gas agon and a maximum oxygen content of 8 x 10 -4 mol.
- a copper alloy melt was produced in an induction furnace.
- the SnSr10 master alloy had the following composition: 90.22% by mass of Sn, 9.50% by mass of Sr and 0.28% by mass of Al.
- Strontium is bound in this as a stable intermetallic phase. So there is no risk due to reactivity and unlike elemental strontium, the alloy is not subject to any hazardous substances regulation.
- This alloy melt was cooled in each case in three different ways. On the one hand, the alloy melt was cooled directly in the Al 2 O 3 crucible used for melting (hereinafter crucible), on the other hand in a mold (hereinafter mold) and thirdly in a cylindrical cavity formed by a sand mold (hereinafter Cylinder) poured off and cooled there.
- crucible Al 2 O 3 crucible used for melting
- mold a mold
- Cylinder sand mold
- FIG. 1a Microscopic micrographs of the mold and the cylinder of the alloys obtained after cooling are shown.
- the bar (bottom right) in each figure indicates a length of 100 ⁇ m.
- FIG. 1a In the pictures in FIG. 1a it can be seen that a two-phase structure is formed.
- a main phase which is like the EDX spectrum in FIG. 1b is formed by a Sr-free Cu-Sn-Zn phase
- the copper alloy matrix phase is distributed in this copper alloy matrix phase, such as the EDX spectrum in FIG. 1b shows Sr-containing phase (first Sr-containing phase).
- the Sr-containing phase has a vein-shaped formation, with increasing cooling rate (cylinder, mold), the fineness of the phases increases.
- FIG. 1b For example, an EDX spectrum is shown in the positions 1 (first Sr-containing phase) and 2 (copper alloy matrix phase) of the alloy shown in this figure from the cylinder.
- the phase in position 2 has the following chemical composition: 89.84 mass% Cu, 3.30 mass% Sn, 6.86 mass% Zn, 0.00 mass% Sr.
- the main phase contains only copper, tin and zinc (in addition to the aforementioned impurities) but is Sr-free.
- the phase 1 phase which is distributed in the main phase, contains strontium.
- the phase in position 1 is, as the EDX analysis shows, a Cu4Sn2Sr phase having the following composition: 43.88 to 44.2% by mass of Cu, 39.90 to 40.90% by mass of Sn, 15.13 up to 15.3 mass percent Sr.
- this first Sr-containing phase takes place in the temperature range between 810 and 797 ° C (see Figure 1c , Graph dT / dt).
- the Sr-rich residual melt forms the Cu 4 Sn 2 Sr phase, which then solidifies in the temperature range of 810 to 797 ° C, which also causes the vein-shaped habit. This phase is not soluble in the Cu-Zn-Sn copper matrix phase.
- An alloy melt was melted together from HCP copper, Zn, SnSr10 and CuP10.
- the alloy melt was covered with coke, so that a CO-atmosphere was formed.
- the resulting copper alloy melt was poured into a sand mold and plates with different plate thickness, namely u.a. manufactured with a plate thickness of 6 mm and 9 mm.
- the cast copper alloy had the following composition determined by ICP-OES analysis: 89.54 mass% Cu, 4.6 mass% Sn, 5.68 mass% Zn, 0.04 mass% P, 0.142 mass% Sr and less than 0.01 mass% Pb.
- FIG. 2a A microscopic image of a microstructure cut after cooling and solidification of the alloy in the sand mold is for the plate with 9 millimeters in FIG. 2a shown.
- main phase which like the EDX spectrum in FIG. 2b 2 (see position 3) is formed by a Sr-free Cu-Sn-Zn phase
- the copper alloy matrix phase two further phases are distributed in this copper alloy matrix phase, one such as the EDX spectrum in FIG. 2b (Position 1) shows Sr-containing phase (first Sr-containing phase), as well as another, such as the EDX spectrum in FIG. 2b (Position 2) shows strontium-containing phase (second strontium-containing phase). Both Sr-containing phases are finely distributed in the copper alloy matrix phase.
- the first Sr-containing phase in position 1 has the following chemical composition (without considering the proportion of O as an undesired impurity): 50.42 to 50.49 mass% Cu, 41.86 to 41.70 mass% Sn, 7 , 72 to 7.81 mass percent Sr.
- the second Sr-containing phase in position 2 has the following chemical composition (excluding the proportion of O as undesirable impurity): 73.00 to 73.46 mass% Cu, 15.04 to 15.81 mass% P, 11 , 18 to 11.50 mass percent Sr.
- the copper alloy matrix phase (position 3) (excluding the proportion of O as undesirable impurity), has the following chemical composition: 88.1 to 89.2 mass% Cu, 3.5 to 3.54 mass% Sn, 7.2 to 7.3 mass% Zn, 0.0 mass% Sr and 0.0 mass% P.
- the Cu 9 P 4 Sr phase in position 2 has an oval or teardrop-like structure, the phase in position 1 having a vein-shaped structure similar to the Cu 4 Sn 2 Sr phase in test series 1 (cf. FIG. 2a combined with FIG. 2b ).
- the Cu 9 P 4 Sr phase (second Sr-containing phase) solidifies in a temperature range of 762 ° C and 729 ° C.
- the Cu 9 Sn 4 Sr phase (first Sr-containing phase) forms with a vein-shaped structure.
- the reason for the different habit of the structures is explained in the general description.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Domestic Plumbing Installations (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14002217.9A EP2960350B1 (fr) | 2014-06-27 | 2014-06-27 | Alliage de fonte au cuivre |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14002217.9A EP2960350B1 (fr) | 2014-06-27 | 2014-06-27 | Alliage de fonte au cuivre |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2960350A1 true EP2960350A1 (fr) | 2015-12-30 |
| EP2960350B1 EP2960350B1 (fr) | 2017-11-29 |
Family
ID=51062615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14002217.9A Not-in-force EP2960350B1 (fr) | 2014-06-27 | 2014-06-27 | Alliage de fonte au cuivre |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP2960350B1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022223673A1 (fr) * | 2021-04-22 | 2022-10-27 | Ks Gleitlager Gmbh | Alliage de coulée continue cuivre-étain |
| DE102023116139A1 (de) * | 2023-06-20 | 2024-12-24 | Sundwiger Messingwerk GmbH | Bleifreie Messinglegierung |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628781B (zh) * | 2019-01-23 | 2020-12-04 | 中南大学 | 高铁含量的Cu-Fe系合金材料及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997000977A1 (fr) | 1995-06-21 | 1997-01-09 | Asarco Incorporated | Alliages de cuivre sans plomb usinables et additifs, et procede de fabrication desdits alliages |
| EP1600516A2 (fr) | 1998-10-12 | 2005-11-30 | Sambo Copper Alloy Co., Ltd | Alliage de cuivre de décolletage sans plomb |
| WO2011121799A1 (fr) | 2010-03-31 | 2011-10-06 | Ｊマテ．カッパープロダクツ 株式会社 | Alliage de bronze de décolletage exempt de plomb |
| EP2530175A1 (fr) * | 2010-01-26 | 2012-12-05 | Mitsubishi Materials Corporation | Alliage de cuivre présentant une grande résistance et une conductivité électrique élevée |
-
2014
- 2014-06-27 EP EP14002217.9A patent/EP2960350B1/fr not_active Not-in-force
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997000977A1 (fr) | 1995-06-21 | 1997-01-09 | Asarco Incorporated | Alliages de cuivre sans plomb usinables et additifs, et procede de fabrication desdits alliages |
| EP1600516A2 (fr) | 1998-10-12 | 2005-11-30 | Sambo Copper Alloy Co., Ltd | Alliage de cuivre de décolletage sans plomb |
| EP2530175A1 (fr) * | 2010-01-26 | 2012-12-05 | Mitsubishi Materials Corporation | Alliage de cuivre présentant une grande résistance et une conductivité électrique élevée |
| WO2011121799A1 (fr) | 2010-03-31 | 2011-10-06 | Ｊマテ．カッパープロダクツ 株式会社 | Alliage de bronze de décolletage exempt de plomb |
Non-Patent Citations (1)
| Title |
|---|
| WIRTSCHAFTSVEREINIGUNG METALLE ET AL: "Published by the Copper Casting Alloy Department (Gesamtverband der Deutschen Buntmetallindustrie) in the Copper c asting alloys C O N T I N U O U S CASTING QUALITY", 1 January 2011 (2011-01-01), pages 1 - 9, XP055155737, Retrieved from the Internet <URL:http://www.msu-ulm.com/cms/upload/Images_Header/MSU_Copper_Casting_Alloys_2011.pdf> [retrieved on 20141128] * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022223673A1 (fr) * | 2021-04-22 | 2022-10-27 | Ks Gleitlager Gmbh | Alliage de coulée continue cuivre-étain |
| DE102023116139A1 (de) * | 2023-06-20 | 2024-12-24 | Sundwiger Messingwerk GmbH | Bleifreie Messinglegierung |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2960350B1 (fr) | 2017-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69417553T2 (de) | Sanitaereinrichtungen | |
| DE102005002763B4 (de) | Kupferlegierung mit hoher Festigkeit und hoher Leitfähigkeit | |
| EP2964797B1 (fr) | Alliage cuivre-zinc pour une robinetterie sanitaire, et procédé de fabrication de ladite robinetterie | |
| AT522440A4 (de) | Mehrschichtgleitlagerelement | |
| DE10065735A1 (de) | Verbindungsstücke aus Kupferlegierungen und Verfahren zur Herstellung derselben | |
| EP2960350B1 (fr) | Alliage de fonte au cuivre | |
| DE69207289T2 (de) | Legierung auf Kupfer-Nickel-Basis | |
| WO2016045770A1 (fr) | Élément de connexion électrique | |
| EP3581667B1 (fr) | Pièces moulées d'un alliage de cuivre résistant à la corrosion et pouvant être usiné | |
| CH673843A5 (fr) | ||
| EP2625300B1 (fr) | Alliage de cuivre | |
| DE3729509C2 (de) | Verbesserte Kupferlegierung, insbesondere für die Herstellung elektronischer Bauteile | |
| DE19800433C2 (de) | Stranggießverfahren zum Vergießen einer Aluminium-Gleitlagerlegierung | |
| DE2241243C2 (de) | Verfahren zur Erhöhung der Beständigkeit von Messing gegen Entzinken | |
| EP1647352B1 (fr) | Matériau de brasure | |
| EP4271846B1 (fr) | Alliage de coulée continue à base de cuivre et d?étain | |
| EP4271847B1 (fr) | Alliage de coulée continue à base de cuivre et d'étain | |
| DE3627282A1 (de) | Legierung zur kornfeinung von kupferwerkstoffen | |
| EP4271848B1 (fr) | Alliage de coulée continue à base de cuivre et d'étain | |
| AT412725B (de) | Mittel zur beeinflussung der erstarrungsstruktur von magnesium und magnesiumlegierungen | |
| EP3024956B1 (fr) | Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore | |
| EP4569148A1 (fr) | Matériau de coulée fait d'un alliage de cuivre-zinc, procédé de fabrication d'un produit coulé et pièce coulée | |
| WO1989007660A1 (fr) | Alliage d'affinage structural de materiaux cuivreux | |
| DE1163033B (de) | Verfahren zur Behandlung von Kupfer und Nickel und ihren Legierungen |
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 |
|
| 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: 20160629 |
|
| 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 |
|
| R17P | Request for examination filed (corrected) |
Effective date: 20160629 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| INTG | Intention to grant announced |
Effective date: 20170508 |
|
| GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| INTC | Intention to grant announced (deleted) | ||
| INTG | Intention to grant announced |
Effective date: 20170915 |
|
| 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: CH Ref legal event code: EP Ref country code: CH Ref legal event code: NV Representative=s name: BOVARD AG PATENT- UND MARKENANWAELTE, CH |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 950464 Country of ref document: AT Kind code of ref document: T Effective date: 20171215 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502014006366 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20171129 |
|
| 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: 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: 20171129 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: 20171129 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: 20171129 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: 20180228 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: 20171129 |
|
| 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: 20171129 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: 20171129 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: 20171129 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: 20180228 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: 20180301 |
|
| 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: 20171129 |
|
| 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: 20171129 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: 20171129 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: 20171129 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: 20171129 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: 20171129 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502014006366 Country of ref document: DE |
|
| 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: 20171129 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: 20171129 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: 20171129 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: 20171129 |
|
| 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: 20171129 |
|
| 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 |
|
| 26N | No opposition filed |
Effective date: 20180830 |
|
| 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: 20171129 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502014006366 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20180627 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180630 |
|
| 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: 20171129 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180627 |
|
| 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: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180627 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180627 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180630 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190101 |
|
| 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: 20180630 |
|
| 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: 20171129 |
|
| 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: 20171129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20171129 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: 20140627 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20171129 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: 20180329 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 950464 Country of ref document: AT Kind code of ref document: T Effective date: 20190627 |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20190627 |