EP3024956B1 - Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore - Google Patents

Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore Download PDF

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Publication number
EP3024956B1
EP3024956B1 EP14735475.7A EP14735475A EP3024956B1 EP 3024956 B1 EP3024956 B1 EP 3024956B1 EP 14735475 A EP14735475 A EP 14735475A EP 3024956 B1 EP3024956 B1 EP 3024956B1
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Prior art keywords
iron
content
boron
weight
copper
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Application number
EP14735475.7A
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German (de)
English (en)
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EP3024956A1 (fr
Inventor
Michael Scharf
Jochen Aufrecht
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Wieland Werke AG
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Wieland Werke AG
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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
    • C22C9/04—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
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising

Definitions

  • the invention relates to a copper-zinc casting alloy.
  • the invention relates to a copper-zinc-silicon alloy in which boron and iron and optionally nickel are added.
  • molded parts made of copper alloys are produced as castings.
  • molded parts are fittings, elbows, T-pieces for media-carrying piping systems, components for pumps and valves as well as structural parts in mechanical and plant engineering and in vehicle construction.
  • silicon-containing brasses are used as material for this purpose.
  • a material In order to ensure the mechanical stability of the molded part, a material is required, which already has a homogeneous structure in the cast state. Inhomogeneities in the structure must be taken into account by costly safety margins or they can lead to failure of the component. With wrought materials, the homogeneity of the structure is achieved by forming. In order to achieve a homogeneous structure without forming steps, the material must already have a fine-grained structure in the cast state. After casting, the molding is in many cases by machining, grinding or polishing, such as sealing surfaces, reworked. For this purpose, the material must be free from voids and hard particles. Furthermore, a coarse dendritic microstructure has a negative effect on the corrosion resistance of the material.
  • the material In the production of castings, the material is usually melted and poured twice: the first time the alloy is melted, the alloy composition is roughly adjusted. The alloy is poured into ingots. For the production of the castings, the ingots are melted down and the alloy is cast into moldings. A change in the alloy composition during this second reflow and pouring operation is undesirable but unavoidable due to the burning of some elements, such as Zn, Zr or P. For the quality of the product, the casting condition after the second casting is crucial.
  • boron as a grain refining agent for copper alloys is known. So will in DE 10 2005 024 037 A1 proposed to add 0.00001 to 0.5% boron to a copper-zinc-silicon alloy. Boron-fines of small amounts of boron are detected by alloys containing approximately 76% copper, 21% zinc and 3% silicon.
  • the publication CN 103114220 A discloses a Cu-Zn-Si alloy containing 0.11-0.2% Fe and 0.001-0.01% B, Ag and / or Ti.
  • the invention has for its object to provide improved copper-zinc casting alloys.
  • a grain refining of the cast structure should be able to be achieved largely independently of the zinc or copper content.
  • grain refining agents for copper contents greater than 80% by weight are particularly desirable.
  • the invention relates to the copper-zinc casting alloy according to claim 1.
  • the others refer back Claims relate to advantageous embodiments and further developments of the invention.
  • the invention is based on the consideration that by the simultaneous addition of boron and iron to a silicon-containing copper-zinc alloy, a grain refining of the cast structure occurs when boron content and iron content are in a certain ratio. Iron can be partially replaced by nickel. The ratio of boron content and the sum of iron and nickel content is at least 0.025 and at most 0.12. The respective element contents are defined as parts by weight of the total alloy. Are boron content and the sum of iron and nickel content in the relation to each other, iron borides or nickel borides or iron-nickel Mischboride can form. These borides lead to the formation of a fine grain in the cast structure of the material.
  • the alloy may contain tin.
  • Tin improves the corrosion resistance of the material. With tin contents greater than 2.0% by weight, unwanted tin blends may occur due to the interaction of all alloy constituents.
  • the alloy may contain phosphorus.
  • phosphorus serves to deoxidize the melt. Furthermore, it can favorably influence the formation of the initial cast structure and the corrosion properties. Phosphorus increases the fluidity of the melt and reduces the susceptibility of the material to stress corrosion cracking.
  • the lead content of the alloy according to the invention is limited to a maximum of 0.25 wt .-%.
  • the lead content of the alloy may preferably be at most 0.1% by weight.
  • the alloy may contain small amounts of antimony and / or arsenic. These two elements reduce the tendency of the material for Entzinkung.
  • the ratio of boron content and the sum of iron and nickel content may be at least 0.05 and at most 0.075.
  • the boron content may be at least 0.005% by weight, more preferably at least 0.01% by weight and at most 0.025% by weight.
  • Boron contents of at least 0.005 wt .-%, preferably at least 0.01 wt .-%, in conjunction with iron and optionally nickel borides can form particularly rapidly. With a boron content greater than 0.025 wt .-% can lead to the formation of undesirable large borides.
  • the iron content may be at least 0.1% by weight and at most 0.5% by weight.
  • This preferred selection of iron content is stoichiometrically particularly favorable conditions for the formation of borides in suitable frequency and size.
  • this preferred iron content is combined with a boron content of not less than 0.01% by weight and not more than 0.025% by weight. -% is already present at the first casting the alloy a fine-grained structure.
  • the nickel content may amount to at most 0.3 wt .-%.
  • nickel can at least partially replace the iron.
  • the sum of iron and nickel content at least 0.1 wt .-% and at most 0.5 wt .-% amount.
  • the copper content of the alloy may be more than 80% by weight, preferably at least 81% by weight. Copper contents of more than 80% by weight make the alloy particularly corrosion-resistant and therefore suitable for use in fluid-carrying piping systems, such as drinking water pipes.
  • the silicon content in this copper content is typically at least 3 wt .-% and at most 4 wt .-%.
  • the zinc content is then below 16 wt .-%, and is preferably at least 8 wt .-% and at most 15 wt .-%.
  • the ratio of boron content of the alloy [in% by weight] and iron content of the alloy [in% by weight] is at least 0.025 and at most 0.12.
  • the copper-zinc-silicon alloy may have the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B From 0.002 to 0.03%, Fe 0.01 to 1.0%, optionally up to 2.0% Sn, optionally up to 0.2% P, optionally up to 0.25% Pb, optionally still up to 0.15% As or Sb, Rest Zn as well as unavoidable impurities.
  • grain refining of the cast structure may occur in a copper-zinc-silicon alloy.
  • the boron content is preferably at least 0.005% by weight and at most 0.025% by weight.
  • the iron content is preferably at least 0.1% by weight and at most 0.5% by weight.
  • the aspect of using boron and iron to refine copper-zinc-silicon alloys includes all of the above-described preferred embodiments of a silicon-containing copper-zinc casting alloy according to the present invention.
  • the copper-zinc-silicon alloy may have the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B From 0.002 to 0.03%, Fe 0.01 to 1.0%, Ni 0.01 to 0.4% optionally up to 2.0% Sn, optionally up to 0.2% P, optionally up to 0.25% Pb, optionally still up to 0.15% As or Sb, Rest Zn as well as unavoidable impurities.
  • grain refining of the cast structure may occur in a copper-zinc-silicon alloy.
  • the boron content is preferably at least 0.005% by weight and at most 0.025% by weight.
  • the iron content is preferably at least 0.1% by weight and at most 0.5% by weight.
  • the nickel content is preferably at least 0.05% by weight and at most 0.3% by weight.
  • the aspect of using boron, iron and nickel for grain refining of copper-zinc-silicon alloys includes all of the above-described preferred embodiments of a silicon-containing copper-zinc casting alloy according to the present invention.
  • Table 1 shows the composition in% by weight of 18 trial alloys, with samples 1, 2, 3, 4, 11 and 18 not belonging to the invention.
  • the penultimate column of the table gives the ratio of boron content and the sum of iron and nickel content.
  • the alloys were melted and poured off.
  • the individual casts were melted down again and poured off a second time.
  • the samples were characterized metallographically.
  • the last column of the table indicates whether the structure after the second casting was coarse or fine grained.
  • Samples 1 to 3 contain no boron.
  • the cast structure is always coarse-grained.
  • Sample 4 and sample 11 contain small amounts of boron. Again, the structure is coarse-grained.
  • Samples 5 to 10 contain both boron (0.01 to 0.02 wt%) and iron (0.1 to 0.3 wt%). Sample 8 additionally contains 0.4% by weight of tin. For samples 5 to 10, a fine-grained cast structure is always observed after the second casting. The quotient of boron content and iron content in these samples is between 0.03 and 0.11. The addition of tin has no influence on the formation of the fine-grained casting structure.
  • the samples 5, 7, 8 and 15, in contrast to the other samples after the first casting have a fine-grained structure.
  • These samples are characterized in that the quotient of boron content and the sum of iron and nickel content is between 0.05 and 0.065. If one chooses the alloy composition so that said quotient is exactly in this window, then the formation of iron borides or nickel borides or iron-nickel Mischboriden is particularly favored. Iron borides with the stoichiometric formula Fe 3 B would correspond exactly to this weight ratio of boron and iron.
  • sample 18 On the basis of sample 18, the influence of manganese on the cast structure was examined in the form of a random sample. Sample 18 contains no boron but about 0.08 wt% manganese. The manganese-containing sample always shows a coarse-grained cast structure.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Claims (8)

  1. Alliage de fonderie cuivre-zinc ayant la composition suivante [en % en poids] : Cu 70,0 à 97,0 %, Si 2,0 à 4,5 %, B 0,002 à 0,03 %, Fe 0,01 à 1,0 %,
    au choix encore jusqu'à 2,0 % de Sn,
    au choix encore jusqu'à 0,4 % de Ni,
    au choix encore jusqu'à 0,2 % de P,
    au choix encore jusqu'à 0,25 % de Pb,
    au choix dans chaque cas encore jusqu'à 0,15 % de As ou de Sb,
    le reste de Zn ainsi que d'impuretés inévitables,
    caractérisé en ce que le rapport de la teneur en bore et de la somme des teneurs en fer et en nickel est d'au moins 0,025 et d'au plus 0,12.
  2. Alliage de fonderie cuivre-zinc selon la revendication 1, caractérisé en ce que le rapport de la teneur en bore et de la somme des teneurs en fer et en nickel est d'au moins 0,05 et d'au plus 0,075.
  3. Alliage de fonderie cuivre-zinc selon la revendication 1 ou 2, caractérisé en ce que la teneur en bore est d'au moins 0,005 % en poids et d'au plus 0,025 % en poids.
  4. Alliage de fonderie cuivre-zinc selon la revendication 3, caractérisé en ce que la teneur en bore est d'au moins 0,01 % en poids et d'au plus 0,025 % en poids.
  5. Alliage de fonderie cuivre-zinc selon l'une des revendications 1 à 4, caractérisé en ce que la teneur en fer est d'au moins 0,1 % en poids et d'au plus 0,5 % en poids.
  6. Alliage de fonderie cuivre-zinc selon l'une des revendications 1 à 5, caractérisé en ce que la teneur en nickel est d'au plus 0,3 % en poids.
  7. Alliage de fonderie cuivre-zinc selon l'une des revendications 1 à 6, caractérisé en ce que la teneur en fer est supérieure à la teneur en nickel.
  8. Alliage de fonderie cuivre-zinc selon l'une des revendications 1 à 7, caractérisé en ce que la teneur en cuivre est d'au moins 81 % en poids.
EP14735475.7A 2013-07-24 2014-07-03 Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore Active EP3024956B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP17001201.7A EP3260561B1 (fr) 2013-07-24 2014-07-03 Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013012288.0A DE102013012288A1 (de) 2013-07-24 2013-07-24 Korngefeinte Kupfer-Gusslegierung
PCT/EP2014/001832 WO2015010768A1 (fr) 2013-07-24 2014-07-03 Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP17001201.7A Division EP3260561B1 (fr) 2013-07-24 2014-07-03 Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore
EP17001201.7A Division-Into EP3260561B1 (fr) 2013-07-24 2014-07-03 Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore

Publications (2)

Publication Number Publication Date
EP3024956A1 EP3024956A1 (fr) 2016-06-01
EP3024956B1 true EP3024956B1 (fr) 2018-06-27

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ID=51063400

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EP17001201.7A Active EP3260561B1 (fr) 2013-07-24 2014-07-03 Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore
EP14735475.7A Active EP3024956B1 (fr) 2013-07-24 2014-07-03 Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore

Family Applications Before (1)

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EP17001201.7A Active EP3260561B1 (fr) 2013-07-24 2014-07-03 Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore

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Country Link
EP (2) EP3260561B1 (fr)
DE (1) DE102013012288A1 (fr)
ES (1) ES2813073T3 (fr)
WO (1) WO2015010768A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060078458A1 (en) 2004-10-11 2006-04-13 Diehl Metall Stiftung & Co. Kg Copper-zinc-silicon alloy, products using the alloy and processes for producing the alloy
CN103114220A (zh) 2013-02-01 2013-05-22 路达(厦门)工业有限公司 一种热成型性能优异的无铅易切削耐蚀黄铜合金

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Publication number Priority date Publication date Assignee Title
GB2234986A (en) 1989-08-18 1991-02-20 London Scandinavian Metall Grain refining of copper-based alloys
JPH03115538A (ja) * 1989-09-29 1991-05-16 Tsuneaki Mikawa 粒子分散強化特殊銅合金
JPH04180531A (ja) * 1990-11-14 1992-06-26 Nikko Kyodo Co Ltd 通電材料
US5893953A (en) * 1997-09-16 1999-04-13 Waterbury Rolling Mills, Inc. Copper alloy and process for obtaining same
WO2005021828A2 (fr) * 2003-08-21 2005-03-10 Honeywell International Inc. Cibles pvd comprenant du cuivre dans des melanges ternaires, et procedes pour former des cibles pvd contenant du cuivre
JP3964930B2 (ja) 2004-08-10 2007-08-22 三宝伸銅工業株式会社 結晶粒が微細化された銅基合金鋳物
DE102005024037A1 (de) 2004-10-11 2006-04-13 Diehl Metall Stiftung & Co.Kg Kupfer-Zink-Silizium-Legierung, deren Verwendung und deren Herstellung
ATE380259T1 (de) 2005-12-14 2007-12-15 Kemper Gebr Gmbh & Co Kg Verwendung einer migrationsarmen kupferlegierung sowie bauteile aus dieser legierung
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WO2009047919A1 (fr) * 2007-10-10 2009-04-16 Toto Ltd. Laiton de décolletage exempt de plomb présentant une excellente aptitude à la coulée
EP2196549B1 (fr) * 2007-10-10 2019-03-13 Toto Ltd. Laiton à coupe rapide, exempt de plomb ayant une excellente aptitude à la coulée
KR101340487B1 (ko) * 2011-09-30 2013-12-12 주식회사 풍산 쾌삭성 무연 구리합금 및 이의 제조방법

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060078458A1 (en) 2004-10-11 2006-04-13 Diehl Metall Stiftung & Co. Kg Copper-zinc-silicon alloy, products using the alloy and processes for producing the alloy
CN103114220A (zh) 2013-02-01 2013-05-22 路达(厦门)工业有限公司 一种热成型性能优异的无铅易切削耐蚀黄铜合金

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M. SADAYAPPAN: "Grain refinement of permanent mold cast copper base alloys", MATERIALS TECHNOLOGY LABORATORY, April 2004 (2004-04-01), XP009115928

Also Published As

Publication number Publication date
EP3260561A1 (fr) 2017-12-27
WO2015010768A1 (fr) 2015-01-29
DE102013012288A1 (de) 2015-01-29
EP3024956A1 (fr) 2016-06-01
EP3260561B1 (fr) 2020-06-24
ES2813073T3 (es) 2021-03-22

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