EP3260561B1 - Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore - Google Patents

Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore Download PDF

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Publication number
EP3260561B1
EP3260561B1 EP17001201.7A EP17001201A EP3260561B1 EP 3260561 B1 EP3260561 B1 EP 3260561B1 EP 17001201 A EP17001201 A EP 17001201A EP 3260561 B1 EP3260561 B1 EP 3260561B1
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Prior art keywords
weight
iron
boron
content
alloy
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German (de)
English (en)
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EP3260561A1 (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 the grain refinement of copper-zinc-silicon cast alloys in which boron and iron and optionally nickel are added for grain refinement.
  • molded parts made of copper alloys are manufactured as castings. Examples of such molded parts are fittings, elbows, T-pieces for media-carrying line systems, components for pumps and valves as well as construction parts in machine and plant construction and in vehicle construction. Among other things, silicon-containing brass is used as the material.
  • a material In order to ensure the mechanical stability of the molded part, a material is required that already has a homogeneous structure when cast. Inhomogeneities in the structure must be taken into account through costly safety supplements or they can lead to component failure. In the case of kneading 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 when cast. After casting, the molded part is in many cases reworked by machining, grinding or polishing, for example sealing surfaces. To do this, the material must be free from cavities and hard particles. Furthermore, a rough dendritic structure has a negative effect on the corrosion resistance of the material.
  • the material When producing cast parts, the material is usually melted and poured twice: the first time the alloy is melted, the alloy composition is roughly adjusted. The alloy is cast into ingots. To produce the cast parts, the cast blocks are melted and the alloy is cast into molded parts. Changing the alloy composition during this second melting and casting process is undesirable, but due to the erosion of some elements, such as Zn, Zr or P, is inevitable. The condition of the casting after the second pour is decisive for the quality of the product.
  • 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 grain refining agents for copper-zinc-silicon casting alloys.
  • grain refiners for copper contents greater than 80% by weight are particularly desirable.
  • the invention is with respect to the use of boron and iron as grain refinement by the features of claim 1 and with respect to Use of boron, iron and nickel as grain refinement represented by the features of claim 4.
  • the further back claims relate to advantageous developments and further developments of the invention.
  • the teaching includes a copper-zinc casting alloy with the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B 0.002 to 0.03%, Fe 0.01 to 1.0%, optionally up to 2.0% Sn, optionally up to 0.4% Ni, optionally up to 0.2% P, optionally up to 0.25% Pb, optionally up to 0.15% As or Sb, Balance Zn and inevitable impurities.
  • the ratio of boron content and the sum of iron and nickel content is at least 0.025 and at most 0.12.
  • the simultaneous addition of boron and iron to a silicon-containing copper-zinc alloy results in grain refinement of the cast structure when the boron content and iron content are in a certain relationship to one another.
  • 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. If the boron content and the sum of the iron and nickel content stand in relation to one another, iron borides or nickel borides or iron-nickel mixed borides can form. These borides lead to the formation of a fine grain in the cast structure of the material.
  • the alloy can optionally contain small amounts of antimony and / or arsenic. These two elements reduce the tendency of the material to dezincify.
  • the ratio of boron content and the sum of iron and nickel content can be at least 0.05 and at most 0.075.
  • the boron content can be at least 0.01% by weight and at most 0.025% by weight. With boron contents of at least 0.005% by weight, preferably at least 0.01% by weight, boron can form particularly quickly in connection with iron and optionally nickel. If the boron content is greater than 0.025% by weight, undesirable large borides can be formed.
  • the iron content of the alloy is at least 0.1% by weight and at most 0.5% by weight. This selection of the iron content represents stoichiometrically particularly favorable conditions for the formation of borides in a suitable frequency and size. In particular when this preferred iron content is combined with a boron content which is not less than 0.01% by weight and not more than 0.025% by weight. %, there is a fine-grained structure already when the alloy is cast for the first time.
  • the alloy can optionally contain small amounts of antimony and / or arsenic. These two elements reduce the tendency of the material to dezincify.
  • the ratio of boron content and the sum of iron and nickel content can be at least 0.05 and at most 0.075.
  • the boron content can be at least 0.01% by weight and at most 0.025% by weight. With boron contents of at least 0.005% by weight, preferably at least 0.01% by weight, boron can form particularly quickly in connection with iron and optionally nickel. If the boron content is greater than 0.025% by weight, undesirable large borides can be formed.
  • the iron content is at least 0.1% by weight and at most 0.5% by weight. This selection of the iron content represents stoichiometrically particularly favorable conditions for the formation of borides in a suitable frequency and size. In particular when this iron content is combined with a boron content which is not less than 0.01% by weight and not more than 0.025% by weight is a fine-grained structure already at the first casting of the alloy.
  • the nickel content can be at most 0.3% by weight.
  • nickel can at least partially replace the iron.
  • the sum of the iron and nickel content can be at least 0.1% by weight and at most 0.5% by weight.
  • the copper content of the alloy can advantageously be more than 80% by weight, preferably at least 81% by weight. Copper contents greater than 80% by weight make the alloy particularly corrosion-resistant and therefore suitable for use in fluid-carrying pipe systems, such as drinking water pipes. With this copper content, the silicon content is typically at least 3% by weight and at most 4% by weight. The zinc content is then less than 16% by weight, and is preferably at least 8% by weight and at most 15% by weight.
  • the invention includes the use of boron and iron as defined in claim 1 in combination as a grain refiner in copper-zinc-silicon cast alloys.
  • 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 casting alloy can have the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B 0.002 to 0.03%, Fe 0.1 to 0.5%, optionally up to 2.0% Sn, optionally up to 0.2% P, optionally up to 0.25% Pb, optionally up to 0.15% As or Sb, Balance Zn and inevitable impurities.
  • the addition of boron and iron in the above-mentioned ratio of the contents can result in grain refinement of the cast structure in a copper-zinc-silicon alloy.
  • the boron content is preferably at most 0.025% by weight.
  • the iron content of the alloy is at least 0.1% by weight and at most 0.5% by weight.
  • the aspect of the use of boron and iron according to the invention for grain refinement of copper-zinc-silicon casting alloys includes all of the preferred embodiments of a silicon-containing copper-zinc casting alloy described above.
  • the invention further comprises the use of boron, iron and nickel as defined in claim 4 in combination as a grain refining agent in copper-zinc-silicon alloys.
  • the ratio of the boron content of the alloy [in% by weight] and the sum of the iron and nickel content of the alloy [in% by weight] is at least 0.025 and at most 0.12.
  • the copper-zinc-silicon casting alloy can have the following composition [in% by weight]: Cu 70.0 to 97.0%, Si 2.0 to 4.5%, B 0.002 to 0.03%, Fe 0.1 to 0.5%, 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 up to 0.15% As or Sb, Balance Zn and inevitable impurities.
  • the addition of boron, iron and nickel in the above-mentioned ratio of the contents can result in grain refinement of the cast structure 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 of the alloy is 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 the use of boron, iron and nickel according to the invention for grain refinement of copper-zinc-silicon alloys includes all of the preferred embodiments of a silicon-containing copper-zinc alloy described above.
  • Table 1 shows the composition in% by weight of 18 test alloys.
  • the penultimate column of the table shows the ratio of boron content and the sum of iron and nickel content.
  • the alloys were melted and cast.
  • the individual casts were melted down again and poured a second time.
  • the samples were characterized metallographically.
  • the last column of the table shows whether the structure was coarse-grained or fine-grained after the second pour.
  • Samples 1 to 3 contain no boron.
  • the casting structure is always coarse-grained.
  • Sample 4 and sample 11 contain small amounts of boron. Here too, the structure is coarse-grained.
  • Samples 5 to 10 contain both boron (0.01 to 0.02% by weight) and iron (0.1 up to 0.3% by weight). Sample 8 additionally contains 0.4% by weight of tin.
  • Samples 5 to 10 a fine-grained casting structure can always be observed after the second casting. The ratio 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.
  • Table 1 Test alloys with composition in% by weight. The samples marked with (*) are comparative examples.
  • samples 12 to 17 part of the iron is replaced by nickel.
  • the boron content varies from 0.005 to 0.013% by weight.
  • the iron content is between 0.1 and 0.2% by weight, the nickel content between 0.08 and 0.18% by weight.
  • the tin content also varies from 0.1 to 0.2% by weight.
  • all samples show a fine-grained structure after the second casting.
  • the quotient of boron content and the sum of iron and nickel content is between 0.025 and 0.06. In sample 13, this quotient is 0.016.
  • the sample 13 contains too much iron and nickel in total, based on the boron content of 0.006% by weight.
  • the tin content has no influence on the formation of the fine cast structure.
  • samples 5, 7, 8 and 15 in contrast to the other samples, already have a fine-grained structure after the first casting. 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 the alloy composition is selected so that the quotient mentioned lies precisely in this window, then the formation of iron borides or nickel borides or iron-nickel mixed borides 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 contains no boron, but approximately 0.08% by weight of manganese.
  • the sample containing manganese 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 (5)

  1. Utilisation du bore et du fer en combinaison comme agent d'affinage des grains dans des alliages de fonderie cuivre-zinc-silicium, caractérisée en ce que la teneur en fer des alliages est d'au moins 0,1 % en poids et d'au plus 0,5 % en poids, en ce que la teneur en bore des alliages est d'au moins 0,005 % en poids et en ce que le rapport de la teneur en bore de l'alliage [en % en poids] et de la teneur en fer de l'alliage [en % en poids] est d'au moins 0,025 et d'au plus 0,12.
  2. Utilisation du bore et du fer en combinaison comme agent d'affinage des grains dans des alliages de fonderie cuivre-zinc-silicium selon la revendication 1, caractérisée en ce que le rapport de la teneur en bore de l'alliage [en % en poids] et de la teneur en fer de l'alliage [en % en poids] est d'au moins 0,05.
  3. Utilisation du bore et du fer en combinaison comme agent d'affinage des grains dans des alliages de fonderie cuivre-zinc-silicium selon la revendication 1 ou la revendication 2, caractérisée en ce que la teneur en bore des alliages est d'au plus 0,025 % en poids.
  4. Utilisation du bore, du fer et du nickel en combinaison comme agent d'affinage des grains dans des alliages de fonderie cuivre-zinc-silicium, caractérisée en ce que la teneur en fer des alliages est d'au moins 0,1 % en poids et d'au plus 0,5 % en poids et en ce que le rapport de la teneur en bore de l'alliage [en % en poids] et de la somme de la teneur en fer et de la teneur en nickel de l'alliage [en % en poids] est d'au moins 0,025 et d'au plus 0,12.
  5. Utilisation du bore, du fer et du nickel en combinaison comme agent d'affinage des grains dans des alliages de fonderie cuivre-zinc-silicium selon la revendication 4, caractérisée en ce que la teneur en bore des alliages est d'au moins 0,005 % en poids et d'au plus 0,025 % en poids.
EP17001201.7A 2013-07-24 2014-07-03 Affinement de grains d'alliages de coulée cuivre/zinc/silicium à l'aide de fer et de bore Active EP3260561B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102013012288.0A DE102013012288A1 (de) 2013-07-24 2013-07-24 Korngefeinte Kupfer-Gusslegierung
EP14735475.7A EP3024956B1 (fr) 2013-07-24 2014-07-03 Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore
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 Parent Applications (2)

Application Number Title Priority Date Filing Date
EP14735475.7A Division-Into EP3024956B1 (fr) 2013-07-24 2014-07-03 Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore
EP14735475.7A Division EP3024956B1 (fr) 2013-07-24 2014-07-03 Alliage de fonderie en cuivre à grains affinés comprenant du fer et du bore

Publications (2)

Publication Number Publication Date
EP3260561A1 EP3260561A1 (fr) 2017-12-27
EP3260561B1 true EP3260561B1 (fr) 2020-06-24

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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

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

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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
EP1656467A2 (fr) * 2003-08-21 2006-05-17 Honeywell International Inc. Cibles pvd comprenant du cuivre dans des melanges ternaires, et procedes pour former des cibles pvd contenant du cuivre
DE602005023737D1 (de) 2004-08-10 2010-11-04 Mitsubishi Shindo Kk Gussteil aus kupferbasislegierung mit raffinierten kristallkörnern
DE102005024037A1 (de) 2004-10-11 2006-04-13 Diehl Metall Stiftung & Co.Kg Kupfer-Zink-Silizium-Legierung, deren Verwendung und deren Herstellung
CN100510132C (zh) 2004-10-11 2009-07-08 迪尔金属合作两合公司 铜-锌-硅合金、其用途和其制备
ES2297598T5 (es) 2005-12-14 2016-06-03 Gebr. Kemper Gmbh + Co. Kg Metallwerke Utilización de una aleación de cobre baja en migración y piezas de esta aleación
US20070253858A1 (en) * 2006-04-28 2007-11-01 Maher Ababneh Copper multicomponent alloy and its use
WO2009047919A1 (fr) * 2007-10-10 2009-04-16 Toto Ltd. Laiton de décolletage exempt de plomb présentant une excellente aptitude à la coulée
JP5454144B2 (ja) * 2007-10-10 2014-03-26 Ｔｏｔｏ株式会社 鋳造性に優れた無鉛快削性黄銅
KR101340487B1 (ko) * 2011-09-30 2013-12-12 주식회사 풍산 쾌삭성 무연 구리합금 및 이의 제조방법
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Also Published As

Publication number Publication date
WO2015010768A1 (fr) 2015-01-29
EP3024956B1 (fr) 2018-06-27
DE102013012288A1 (de) 2015-01-29
ES2813073T3 (es) 2021-03-22
EP3260561A1 (fr) 2017-12-27
EP3024956A1 (fr) 2016-06-01

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