EP3377663B1 - Copper-nickel-zinc alloy and use thereof - Google Patents

Copper-nickel-zinc alloy and use thereof Download PDF

Info

Publication number
EP3377663B1
EP3377663B1 EP16784134.5A EP16784134A EP3377663B1 EP 3377663 B1 EP3377663 B1 EP 3377663B1 EP 16784134 A EP16784134 A EP 16784134A EP 3377663 B1 EP3377663 B1 EP 3377663B1
Authority
EP
European Patent Office
Prior art keywords
nickel
copper
zinc alloy
manganese
alloy according
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
Application number
EP16784134.5A
Other languages
German (de)
French (fr)
Other versions
EP3377663A1 (en
Inventor
Susanne HÜTTNER
Timo ALLMENDINGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
Original Assignee
Wieland Werke AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Priority to PL16784134T priority Critical patent/PL3377663T3/en
Publication of EP3377663A1 publication Critical patent/EP3377663A1/en
Application granted granted Critical
Publication of EP3377663B1 publication Critical patent/EP3377663B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/02Alloys containing less than 50% by weight of each constituent containing copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/04Alloys containing less than 50% by weight of each constituent containing tin or lead
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/06Alloys containing less than 50% by weight of each constituent containing zinc
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/04Alloys based on copper with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing 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 invention relates to a copper-nickel-zinc alloy, in which ⁇ - and ⁇ -phase structure consisting of nickel, iron and manganese and / or nickel, cobalt and manganese mixed silicides are incorporated as spherical or ellipsoidal particles, and the use of such a copper-nickel-zinc alloy.
  • Alloys of copper, nickel and zinc are called nickel silver because of their silver-like colors. Commonly used alloys have between 47 and 64% by weight of copper and between 7 and 25% by weight of nickel. In turnable and drillable alloys usually lead up to 3 wt .-% lead are added as a chip breaker, in cast alloys even up to 9 wt .-%. The rest is zinc. As admixtures commercial nickel silver alloys may also contain 0.2 to 0.7 wt .-% manganese to reduce the Glühbrüchmaschine. Also, the manganese additive acts deoxidizing and desulfurizing.
  • Nickel-silver alloys such as CuNi12Zn24 or CuNi18Zn20, are used in the optical industry, among others, for the manufacture of spectacle hinges.
  • the progressive miniaturization of these products requires materials with higher strength.
  • these products have high demands on the quality of the surface.
  • Nickel silver alloys are also used to make jewelery and watch parts. These products are particularly demanding on the Quality of the surface.
  • Even when pulled, the material must have a glossy and polished surface that is free from defects such as grooves or voids.
  • the material must be very easy to machine and, if necessary, also be polishable.
  • the color of the material must not change during use. Very similar requirements apply to materials used in medical technology or for the production of musical instruments.
  • the publication JP 01177327 describes easily machinable nickel silver alloys with good hot and cold workability. These alloys consist of 6 to 15% Ni, 3 to 8% Mn, 0.1 to 2.5% Pb, 31 to 47% Zn, balance Cu with unavoidable impurities. Optionally, small amounts of Fe, Co, B, Si or P may be added to prevent grain growth on warming prior to hot working.
  • the invention has for its object to provide a copper-nickel-zinc alloy with improved surface quality with high strength.
  • the surface should already look like polished when pulled.
  • the alloy should have a good machinability and excellent color fastness.
  • the invention has for its object to provide a use for such a copper-nickel-zinc alloy.
  • the invention includes a copper-nickel-zinc alloy having the following composition in% by weight: Cu 46.0 to 51.0%, Ni 8.0 to 11.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.5%, Fe and / or Co each up to 0.8%, wherein the sum of Fe content and twice the Co content is at least 0.1 wt .-%, Residual Zn as well as unavoidable impurities, wherein in a microstructure consisting of ⁇ - and ⁇ -phase nickel-, iron- and manganese-containing and / or nickel, cobalt and manganese mixed silicides are incorporated as spherical or ellipsoidal particles.
  • the invention is based on the consideration that the structure of nickel silver materials by alloying of silicon is varied so that silicide precipitates are formed.
  • Silicides as intermetallic compounds have about 800 HV significantly higher hardness than the ⁇ and ⁇ phase of the matrix structure.
  • manganese is added to improve the cold and hot forming capacity and to increase the strength.
  • manganese acts deoxidizing and desulfurizing.
  • silicon forms mixed silicides of approximate composition predominantly between (Mn, Fe, Ni) 2 Si and (Mn, Fe, Ni) 3 Si.
  • mixed silicides of approximate composition (Mn, Co, Ni) x Si y , where x ⁇ y.
  • mixed silicides can be formed which contain both iron and cobalt in addition to manganese and nickel.
  • the mixed silicides are finely distributed as spherical or ellipsoidal particles in the matrix structure. The mean value of the volume-equivalent diameter of the particles is 0.5 to 2 ⁇ m.
  • the microstructure does not contain large-scale silicides, which therefore easily break out of the matrix structure. This advantageous property is achieved in the alloy according to the invention in particular by the low levels of manganese and iron or cobalt.
  • Both iron and cobalt act as nucleation sites for silicide formation, ie in the presence of iron and / or cobalt even small deviations from the thermodynamic equilibrium are sufficient, so that small precipitates are formed.
  • These precipitation nuclei which may also contain nickel in the present alloy composition, are finely distributed in the microstructure. They are further silicides, which now also contain manganese, preferably on. The low manganese content of the alloy limits the size of the individual silicides. Small amounts of iron and / or cobalt in Combination with a small amount of manganese are therefore the prerequisite for the formation of mixed silicides.
  • the minimum amount of iron or cobalt is defined by the fact that the sum of the iron content and twice the cobalt content is at least 0.1 wt .-%.
  • the copper-nickel-zinc alloy according to the invention has an excellent surface quality. Even when pulled, the surface of the material is very smooth, silvery shiny and free of visible defects. The surface looks like it's already polished. Thus, the surface of a semi-finished product produced by a forming process, such as a drawing or rolling process from an alloy according to the invention in many cases already meets the quality requirements of the final product. Further processing to improve the surface is no longer necessary.
  • the average roughness Ra of the surface of such a semifinished product is typically at most 0.2 ⁇ m. The average roughness Ra is determined over a measuring length of at least 4 mm.
  • the surface quality of the copper-nickel-zinc alloy according to the invention is at least as good as the materials previously used in the optics industry.
  • the strength of the copper-nickel-zinc alloy according to the invention is significantly higher than that of the materials used hitherto. This increase in strength allows the components to be made smaller and more filigree and thus meet the current design requirements.
  • the tensile strength of the copper-nickel-zinc alloy according to the invention is between 700 and 900 MPa, depending on the degree of deformation of the material. In the hard state, it is at least 800 MPa.
  • Workpieces made of a copper-nickel-zinc alloy according to the invention are characterized by a very high-quality surface and an attractive appearance, so that this alloy for the production of jewelry and watch parts are suitable. Furthermore, workpieces of a copper-nickel-zinc alloy according to the invention can be polished very well, whereby the visual impression of the workpiece can be further improved if necessary and the value of the product can be increased. Furthermore, the surface of the copper-nickel-zinc alloy according to the invention is readily coatable because of its excellent flatness.
  • the surface quality of a copper-nickel-zinc alloy according to the invention is significantly better than that of lead-containing copper-nickel-zinc alloys of similar composition.
  • a copper-nickel-zinc alloy according to the invention small amounts of lead of up to 0.1 wt .-% may be contained in the impurities, which are neither matrix effective nor have an influence on the formation of Mischsilicide.
  • the lead content of a copper-nickel-zinc alloy according to the invention is preferably at most 0.05% by weight.
  • a copper-nickel-zinc alloy according to the invention is particularly preferably lead-free.
  • Another advantage of a copper-nickel-zinc alloy according to the invention is its high zinc content of about 40 wt .-%. This makes the material cheaper than, for example, the nickel silver alloys CuNi12Zn24 or CuNi18Zn20.
  • a copper-nickel-zinc alloy according to the invention has a good machinability.
  • the alloy can be well formed both warm and cold. The production costs of semi-finished products and end products are thereby reduced.
  • the copper-nickel-zinc alloy according to the invention has a very good machinability, although it contains at most very small amounts of lead. Even at Pb levels well below the threshold of unavoidable impurities, a copper-nickel-zinc alloy of the invention is readily machinable.
  • the reasons for the good machinability of the alloy are the finely divided mixed silicides, which act as chip breakers.
  • either the Fe content or the Co content can be at least 0.1% by weight. This favors the formation of finely divided mixed silicides.
  • the copper-nickel-zinc alloy according to the invention may have the following composition [in% by weight]: Cu 47.5 to 49.5%, Ni 8.0 to 10.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.4%, Fe 0.2 to 0.8%, optionally up to 0.8% Co, Rest Zn as well as unavoidable impurities.
  • nickel-, iron- and manganese-containing mixed silicides may be incorporated as spherical or ellipsoidal particles in an ⁇ - and ⁇ -phase microstructure.
  • the selective alloying of iron produces very fine mixed silicides which have an advantageous effect on the surface quality of the material.
  • the copper-nickel-zinc alloy according to the invention may have the following composition [in% by weight]: Cu 47.5 to 49.5%, Ni 8.0 to 10.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.4%, Co 0.1 to 0.8%, optionally up to 0.8% Fe, Rest Zn as well as unavoidable impurities.
  • nickel-, cobalt- and manganese-containing mixed silicides may be incorporated as spherical or ellipsoidal particles in a microstructure consisting of ⁇ - and ⁇ -phase.
  • the deliberate alloying of cobalt produces mixed silicides which have an advantageous effect on the strength of the material with at the same time good surface quality.
  • a further aspect of the invention includes the use of an alloy according to the invention for the production of consumer goods with high demands on the surface quality such as jewelry, watch parts, eyeglass hinges, musical instruments or devices for medical technology. Due to the excellent surface quality of workpieces made of an alloy according to the invention, this is particularly suitable for the production of jewelry, watch parts and musical instruments. Also advantageous in these applications is the high color stability of the alloy. The color fastness follows from the high corrosion resistance of the alloy. Devices used in medical technology must be easy to clean. The smoother the surface of the devices, the easier it is to remove unwanted substances. The combination of good surface quality and high strength predestines the copper-nickel-zinc alloy according to the invention for the production of spectacle hinges.
  • Another aspect of the invention involves the use of an alloy according to the invention for the production of keys, locks, connectors or lead tips for ballpoint pens.
  • the advantageous properties of a copper-nickel-zinc alloy according to the invention with respect to workability, namely good formability and good machinability come into play.
  • the good corrosion resistance of the copper-nickel-zinc alloy according to the invention has an advantageous effect.
  • a copper-nickel-zinc alloy according to the invention and three comparative alloys were melted and poured into bolts. From the bolts, wires and rods with an outer diameter of 4 mm were produced by means of hot pressing and cold forming.
  • Table 1 shows the composition of the individual alloys in% by weight. Table 1: Composition of the individual alloys in% by weight Cu Ni Mn Si Fe pb Zn inventive alloy 48.5 9.5 0.4 0.2 0.5 ⁇ 0.05 rest Comparative sample 1 49.0 7.5 3.0 - - 3.0 rest Comparative sample 2 62.5 17.5 0.4 - - - rest Comparative sample 3 48.4 9.5 0.4 0.3 0.5 1.3 rest
  • Table 2 compares the values found on the samples. Table 2: Roughness measurements, data in ⁇ m measuring direction inventive alloy Comparative sample 1 Comparative sample 2 Comparative sample 3 Ra along 0,039 0,100 0.103 0.113 crosswise 0.174 0.315 0.182 0.317 March along 0.36 1.48 0.76 1.56 crosswise 0.99 1.81 1.47 1.91 Rmax along 0.49 2.03 1.15 2.16 crosswise 1.28 2.29 1.92 2.42 Rt along 0.56 2.05 1.15 2.17 crosswise 2.26 2.66 2.11 2.63
  • the measured values documented in Table 2 show that the surface of the inventive alloy has the lowest roughness or roughness depth in seven out of eight measured values.
  • the inventive alloy thus has the best surface quality in the drawn state.
  • the measured values determined on the inventive alloy are always lower than the measured values determined on the lead-containing comparative samples 1 and 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Adornments (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)

Description

Die Erfindung betrifft eine Kupfer-Nickel-Zink-Legierung, in deren aus α- und β-Phase bestehenden Gefüge nickel-, eisen- und manganhaltige und/oder nickel-, kobalt- und manganhaltige Mischsilicide als kugelförmige oder ellipsiodale Partikel eingelagert sind, sowie die Verwendung einer derartigen Kupfer-Nickel-Zink-Legierung.The invention relates to a copper-nickel-zinc alloy, in which α- and β-phase structure consisting of nickel, iron and manganese and / or nickel, cobalt and manganese mixed silicides are incorporated as spherical or ellipsoidal particles, and the use of such a copper-nickel-zinc alloy.

Legierungen aus Kupfer, Nickel und Zink werden wegen ihrer silberähnlichen Farben als Neusilber bezeichnet. Technisch gebräuchliche Legierungen haben zwischen 47 und 64 Gew.-% Kupfer und zwischen 7 und 25 Gew.-% Nickel. Bei dreh- und bohrfähigen Legierungen werden üblicherweise bis zu 3 Gew.-% Blei als Spanbrecher zugesetzt, bei Gusslegierungen sogar bis zu 9 Gew.-%. Der Rest ist Zink. Als Beimengungen können handelsübliche Neusilberlegierungen zudem 0,2 bis 0,7 Gew.-% Mangan enthalten, um die Glühbrüchigkeit zu vermindern. Auch wirkt der Manganzusatz desoxidierend und entschwefelnd.Alloys of copper, nickel and zinc are called nickel silver because of their silver-like colors. Commonly used alloys have between 47 and 64% by weight of copper and between 7 and 25% by weight of nickel. In turnable and drillable alloys usually lead up to 3 wt .-% lead are added as a chip breaker, in cast alloys even up to 9 wt .-%. The rest is zinc. As admixtures commercial nickel silver alloys may also contain 0.2 to 0.7 wt .-% manganese to reduce the Glühbrüchigkeit. Also, the manganese additive acts deoxidizing and desulfurizing.

Neusilberlegierungen, wie beispielsweise CuNi12Zn24 oder CuNi18Zn20, werden unter anderem in der Optikindustrie zur Herstellung von Brillenscharnieren verwendet. Die fortschreitende Miniaturisierung dieser Produkte erfordert Werkstoffe mit höherer Festigkeit. Darüber hinaus sind bei diesen Produkten hohe Anforderungen an die Qualität der Oberfläche gestellt.
Neusilberlegierungen werden auch zur Herstellung von Schmuck und Uhrenteilen verwendet. Bei diesen Produkten sind besonders hohe Anforderungen an die Qualität der Oberfläche gestellt. Der Werkstoff muss schon im gezogenen Zustand eine glänzende und wie poliert wirkende Oberfläche aufweisen, die frei von Fehlern, wie beispielsweise Riefen oder Lunkern ist. Ferner muss der Werkstoff sehr gut zerspanbar und bei Bedarf auch polierbar sein. Auch darf sich die Farbe des Werkstoffs während des Gebrauchs nicht ändern. Ganz ähnliche Anforderungen gelten für Werkstoffe, die in der Medizintechnik oder zur Herstellung von Musikinstrumenten eingesetzt werden.
Nickel-silver alloys, such as CuNi12Zn24 or CuNi18Zn20, are used in the optical industry, among others, for the manufacture of spectacle hinges. The progressive miniaturization of these products requires materials with higher strength. In addition, these products have high demands on the quality of the surface.
Nickel silver alloys are also used to make jewelery and watch parts. These products are particularly demanding on the Quality of the surface. Even when pulled, the material must have a glossy and polished surface that is free from defects such as grooves or voids. Furthermore, the material must be very easy to machine and, if necessary, also be polishable. Also, the color of the material must not change during use. Very similar requirements apply to materials used in medical technology or for the production of musical instruments.

Aus der Druckschrift DE 1 120 151 sind hochfeste Neusilber-Legierungen mit günstigen Eigenschaften bezüglich Gießbarkeit und Warmumformbarkeit bekannt. Diese Legierungen bestehen aus 0,01 bis 5 % Si, über 10 bis 30 % Ni, 45 bis 70 % Cu, 0,3 bis 5 % Mn, Rest mindestens 10 % Zink. Geringe Zusätze von Si dienen zur Desoxidation der Legierung und zur Verbesserung der Gießbarkeit. Der Manganzusatz hat die Aufgabe, die Zähigkeit und damit die Kaltverarbeitbarkeit der Legierung zu erhöhen, und er dient auch der Nickelersparnis. Wahlweise kann Mangan vollständig durch Aluminium, und Nickel teilweise durch Kobalt ersetzt werden. Das Zulegieren von Eisen soll vermieden werden, da Eisen die Korrosionsbeständigkeit der Legierung herabsetzt. Mit einem Mangangehalt von 1 % werden Festigkeitswerte von ca. 400 MPa erreicht. Zur Verbesserung der mechanischen Eigenschaften wird eine Wärmebehandlung vorgeschlagen.From the publication DE 1 120 151 are known high strength nickel silver alloys with favorable properties in terms of castability and hot workability. These alloys consist of 0.01 to 5% Si, about 10 to 30% Ni, 45 to 70% Cu, 0.3 to 5% Mn, balance at least 10% zinc. Small additions of Si serve to deoxidize the alloy and improve castability. The manganese addition has the task to increase the toughness and thus the cold workability of the alloy, and it also serves the nickel savings. Alternatively, manganese can be completely replaced by aluminum, and nickel in part by cobalt. The alloying of iron should be avoided as iron reduces the corrosion resistance of the alloy. With a manganese content of 1%, strength values of approx. 400 MPa are achieved. To improve the mechanical properties, a heat treatment is proposed.

Die Druckschrift JP 01177327 beschreibt leicht zerspanbare Neusilber-Legierungen mit guter Warm- und Kaltumformbarkeit. Diese Legierungen bestehen aus 6 bis 15 % Ni, 3 bis 8 % Mn, 0,1 bis 2,5 % Pb, 31 bis 47 % Zn, Rest Cu mit unvermeidbaren Verunreinigungen. Wahlweise können geringe Mengen an Fe, Co, B, Si oder P zugegeben werden, um das Kornwachstum beim Aufwärmen vor der Warmumformung zu verhindern.The publication JP 01177327 describes easily machinable nickel silver alloys with good hot and cold workability. These alloys consist of 6 to 15% Ni, 3 to 8% Mn, 0.1 to 2.5% Pb, 31 to 47% Zn, balance Cu with unavoidable impurities. Optionally, small amounts of Fe, Co, B, Si or P may be added to prevent grain growth on warming prior to hot working.

Aus der Druckschrift DE 10 2012 004 725 A1 sind bleihaltige Kupfer-Nickel-Zink-Legierungen bekannt, in deren Gefüge nickel-, eisen- und manganhaltige und/oder nickel-, kobalt- und manganhaltige Mischsilicide als kugelförmige oder ellipsiodale Partikel eingelagert sind. Die Legierungen zeichnen sich durch eine hohe Zugfestigkeit, ein großes Kaltumformvermögen und eine gute Zerspanbarkeit aus. Der Bleianteil von 1,0 bis 1,5 Gew.-% stellt die gute Zerspanbarkeit der Legierungen sicher. Die Legierungen dienen zur Herstellung von hochwertigen Minenspitzen für Kugelschreiber. Die Oberflächeneigenschaften des Werkstoffs sind für Anwendungen mit besonders hohen Anforderungen an die Oberflächenqualität nicht immer ausreichend.From the publication DE 10 2012 004 725 A1 are lead-containing copper-nickel-zinc alloys known in their structure nickel-, iron- and manganese-containing and / or nickel, cobalt and manganese mixed silicides are incorporated as spherical or ellipsoidal particles. The alloys are characterized by high tensile strength, high cold workability and good machinability. The lead content of 1.0 to 1.5 wt .-% ensures the good machinability of the alloys. The alloys are used to produce high quality lead tips for ballpoint pens. The surface properties of the material are not always sufficient for applications with particularly high surface quality requirements.

Der Erfindung liegt die Aufgabe zugrunde, eine Kupfer-Nickel-Zink-Legierung mit verbesserter Oberflächenqualität bei gleichzeitig hoher Festigkeit anzugeben. Die Oberfläche soll bereits im gezogenen Zustand wie poliert aussehen. Ferner soll die Legierung eine gute Zerspanbarkeit und eine hervorragende Farbbeständigkeit aufweisen. Des Weiteren liegt der Erfindung die Aufgabe zugrunde, eine Verwendung für eine derartige Kupfer-Nickel-Zink-Legierung anzugeben.The invention has for its object to provide a copper-nickel-zinc alloy with improved surface quality with high strength. The surface should already look like polished when pulled. Furthermore, the alloy should have a good machinability and excellent color fastness. Furthermore, the invention has for its object to provide a use for such a copper-nickel-zinc alloy.

Die Erfindung wird bezüglich einer Kupfer-Nickel-Zink-Legierung durch die Merkmale des Anspruchs 1 und bezüglich einer Verwendung durch die Merkmale der Ansprüche 4 und 5 wiedergegeben. Die weiteren rückbezogenen Ansprüche betreffen vorteilhafte Aus- und Weiterbildungen der Erfindung.The invention with respect to a copper-nickel-zinc alloy by the features of claim 1 and for use by the features of claims 4 and 5 reproduced. The other dependent claims relate to advantageous embodiments and further developments of the invention.

Die Erfindung schließt eine Kupfer-Nickel-Zink-Legierung mit folgender Zusammensetzung in Gewichts-% ein: Cu 46,0 bis 51,0 %, Ni 8,0 bis 11,0 %, Mn 0,2 bis 0,6 %, Si 0,05 bis 0,5 %, Fe und/oder Co jeweils bis zu 0,8 %, wobei die Summe aus Fe-Gehalt und dem Doppelten des Co-Gehalts mindestens 0,1 Gew.-% beträgt,
Rest Zn sowie unvermeidbare Verunreinigungen,
wobei in einem aus α- und β-Phase bestehenden Gefüge nickel-, eisen- und manganhaltige und/oder nickel-, kobalt- und manganhaltige Mischsilicide als kugelförmige oder ellipsoidale Partikel eingelagert sind.
The invention includes a copper-nickel-zinc alloy having the following composition in% by weight: Cu 46.0 to 51.0%, Ni 8.0 to 11.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.5%, Fe and / or Co each up to 0.8%, wherein the sum of Fe content and twice the Co content is at least 0.1 wt .-%,
Residual Zn as well as unavoidable impurities,
wherein in a microstructure consisting of α- and β-phase nickel-, iron- and manganese-containing and / or nickel, cobalt and manganese mixed silicides are incorporated as spherical or ellipsoidal particles.

Die Erfindung geht dabei von der Überlegung aus, dass das Gefüge von Neusilber-Werkstoffen durch Zulegieren von Silicium so variiert wird, dass Silicid-Ausscheidungen gebildet werden. Silicide als intermetallische Verbindungen besitzen mit ca. 800 HV eine deutlich höhere Härte als die α- und β-Phase des Matrixgefüges. Prinzipiell wird zur Verbesserung des Kalt- und Warmumformvermögens und zur Steigerung der Festigkeit Mangan zulegiert. Zudem wirkt Mangan desoxidierend und entschwefelnd. Silicium bildet bei gleichzeitiger Anwesenheit von Mangan, Eisen und Nickel Mischsilicide mit ungefähren Zusammensetzungen vorwiegend zwischen (Mn,Fe,Ni)2Si und (Mn,Fe,Ni)3Si. Analog bildet Silicium bei gleichzeitiger Anwesenheit von Mangan, Kobalt und Nickel Mischsilicide der ungefähren Zusammensetzungen (Mn,Co,Ni)xSiy, wobei x ≥ y. Ferner können auch Mischsilicide gebildet werden, die neben Mangan und Nickel sowohl Eisen als auch Kobalt enthalten. Die Mischsilicide liegen fein verteilt als kugelförmige oder ellipsoidale Partikel im Matrixgefüge vor. Der Mittelwert des volumenäquivalenten Durchmessers der Partikel beträgt 0,5 bis 2 µm. Das Gefüge enthält keine großflächigen und daher leicht aus dem Matrixgefüge heraus brechenden Silicide. Diese vorteilhafte Eigenschaft wird bei der erfindungsgemäßen Legierung insbesondere durch die geringen Anteile an Mangan und Eisen bzw. Kobalt erzielt. Sowohl Eisen als auch Kobalt wirken als Keimstellen für die Silicidbildung, d.h. bei Anwesenheit von Eisen und/oder Kobalt genügen bereits geringe Abweichungen vom thermodynamischen Gleichgewicht, so dass kleine Ausscheidungen entstehen. Diese Ausscheidungskeime, die bei der vorliegenden Legierungszusammensetzung auch Nickel enthalten können, sind im Gefüge fein verteilt. An sie lagern sich weitere Silicide, die nun auch Mangan enthalten, bevorzugt an. Durch den geringen Mangangehalt der Legierung wird die Größe der einzelnen Silicide begrenzt. Geringe Mengen an Eisen und/oder Kobalt in Kombination mit einer geringen Menge Mangan sind also die Voraussetzung für die Bildung der Mischsilicide. Die Mindestmenge an Eisen beziehungsweise Kobalt wird dadurch definiert, dass die Summe aus dem Eisengehalt und dem Doppelten des Kobaltgehalts mindestens 0,1 Gew.-% beträgt.The invention is based on the consideration that the structure of nickel silver materials by alloying of silicon is varied so that silicide precipitates are formed. Silicides as intermetallic compounds have about 800 HV significantly higher hardness than the α and β phase of the matrix structure. In principle, manganese is added to improve the cold and hot forming capacity and to increase the strength. In addition, manganese acts deoxidizing and desulfurizing. In the presence of manganese, iron and nickel, silicon forms mixed silicides of approximate composition predominantly between (Mn, Fe, Ni) 2 Si and (Mn, Fe, Ni) 3 Si. Similarly, silicon in the coexistence of manganese, cobalt and nickel forms mixed silicides of approximate composition (Mn, Co, Ni) x Si y , where x ≥ y. Furthermore, mixed silicides can be formed which contain both iron and cobalt in addition to manganese and nickel. The mixed silicides are finely distributed as spherical or ellipsoidal particles in the matrix structure. The mean value of the volume-equivalent diameter of the particles is 0.5 to 2 μm. The microstructure does not contain large-scale silicides, which therefore easily break out of the matrix structure. This advantageous property is achieved in the alloy according to the invention in particular by the low levels of manganese and iron or cobalt. Both iron and cobalt act as nucleation sites for silicide formation, ie in the presence of iron and / or cobalt even small deviations from the thermodynamic equilibrium are sufficient, so that small precipitates are formed. These precipitation nuclei, which may also contain nickel in the present alloy composition, are finely distributed in the microstructure. They are further silicides, which now also contain manganese, preferably on. The low manganese content of the alloy limits the size of the individual silicides. Small amounts of iron and / or cobalt in Combination with a small amount of manganese are therefore the prerequisite for the formation of mixed silicides. The minimum amount of iron or cobalt is defined by the fact that the sum of the iron content and twice the cobalt content is at least 0.1 wt .-%.

Überraschenderweise zeigt sich, dass die erfindungsgemäße Kupfer-Nickel-Zink-Legierung eine ausgezeichnete Oberflächenqualität aufweist. Bereits im gezogenen Zustand ist die Oberfläche des Werkstoffs sehr glatt, silbrig glänzend und frei von sichtbaren Fehlern. Die Oberfläche sieht aus, als wäre sie bereits poliert. Damit genügt die Oberfläche eines durch einen Umformprozess, wie beispielsweise einem Zieh- oder Walzprozess, aus einer erfindungsgemäßen Legierung hergestellten Halbzeugs in vielen Fällen bereits den Qualitätsanforderungen des Endprodukts. Eine weitere Bearbeitung zur Verbesserung der Oberfläche ist nicht mehr erforderlich. Die mittlere Rauheit Ra der Oberfläche eines derartigen Halbzeugs beträgt typischerweise höchstens 0,2 µm. Die mittlere Rauheit Ra wird dabei über eine Messlänge von mindestens 4 mm ermittelt.Surprisingly, it has been found that the copper-nickel-zinc alloy according to the invention has an excellent surface quality. Even when pulled, the surface of the material is very smooth, silvery shiny and free of visible defects. The surface looks like it's already polished. Thus, the surface of a semi-finished product produced by a forming process, such as a drawing or rolling process from an alloy according to the invention in many cases already meets the quality requirements of the final product. Further processing to improve the surface is no longer necessary. The average roughness Ra of the surface of such a semifinished product is typically at most 0.2 μm. The average roughness Ra is determined over a measuring length of at least 4 mm.

Die Oberflächenqualität der erfindungsgemäßen Kupfer-Nickel-Zink-Legierung ist mindestens so gut wie die bislang in der Optikindustrie eingesetzten Werkstoffe. Die Festigkeit der erfindungsgemäßen Kupfer-Nickel-Zink-Legierung ist jedoch deutlich höher als die der bislang verwendeten Werkstoffe. Diese Steigerung der Festigkeit erlaubt, die Bauteile kleiner und filigraner auszuführen und somit den aktuellen Design-Anforderungen gerecht zu werden. Die Zugfestigkeit der erfindungsgemäßen Kupfer-Nickel-Zink-Legierung liegt je nach Umformgrad des Werkstoffs zwischen 700 und 900 MPa. Im harten Zustand beträgt sie mindestens 800 MPa.The surface quality of the copper-nickel-zinc alloy according to the invention is at least as good as the materials previously used in the optics industry. However, the strength of the copper-nickel-zinc alloy according to the invention is significantly higher than that of the materials used hitherto. This increase in strength allows the components to be made smaller and more filigree and thus meet the current design requirements. The tensile strength of the copper-nickel-zinc alloy according to the invention is between 700 and 900 MPa, depending on the degree of deformation of the material. In the hard state, it is at least 800 MPa.

Werkstücke aus einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung zeichnen sich durch eine sehr hochwertige Oberfläche und ein ansprechendes Aussehen aus, so dass diese Legierung zur Herstellung von Schmuck und Uhrenteilen geeignet sind. Ferner lassen sich Werkstücke aus einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung sehr gut polieren, wodurch der optische Eindruck des Werkstücks bei Bedarf weiter verbessert und der Wert des Produkts gesteigert werden kann. Ferner ist die Oberfläche der erfindungsgemäßen Kupfer-Nickel-Zink-Legierung aufgrund ihrer hervorragenden Ebenheit gut beschichtbar.Workpieces made of a copper-nickel-zinc alloy according to the invention are characterized by a very high-quality surface and an attractive appearance, so that this alloy for the production of jewelry and watch parts are suitable. Furthermore, workpieces of a copper-nickel-zinc alloy according to the invention can be polished very well, whereby the visual impression of the workpiece can be further improved if necessary and the value of the product can be increased. Furthermore, the surface of the copper-nickel-zinc alloy according to the invention is readily coatable because of its excellent flatness.

Insbesondere ist die Oberflächenqualität einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung deutlich besser als die von bleihaltigen Kupfer-Nickel-Zink-Legierungen ähnlicher Zusammensetzung. Bei einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung können in den Verunreinigungen geringe Bleianteile von bis zu 0,1 Gew.-% enthalten sein, welche weder matrixwirksam sind noch einen Einfluss auf die Ausbildung der Mischsilicide haben. Bevorzugt beträgt der Bleianteil einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung höchstens 0,05 Gew.-%. Besonders bevorzugt ist eine erfindungsgemäße Kupfer-Nickel-Zink-Legierung bleifrei.In particular, the surface quality of a copper-nickel-zinc alloy according to the invention is significantly better than that of lead-containing copper-nickel-zinc alloys of similar composition. In a copper-nickel-zinc alloy according to the invention small amounts of lead of up to 0.1 wt .-% may be contained in the impurities, which are neither matrix effective nor have an influence on the formation of Mischsilicide. The lead content of a copper-nickel-zinc alloy according to the invention is preferably at most 0.05% by weight. A copper-nickel-zinc alloy according to the invention is particularly preferably lead-free.

Ein weiterer Vorteil einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung ist deren hoher Zink-Anteil von ungefähr 40 Gew.-%. Dies macht den Werkstoff preiswerter als beispielsweise die Neusilberlegierungen CuNi12Zn24 oder CuNi18Zn20.Another advantage of a copper-nickel-zinc alloy according to the invention is its high zinc content of about 40 wt .-%. This makes the material cheaper than, for example, the nickel silver alloys CuNi12Zn24 or CuNi18Zn20.

Darüber hinaus weist eine erfindungsgemäße Kupfer-Nickel-Zink-Legierung eine gute Bearbeitbarkeit auf. Die Legierung lässt sich sowohl warm als auch kalt gut umformen. Die Herstellkosten von Halbzeugen und Endprodukten werden dadurch reduziert. Insbesondere weist die erfindungsgemäße Kupfer-Nickel-Zink-Legierung eine sehr gute Zerspanbarkeit auf, obwohl sie höchstens sehr geringe Mengen an Blei enthält. Selbst bei Pb-Gehalten, die deutlich unter der Schwelle von unvermeidbaren Verunreinigungen liegen, ist eine erfindungsgemäße Kupfer-Nickel-Zink-Legierung gut zerspanbar. Ursache für die gute Zerspanbarkeit der Legierung sind die fein verteilten Mischsilicide, die als Spanbrecher wirken.Moreover, a copper-nickel-zinc alloy according to the invention has a good machinability. The alloy can be well formed both warm and cold. The production costs of semi-finished products and end products are thereby reduced. In particular, the copper-nickel-zinc alloy according to the invention has a very good machinability, although it contains at most very small amounts of lead. Even at Pb levels well below the threshold of unavoidable impurities, a copper-nickel-zinc alloy of the invention is readily machinable. The reasons for the good machinability of the alloy are the finely divided mixed silicides, which act as chip breakers.

Vorteilhafterweise kann entweder der Fe-Gehalt oder der Co-Gehalt mindestens 0,1 Gewichts-% betragen. Dies begünstigt die Ausbildung fein verteilter Mischsilicide.Advantageously, either the Fe content or the Co content can be at least 0.1% by weight. This favors the formation of finely divided mixed silicides.

In bevorzugter Ausgestaltung der Erfindung kann die erfindungsgemäße Kupfer-Nickel-Zink-Legierung folgende Zusammensetzung [in Gew.-%] aufweisen: Cu 47,5 bis 49,5 %, Ni 8,0 bis 10,0 %, Mn 0,2 bis 0,6 %, Si 0,05 bis 0,4 %, Fe 0,2 bis 0,8 %, wahlweise bis zu 0,8 % Co,
Rest Zn sowie unvermeidbare Verunreinigungen.
In a preferred embodiment of the invention, the copper-nickel-zinc alloy according to the invention may have the following composition [in% by weight]: Cu 47.5 to 49.5%, Ni 8.0 to 10.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.4%, Fe 0.2 to 0.8%, optionally up to 0.8% Co,
Rest Zn as well as unavoidable impurities.

Bei dieser Zusammensetzung können in einem aus α- und β-Phase bestehenden Gefüge nickel-, eisen- und manganhaltige Mischsilicide als kugelförmige oder ellipsiodale Partikel eingelagert sein. Durch das gezielte Zulegieren von Eisen werden sehr feine Mischsilicide gebildet, die sich vorteilhaft auf die Oberflächenqualität des Werkstoffs auswirken.In this composition, nickel-, iron- and manganese-containing mixed silicides may be incorporated as spherical or ellipsoidal particles in an α- and β-phase microstructure. The selective alloying of iron produces very fine mixed silicides which have an advantageous effect on the surface quality of the material.

Bei einer alternativen vorteilhaften Ausgestaltung der Erfindung kann die erfindungsgemäße Kupfer-Nickel-Zink-Legierung folgende Zusammensetzung [in Gew.-%] aufweisen: Cu 47,5 bis 49,5 %, Ni 8,0 bis 10,0 %, Mn 0,2 bis 0,6 %, Si 0,05 bis 0,4 %, Co 0,1 bis 0,8 %, wahlweise bis zu 0,8 % Fe,
Rest Zn sowie unvermeidbare Verunreinigungen.
In an alternative advantageous embodiment of the invention, the copper-nickel-zinc alloy according to the invention may have the following composition [in% by weight]: Cu 47.5 to 49.5%, Ni 8.0 to 10.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.4%, Co 0.1 to 0.8%, optionally up to 0.8% Fe,
Rest Zn as well as unavoidable impurities.

Bei dieser Zusammensetzung können in einem aus α- und β-Phase bestehenden Gefüge nickel-, kobalt- und manganhaltige Mischsilicide als kugelförmige oder ellipsiodale Partikel eingelagert sein. Durch das gezielte Zulegieren von Kobalt werden Mischsilicide gebildet, die sich vorteilhaft auf die Festigkeit des Werkstoffs bei gleichzeitig guter Oberflächenqualität auswirken.In this composition, nickel-, cobalt- and manganese-containing mixed silicides may be incorporated as spherical or ellipsoidal particles in a microstructure consisting of α- and β-phase. The deliberate alloying of cobalt produces mixed silicides which have an advantageous effect on the strength of the material with at the same time good surface quality.

Ein weiterer Aspekt der Erfindung schließt die Verwendung einer erfindungsgemäßen Legierung zur Herstellung von Konsumgütern mit hohen Anforderungen an die Oberflächenqualität wie beispielsweise Schmuck, Uhrenteilen, Brillenscharnieren, Musikinstrumenten oder Geräten für die Medizintechnik ein. Aufgrund der ausgezeichneten Oberflächenqualität von Werkstücken aus einer erfindungsgemäßen Legierung eignet sich diese besonders zur Herstellung von Schmuck, Uhrenteilen und Musikinstrumenten. Vorteilhaft ist in diesen Anwendungen auch die hohe Farbbeständigkeit der Legierung. Die Farbbeständigkeit folgt aus der hohen Korrosionsbeständigkeit der Legierung. Geräte, die in der Medizintechnik eingesetzt werden, müssen gut zu reinigen sein. Je glatter die Oberfläche der Geräte ist, desto leichter können unerwünschte Substanzen entfernt werden. Die Kombination aus guter Oberflächenqualität und hoher Festigkeit prädestiniert die erfindungsgemäße Kupfer-Nickel-Zink-Legierung für die Herstellung von Brillenscharnieren.A further aspect of the invention includes the use of an alloy according to the invention for the production of consumer goods with high demands on the surface quality such as jewelry, watch parts, eyeglass hinges, musical instruments or devices for medical technology. Due to the excellent surface quality of workpieces made of an alloy according to the invention, this is particularly suitable for the production of jewelry, watch parts and musical instruments. Also advantageous in these applications is the high color stability of the alloy. The color fastness follows from the high corrosion resistance of the alloy. Devices used in medical technology must be easy to clean. The smoother the surface of the devices, the easier it is to remove unwanted substances. The combination of good surface quality and high strength predestines the copper-nickel-zinc alloy according to the invention for the production of spectacle hinges.

Ein weiterer Aspekt der Erfindung schließt die Verwendung einer erfindungsgemäßen Legierung zur Herstellung von Schlüsseln, Schlössern, Steckverbindern oder Minenspitzen für Kugelschreiber ein. Bei der Herstellung von Gebrauchsgegenständen wie Schlüsseln oder Schlössern kommen die vorteilhaften Eigenschaften einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung bezüglich Bearbeitbarkeit, nämlich gute Umformbarkeit und gute Zerspanbarkeit, zum Tragen. Gleiches gilt für die Verwendung einer erfindungsgemäßen Kupfer-Nickel-Zink-Legierung als Steckverbinder, die aus einem Profil, einer Stange oder einem Rohr durch Zerspanung hergestellt werden. Bei der Verwendung als Minenspitze für Kugelschreiber wirkt sich darüber hinaus die gute Korrosionsbeständigkeit der erfindungsgemäßen Kupfer-Nickel-Zink-Legierung vorteilhaft aus.Another aspect of the invention involves the use of an alloy according to the invention for the production of keys, locks, connectors or lead tips for ballpoint pens. In the production of commodities such as keys or locks, the advantageous properties of a copper-nickel-zinc alloy according to the invention with respect to workability, namely good formability and good machinability, come into play. The same applies to the use of a copper-nickel-zinc alloy according to the invention as connectors made from a profile, rod or tube by machining. When used as a lead tip for ballpoint moreover, the good corrosion resistance of the copper-nickel-zinc alloy according to the invention has an advantageous effect.

Die Erfindung wird anhand eines Ausführungsbeispiels näher erläutert.The invention will be explained in more detail with reference to an embodiment.

Eine erfindungsgemäße Kupfer-Nickel-Zink-Legierung sowie drei Vergleichslegierungen wurden erschmolzen und zu Bolzen abgegossen. Aus den Bolzen wurden mittels Warmpressen und Kaltumformungen Drähte und Stangen mit einem Außendurchmesser von 4 mm hergestellt. Tabelle 1 zeigt die Zusammensetzung der einzelnen Legierungen in Gew.-%. Tabelle 1: Zusammensetzung der einzelnen Legierungen in Gew.-% Cu Ni Mn Si Fe Pb Zn erfinderische Legierung 48,5 9,5 0,4 0,2 0,5 < 0,05 Rest Vergleichsprobe 1 49,0 7,5 3,0 - - 3,0 Rest Vergleichsprobe 2 62,5 17,5 0,4 - - - Rest Vergleichsprobe 3 48,4 9,5 0,4 0,3 0,5 1,3 Rest A copper-nickel-zinc alloy according to the invention and three comparative alloys were melted and poured into bolts. From the bolts, wires and rods with an outer diameter of 4 mm were produced by means of hot pressing and cold forming. Table 1 shows the composition of the individual alloys in% by weight. Table 1: Composition of the individual alloys in% by weight Cu Ni Mn Si Fe pb Zn inventive alloy 48.5 9.5 0.4 0.2 0.5 <0.05 rest Comparative sample 1 49.0 7.5 3.0 - - 3.0 rest Comparative sample 2 62.5 17.5 0.4 - - - rest Comparative sample 3 48.4 9.5 0.4 0.3 0.5 1.3 rest

An den gezogenen Drähten wurden Rauheitsmessungen durchgeführt. Folgende Kennwerte wurden über eine Messlänge von 4 mm jeweils längs und quer zur Ziehrichtung ermittelt:

Ra
mittlere Rauheit
Rz
gemittelte Rautiefe
Rmax
maximale Rautiefe
Rt
Gesamthöhe des Profils
Roughness measurements were made on the drawn wires. The following characteristic values were determined over a measuring length of 4 mm in each case longitudinally and transversely to the drawing direction:
Ra
average roughness
March
average roughness
Rmax
maximum roughness
Rt
Total height of the profile

Tabelle 2 stellt die an den Proben ermittelten Werte einander gegenüber. Tabelle 2: Rauheitsmesswerte, Angaben in µm Messrichtung erfinderische Legierung Vergleichsprobe 1 Vergleichsprobe 2 Vergleichsprobe 3 Ra längs 0,039 0,100 0,103 0,113 quer 0,174 0,315 0,182 0,317 Rz längs 0,36 1,48 0,76 1,56 quer 0,99 1,81 1,47 1,91 Rmax längs 0,49 2,03 1,15 2,16 quer 1,28 2,29 1,92 2,42 Rt längs 0,56 2,05 1,15 2,17 quer 2,26 2,66 2,11 2,63 Table 2 compares the values found on the samples. Table 2: Roughness measurements, data in μm measuring direction inventive alloy Comparative sample 1 Comparative sample 2 Comparative sample 3 Ra along 0,039 0,100 0.103 0.113 crosswise 0.174 0.315 0.182 0.317 March along 0.36 1.48 0.76 1.56 crosswise 0.99 1.81 1.47 1.91 Rmax along 0.49 2.03 1.15 2.16 crosswise 1.28 2.29 1.92 2.42 Rt along 0.56 2.05 1.15 2.17 crosswise 2.26 2.66 2.11 2.63

Die in Tabelle 2 dokumentierten Messwerte zeigen, dass die Oberfläche der erfinderischen Legierung bei sieben von acht Messwerten die geringste Rauheit beziehungsweise Rautiefe aufweist. Die erfinderische Legierung besitzt also im gezogenen Zustand die beste Oberflächenqualität. Insbesondere sind die an der erfinderischen Legierung ermittelten Messwerte stets geringer als die an den bleihaltigen Vergleichsproben 1 und 3 ermittelten Messwerte.The measured values documented in Table 2 show that the surface of the inventive alloy has the lowest roughness or roughness depth in seven out of eight measured values. The inventive alloy thus has the best surface quality in the drawn state. In particular, the measured values determined on the inventive alloy are always lower than the measured values determined on the lead-containing comparative samples 1 and 3.

An den vier Proben wurden Zerspanungsversuche durchgeführt. Hierzu wurde in die Drähte eine achsparallele Zentralbohrung mit Innendurchmesser von 2 mm eingebracht. Die erfindungsgemäße Legierung sowie die beiden bleihaltigen Vergleichsproben 1 und 3 ließen sich ohne Probleme zerspanen. Die Bohrspäne waren fein. Die bleifreie Vergleichsprobe 2 wurde beim Bohrversuch sehr heiß und der Bohrer brach während des Versuchs ab.
An Proben einer erfindungsgemäßen Legierung mit einer Zusammensetzung gemäß Tabelle 1 wurden die in Tabelle 3 dokumentieren mechanischen Eigenschaften ermittelt: Tabelle 3: Mechanische Eigenschaften einer erfindungsgemäßen Legierung Zugfestigkeit Rm Streckgrenze Rp0,2 Bruchdehnung A10 Rundstange Durchmesser 8 mm 735 MPa 561 MPa 11% Runddraht Durchmesser 2,5 mm 835 MPa 619 MPa 12%
Cutting tests were carried out on the four samples. For this purpose, an axially parallel central bore with an inner diameter of 2 mm was inserted into the wires. The alloy according to the invention and the two lead-containing comparative samples 1 and 3 could be machined without problems. The drill chips were fine. The lead-free control 2 became very hot during the trial and the drill broke off during the trial.
The mechanical properties documented in Table 3 were determined on samples of an alloy according to the invention having a composition according to Table 1: Table 3: Mechanical properties of an alloy according to the invention Tensile strength R m Yield strength R p0.2 Elongation at break A 10 Round bar diameter 8 mm 735 MPa 561 MPa 11% Round wire diameter 2.5 mm 835 MPa 619 MPa 12%

Die Versuche zeigen, dass eine Kupfer-Nickel-Zink-Legierung gemäß der Erfindung in vorteilhafter Weise Eigenschaften vereint, wie sie in dieser Kombination bei aus dem Stand der Technik bekannten Legierungen nicht zu finden sind.The experiments show that a copper-nickel-zinc alloy according to the invention advantageously combines properties which are not found in this combination in alloys known from the prior art.

Claims (5)

  1. Copper/nickel/zinc alloy having the following composition [in % by weight]:
    Cu 46.0 to 51.0%,
    Ni 8.0 to 11.0%,
    Mn 0.2 to 0.6%,
    Si 0.05 to 0.5%,
    Fe and/or Co up to 0.8%, respectively,
    wherein the sum of Fe content and double the Co content is at least 0.1%,
    balance Zn and inevitable impurities,
    wherein nickel-, iron- and manganese-containing and/or
    nickel-, cobalt- and manganese-containing mixed silicides are embedded as spherical or ellipsoidal particles in a structure comprising α phase and β phase.
  2. Copper/nickel/zinc alloy according to claim 1 having the following composition [in % by weight]:
    Cu 47.5 to 49.5%,
    Ni 8.0 to 10.0%,
    Mn 0.2 to 0.6%,
    Si 0.05 to 0.4%,
    Fe 0.2 to 0.8%,
    optionally up to 0.8% Co,
    balance Zn and inevitable impurities,
    wherein nickel-, iron- and manganese-containing mixed silicides are embedded as spherical or ellipsoidal particles in a structure comprising α phase and β phase.
  3. Copper/nickel/zinc alloy according to claim 1 having the following composition [in % by weight]:
    Cu 47.5 to 49.5%,
    Ni 8.0 to 10.0%,
    Mn 0.2 to 0.6%,
    Si 0.05 to 0.4%,
    Co 0.1 to 0.8%,
    optionally up to 0.8% Fe,
    balance Zn and inevitable impurities,
    wherein nickel-, cobalt- and manganese-containing mixed silicides are embedded as spherical or ellipsoidal particles in a structure comprising α phase and β phase.
  4. Use of a copper/nickel/zinc alloy according to any one of claims 1 to 3 for producing consumer goods having high levels of requirement with regard to the surface quality.
  5. Use of a copper/nickel/zinc alloy according to any one of claims 1 to 3 for producing keys, locks, plug-type connectors or refill tips for ballpoint pens.
EP16784134.5A 2015-11-17 2016-10-12 Copper-nickel-zinc alloy and use thereof Active EP3377663B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL16784134T PL3377663T3 (en) 2015-11-17 2016-10-12 Copper-nickel-zinc alloy and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015014856.7A DE102015014856A1 (en) 2015-11-17 2015-11-17 Copper-nickel-zinc alloy and its use
PCT/EP2016/001697 WO2017084731A1 (en) 2015-11-17 2016-10-12 Copper-nickel-zinc alloy and use thereof

Publications (2)

Publication Number Publication Date
EP3377663A1 EP3377663A1 (en) 2018-09-26
EP3377663B1 true EP3377663B1 (en) 2019-11-20

Family

ID=57153441

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16784134.5A Active EP3377663B1 (en) 2015-11-17 2016-10-12 Copper-nickel-zinc alloy and use thereof

Country Status (9)

Country Link
US (1) US10808303B2 (en)
EP (1) EP3377663B1 (en)
JP (1) JP6615334B2 (en)
CN (1) CN108350552B (en)
DE (1) DE102015014856A1 (en)
MY (1) MY185851A (en)
PL (1) PL3377663T3 (en)
TW (1) TWI694163B (en)
WO (1) WO2017084731A1 (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018003216B4 (en) 2018-04-20 2020-04-16 Wieland-Werke Ag Copper-zinc-nickel-manganese alloy
CN111380782B (en) * 2019-05-25 2023-07-28 郑州普湾医疗技术有限公司 Sensor alloy suspension wire and thromboelastography instrument with same
CN112030056A (en) * 2020-08-31 2020-12-04 江苏腾征新材料研究院有限公司 Composite spherical energy-containing alloy damaged element and manufacturing method thereof
EP3971312A1 (en) * 2020-09-17 2022-03-23 Société BIC Brass alloy for writing instrument tips
CN113403500B (en) * 2021-06-21 2022-04-22 宁波博威合金材料股份有限公司 High-strength high-elasticity corrosion-resistant high-nickel-manganese-white copper alloy and preparation method and application thereof
KR102403909B1 (en) * 2021-10-26 2022-06-02 주식회사 풍산 Method for preparing copper alloy material with excellent workability and machinability and copper alloy material prepared thereby
CN114606411B (en) * 2022-04-21 2022-09-16 宁波金田铜业(集团)股份有限公司 Free-cutting cupronickel

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1120151B (en) 1954-04-26 1961-12-21 Dr Eugen Vaders High-strength nickel silver alloy
DE1205285B (en) 1962-12-28 1965-11-18 Ver Deutsche Metallwerke Ag Use of manganese and silicon-containing copper alloys for items subject to wear and tear
DE3309365C1 (en) * 1983-03-16 1983-12-15 Vacuumschmelze Gmbh, 6450 Hanau Use of a hardenable copper-nickel-manganese alloy as a material for the manufacture of spectacle parts
US4631171A (en) * 1985-05-16 1986-12-23 Handy & Harman Copper-zinc-manganese-nickel alloys
DE3735783C1 (en) * 1987-10-22 1989-06-15 Diehl Gmbh & Co Use of a copper-zinc alloy
JPH01177327A (en) * 1988-01-06 1989-07-13 Sanpo Shindo Kogyo Kk Free cutting copper-based alloy showing silver-white
JPH0368732A (en) * 1989-08-08 1991-03-25 Nippon Mining Co Ltd Manufacture of copper alloy and copper alloy material for radiator plate
JPH03111529A (en) * 1989-09-26 1991-05-13 Nippon Mining Co Ltd High-strength and heat-resistant spring copper alloy
DE4240157A1 (en) 1992-11-30 1994-06-01 Chuetsu Metal Works Brass-alloy coated synchroniser ring surface - exhibits good wear-resistance and adhesion, said synchroniser rings for use in gears of high performance vehicles.
DE4339426C2 (en) 1993-11-18 1999-07-01 Diehl Stiftung & Co Copper-zinc alloy
JPH07166279A (en) * 1993-12-09 1995-06-27 Kobe Steel Ltd Copper-base alloy excellent in corrosion resistance, punchability, and machinability and production thereof
JPH10121169A (en) * 1996-10-15 1998-05-12 Mitsubishi Materials Corp Copper alloy resistance wire for electrofusion joint
JPH111735A (en) * 1997-04-14 1999-01-06 Mitsubishi Shindoh Co Ltd High strength cu alloy with excellent press blankability and corrosion resistance
JP3022488B2 (en) 1997-06-04 2000-03-21 社団法人高等技術研究院研究組合 Resistance spot welding quality control device
DE102005015467C5 (en) 2005-04-04 2024-02-29 Diehl Brass Solutions Stiftung & Co. Kg Using a copper-zinc alloy
DE102009021336B9 (en) * 2009-05-14 2024-04-04 Wieland-Werke Ag Copper-nickel-zinc alloy and its use
TW201100564A (en) * 2009-06-26 2011-01-01 Chan Wen Copper Industry Co Ltd Lead free copper zinc alloy
JP5281031B2 (en) * 2010-03-31 2013-09-04 Jx日鉱日石金属株式会社 Cu-Ni-Si alloy with excellent bending workability
DE102012004725B4 (en) 2012-03-07 2018-07-19 Wieland-Werke Ag Silicon-containing copper-nickel-zinc alloy
DE102013008822A1 (en) * 2013-05-24 2014-11-27 Wieland-Werke Ag Mine for pens and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP2018538431A (en) 2018-12-27
WO2017084731A1 (en) 2017-05-26
CN108350552B (en) 2020-07-31
JP6615334B2 (en) 2019-12-04
US10808303B2 (en) 2020-10-20
MY185851A (en) 2021-06-14
PL3377663T3 (en) 2020-05-18
DE102015014856A1 (en) 2017-05-18
TW201732047A (en) 2017-09-16
EP3377663A1 (en) 2018-09-26
CN108350552A (en) 2018-07-31
US20180291484A1 (en) 2018-10-11
TWI694163B (en) 2020-05-21

Similar Documents

Publication Publication Date Title
EP3377663B1 (en) Copper-nickel-zinc alloy and use thereof
DE102009021336B4 (en) Copper-nickel-zinc alloy and its use
EP3004413B1 (en) Refill for a ball-point pen and use thereof
DE102009048450A1 (en) High ductile and high-strength magnesium alloys
EP0545231B1 (en) Application of a copper-manganese-zinc alloy for spectacle frames
DE69224138T2 (en) Gold alloys of exceptionally beautiful yellow color and with reversible hardening properties
DE19756815C2 (en) Wrought copper alloy, process for producing a semi-finished product therefrom and its use
EP2823077B1 (en) Copper-nickel-zinc alloy containing silicon
DE3854682T2 (en) Iron-copper-chromium alloy for a high-strength lead frame or a pin grid and process for their production.
EP3075870B1 (en) Copper-zinc alloy, strip material made from this alloy, method for producing a semifinished product made from this alloy and sliding element made from this alloy
EP3992320A1 (en) Lead-free cu-zn alloy
EP0621346B1 (en) Use of a copper-zinc alloy for making nickel-free consumer articles
DE202017103901U1 (en) Special brass alloy as well as special brass alloy product
EP3992319A1 (en) Alloy product made of a lead-free copper-zinc alloy and method for producing the same
DE1092218B (en) Process for the production of hardened objects from copper-nickel-manganese-zinc alloys
WO2009059736A1 (en) Platinum alloy for jewelry
DE670570C (en) Aluminum alloy
DE763758C (en) Use of aluminum alloys for pressed and rolled products
WO2022096276A1 (en) Brass alloy
DE531693C (en) Process for the production of aluminum with high electrical conductivity and great strength
DE3518021A1 (en) COATED MATERIAL FOR ORNAMENTAL USE
DE69429193T2 (en) COMPOSITION OF A SILVER ALLOY
EP3274481B1 (en) Copper-zinc alloy and use thereof
EP3992318A1 (en) Alloy product made of a lead-free copper-zinc alloy and method for producing the same
DE1558624B1 (en) COPPER ALLOY WITH IMPROVED STRENGTH AND ELONGATION

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180424

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190619

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

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

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: 502016007669

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOHEST AG, CH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1204272

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191215

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20191120

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: 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: 20191120

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: 20191120

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: 20200221

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: 20200220

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: 20191120

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: 20191120

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: 20191120

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: 20200220

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

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: 20191120

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: 20200320

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: 20191120

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: 20191120

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: 20200412

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: 20191120

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: 20191120

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: 20191120

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: 20191120

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: 20191120

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502016007669

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

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: 20191120

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: 20191120

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: 20200821

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: 20191120

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201012

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: 20191120

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201031

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: 20201031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201012

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: 20201012

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: 20191120

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: 20191120

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: 20191120

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191120

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230913

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230911

Year of fee payment: 8

Ref country code: PL

Payment date: 20230830

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20230925

Year of fee payment: 8

Ref country code: CH

Payment date: 20231102

Year of fee payment: 8

Ref country code: DE

Payment date: 20231031

Year of fee payment: 8