EP1749897B1 - Process including annealing for producing water-bearing copper cast parts with lowered tendency of migration - Google Patents
Process including annealing for producing water-bearing copper cast parts with lowered tendency of migration Download PDFInfo
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- EP1749897B1 EP1749897B1 EP05016381A EP05016381A EP1749897B1 EP 1749897 B1 EP1749897 B1 EP 1749897B1 EP 05016381 A EP05016381 A EP 05016381A EP 05016381 A EP05016381 A EP 05016381A EP 1749897 B1 EP1749897 B1 EP 1749897B1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Definitions
- the present invention relates to a process for the production of water-bearing components of a drinking water installation with a reduced tendency to migrate.
- the present invention particularly relates to fittings and fittings that come into contact with the guided in the water pipes drinking water.
- the Drinking Water Ordinance limits the maximum permissible metal ions in drinking water, in particular with regard to copper, lead, nickel and arsenic ions. These ions can be originally contained in drinking water. In addition, a migration from the metallic components into the drinking water can take place. The higher the proportion of the ions originally contained in the drinking water, the higher the requirements for the components of the drinking water pipeline with regard to migration.
- DIN 50930-6 of August 2001 regulates the influence of dissolved metallic metal ions on drinking water conditions and restricts the permissible upper limits of alloying elements of fittings and fittings made of copper alloy in order to minimize their migration into the drinking water. Nevertheless, today's components in drinking water installations, for the production of which copper alloys are used, exhibit a certain migration of copper, zinc, tin, lead, nickel and arsenic and so the experts endeavor to propose suitable measures with which the migration of metal ions into the water can be further reduced without the benefits of to dispense with metallic components for drinking water installation.
- the GB-1 443 090 discloses a dezincification-enhanced copper alloy having between 80 and 90 weight percent copper, between 6.3 and 17.5 weight percent zinc and between 2.8 and 4.75 weight percent silicon as essential alloying ingredients between 0.03 and 0.05% by weight of arsenic.
- 443,090 proposed a heat treatment of the cast parts. In this heat treatment, the cast parts are annealed at temperatures between 600 ° C and 750 ° C for a period of 5 to 10 days and then quenched. This heat treatment is carried out with the aim of obtaining the alpha and zeta phase to be preferred in view of the corrosion. By quenching in particular the formation of phases is to be avoided, the corrosion resistance is low, so the ⁇ - and ⁇ -phase.
- the EP 0 147 592 discloses the production of brass extrusions from brass castings.
- the brass parts are forged and after a heat treatment with a cooling rate of 0.8 K / sec. cooled per second. As a result, a component for a water-bearing pipeline with high strength to be created.
- the present invention has for its object to provide a method for producing water-bearing components of a drinking water installation, which show a reduced tendency to migrate metal ions in the drinking water.
- the present invention further specifies a component of a drinking water installation with improved migration values.
- the present invention provides a method having the features of claim 1.
- the casting which is in particular a fitting or a fitting, is made by casting a copper alloy containing at least 80% by weight of copper.
- This copper alloy may be a copper-tin casting alloy (tin bronze), a copper-tin-zinc casting alloy (gunmetal) or a copper-silicon-zinc casting alloy (silicon bronze), wherein manganese, phosphorus and / or Arsenic can be added.
- the copper-tin casting alloys those alloys having up to 12% by weight of tin and up to 5% by weight of lead are preferred. The latter is added to improve the workability, in particular the machinability.
- silicon bronzes preferred are those having a silicon content of not more than 4.5 wt%, a tin content of not more than 8 wt%, and a manganese content of not more than 1 wt%.
- These well-known copper alloys are cast to form a casting, for example in sand, mold or centrifugal casting. This is followed by a heat treatment of the casting at between 400 ° C and 800 ° C for at least one half a hour. This heat treatment is carried out at a temperature interval of between 400 and 800 ° C, preferably at an interval of 650 to 700 ° C.
- the annealing time should be limited to 36 hours. Particularly preferred are annealing times of between 2 and 16 hours. The heating phase is not included in these annealing times.
- the aforementioned annealing treatment takes place after forming. If a hot forming process is used here, the remaining heat of the formed component can be used as the initial heat of the annealing treatment.
- a surface of the material which is as clean as possible it is proposed according to a preferred embodiment of the present invention to carry out the annealing treatment in an annealing atmosphere which contains nitrogen, hydrogen and / or argon.
- an annealing atmosphere which contains nitrogen, hydrogen and / or argon.
- a mixture of the three gases mentioned is used.
- the alloys used in the process are preferably limited to the specific values given for the following alloy constituents: Pb ⁇ 3.0% by weight; Ni ⁇ 2.0 wt%, P ⁇ 0.04 wt%.
- As unavoidable impurities are allowed: Fe ⁇ 0.5 wt .-%; S ⁇ 0.05 wt%; Sb ⁇ 0.2 wt%; As ⁇ 0.03 wt%.
- the specified upper limits should preferably be observed for the following elements or impurities: Al ⁇ 0.01 wt .-% ; Fe ⁇ 0.5% by weight, more preferably Fe ⁇ 0.15% by weight; Mn ⁇ 0.20 wt%; Se ⁇ 0.1 wt%, more preferably ⁇ 0.05 wt%; Sb ⁇ 0.2 wt%; Si ⁇ 0.01 wt .-%.
- the zinc content should be ⁇ 0.5 wt .-%; in a copper-tin-zinc alloy, zinc is preferably provided in a proportion of between 7 and 10% by weight.
- the aforementioned preferred limits for Fe, Mn, S, Sb and Pb apply, preferably in the same way.
- the silicon content is preferably between 0.01 and 5.0% by weight. This proportion of silicon can be replaced in whole or in part by an aluminum content.
- the following limit values are further preferably specified for the elements mentioned below.
- the alloy constituents more than 80% by weight of copper and furthermore unavoidable impurities in copper alloys are otherwise contained.
- unavoidable impurities the following elements can be tolerated with the following upper limits (in% by weight): Al: 0.01%; Sb: 0.1%; As: 0.03%; Bi: 0.02%; Cd: 0.02%; Cr: 0.02%; Fe: 0.3%; Si: 0.01%.
- copper alloys which are particularly suitable for carrying out the method according to the invention. These include first the copper-tin alloys, for example CuSn12 with not more than 2 wt .-% nickel, not more than 0.6 wt .-% phosphorus, not more than 0.7 wt .-% lead and between 11 and 13 wt% tin as the major alloying elements with copper between 85 and 88.5 wt%.
- copper-tin alloys for example CuSn12 with not more than 2 wt .-% nickel, not more than 0.6 wt .-% phosphorus, not more than 0.7 wt .-% lead and between 11 and 13 wt% tin as the major alloying elements with copper between 85 and 88.5 wt%.
- impurities aluminum and silicon each with up to 0.01 wt .-%, iron and manganese with up to 0.2 wt .-%, sulfur with up to 0.05 wt .-%, antimony with up to
- a CuSn12Ni2 alloy can be used which contains as essential alloying constituents between 1.5 and 2.5% by weight of nickel, between 11 and 13% by weight of tin and between 84 and 87.5% by weight of copper , Phosphorus may be included at up to 0.05% by weight.
- Other possible unavoidable impurities are Aluminum and silicon in each case up to 0.01 wt .-%, iron and manganese with 0.2 wt .-%, lead with 0.3 wt .-%, sulfur with 0.05 wt .-%, antimony with 0 , 1 wt .-% and zinc containing not more than 0.4 wt .-%.
- the former alloy contains, as essential alloy constituents, lead with between 2.5 and 6.0% by weight, tin with between 2.0 and 3.5% by weight and zinc with between 7.5 and 10.0% by weight. %, wherein the copper content is between 81 and 86 wt .-%.
- phosphorus can be contained with up to 0.05 wt .-%.
- Further unavoidable impurities are aluminum with up to 0.01% by weight and silicon with up to 0.01% by weight. Iron may be present at up to 0.5% by weight, sulfur at up to 0.1% by weight, and antimony at up to 0.3% by weight.
- the CuSn5Zn5Pb5 alloy contains between 4.0 and 6.0 wt% lead, 4.0 and 6.0 wt% tin, and 4.0 to 6.5 wt% zinc.
- Phosphorus may be included at up to 0.1% by weight.
- the nickel content can be up to 2 wt .-%.
- Possible further impurities may be aluminum or silicon, each with a weight fraction of 0.1% by weight.
- Iron may be contained in the alloy at 0.3% by weight, sulfur at 0.1% by weight and antimony at up to 0.25% by weight. Copper is contained in a proportion by weight of 83 to 87%.
- the alloy CuSn7Zn2Pb3 As another possible alloy with a copper content of between 85 and 89 wt .-%, the alloy CuSn7Zn2Pb3 called. This contains as further essential alloy constituents between 2.5 and 3.5 wt .-% lead, between 6.0 and 8.0 wt .-% tin and between 1.5 and 3.2 wt .-% zinc. Further, nickel may be contained at up to 2.0% by weight and phosphorus at up to 0.1% by weight. As impurities, aluminum and silicon may each be contained at up to 0.01% by weight, iron at up to 0.2% by weight, antimony at up to 0.25% by weight and sulfur at up to 0, 10% by weight.
- CuSn7Zn4Pb7 is to be mentioned with a copper content of between 81 and 85 wt .-% and between 5.2 and 8.0 wt .-% lead, 6, 0 and 8.0 wt .-% tin and between 2.0 and 5 wt .-% zinc.
- alloying components are Nickel containing up to 2.0% by weight and phosphorus containing up to 0.10% by weight in the alloy.
- aluminum and silicon at 0.01% by weight may be contained as impurities, respectively.
- the amount of iron is limited to 0.2%.
- Sulfur may be present at up to 0.1% by weight, antimony at up to 0.3% by weight.
- the alloy CuSn6Zn4Pb2 which contained between 86 and 90% by weight of copper, 1.0 and 2.0% of lead, 5.5 and 6.5% by weight of tin and 3.0, was also found to be suitable and 5.0 wt% zinc.
- Other alloying constituents may be nickel at not more than 1.0% by weight and phosphorus at not more than 0.05% by weight.
- unavoidable impurities are permitted: aluminum with not more than 0.01 wt .-%, iron is 0.25 wt .-%, the proportion of sulfur to 0.1 wt .-% and the proportion of antimony to 0, 25 wt .-% limited. Silicon may eventually interfere with the proportion of aluminum, i. containing up to 0.01%.
- copper-tin alloys such as CuSn10 with between 88.5 and 90.5 wt .-% copper and tin with between 9 and 11 wt .-% as necessary alloying constituents and with up to 2 wt. -% nickel, with up to 0.2 wt .-% phosphorus and up to 1.0 wt .-% lead.
- aluminum may be contained at up to 0.01% by weight, iron at up to 0.2% by weight, manganese at up to 0.1% by weight, sulfur at up to 0.05% by weight. -%, antimony with up to 0.2 wt .-%, silicon with up to 0.02 wt .-% and zinc with up to 0.5 wt .-%.
- the alloy CuSn11P which contains between 10 and 11.5% by weight of tin and between 0.5 and 1.0% by weight of phosphorus and between 87% by weight and 89.5% by weight. Contains% Cu as necessary alloying constituents.
- the impurities may be aluminum and silicon, each containing up to 0.01% by weight, iron and nickel each containing up to 0.1% by weight, manganese, sulfur and antimony each having up to 0.05% by weight. % and lead with up to 0.25 wt .-%.
- the alloy CuSn11Pb2 has proven to be suitable for carrying out the process base material consisting of between 83.5 and 87.0 wt .-% copper and between 0.7 and 2.5 wt .-% lead and between 10.5 and Contains 12.5 wt .-% tin as necessary alloying constituents.
- Nickel can with up to 2.0 wt .-%, phosphorus with up to 0.4% by weight and zinc with up to 2.0% by weight.
- the aluminum content should be limited to a content of 0.01 wt%. Equally, the proportion of silicon in the alloy should also be limited.
- Manganese and antimony can each be contained at 0.2% by weight, as well as iron. Sulfur is tolerated up to 0.08% by weight.
- the measurement curve with the square black symbols as support points was determined by means of a cast sample prepared according to the method according to the invention and subsequently annealed.
- Support points with triangular symbols are the measurement results of a conventional cast sample of the same material without annealing.
- the rhombus line shows the limit value according to the Drinking Water Ordinance (TrinkwV).
- FIG. 1 shows the copper release in mg / l in the migration test. After a start-up time, a copper release of less than 1000 ⁇ g / l appears in the sample according to the invention, which drops to a level of less than 500 ⁇ g / l after a test duration of more than 26 weeks.
- the values of the conventional sample are about twice as high and are significantly higher even after a test period of 26 weeks.
- FIG. 2 shows the lead delivery in ⁇ g / l.
- a very high lead levy appears, which decreases sharply after a trial period of a few weeks.
- the lead release of the sample according to the invention is below 5 ⁇ g / l, whereas the conventional sample shows a lead release of slightly above 5 ⁇ g / l.
- FIG. 3 shows the nickel release of the same sample, specifically in ⁇ g / l as a function of the duration of the experiment. Again, after an initial phase, a significant increase in the conventional sample to about 15 ug / l. At the same time point (12 weeks test duration), the nickel release of the sample according to the invention is about 5 ⁇ g / l and, after a test duration of more than 18 weeks, enters a range of less than 5 ⁇ g / l.
- the lead output can be reduced by adding a smaller amount of lead to the cast alloy. This measure will be taken in particular when it does not depend on machining properties.
- FIG. 4 shows a typical structure of a cast component made from a gunmetal alloy after casting (FIG. 4.1) and after the annealing treatment at 700 ° C. over the duration of 5 hours at two different points of the sample on the basis of two representations of different magnifications (FIG 4.2 and 4.3).
- FIG. 5 shows corresponding sections of a gunmetal sample after an annealing treatment at 700 ° C. for 13 hours.
- a clear, combed structure is shown in relation to the cast structure (left representations), whereby the dendritic formation of the cast structure can still occasionally be recognized within the grain boundaries.
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von wasserführenden Bauteilen einer Trinkwasserinstallation mit verminderter Migrationsneigung. Die vorliegende Erfindung betrifft insbesondere Fittings und Armaturen, die mit dem in den Wasserleitungen geführten Trinkwasser in Kontakt kommen.The present invention relates to a process for the production of water-bearing components of a drinking water installation with a reduced tendency to migrate. The present invention particularly relates to fittings and fittings that come into contact with the guided in the water pipes drinking water.
Heutzutage werden Rohrleitungssysteme mit wasserführenden Rohren - sofern diese aus einem metallischen Werkstoff hergestellt sind - insbesondere Trinkwasserrohren in Gebäuden aus Edelstahl oder Kupfer hergestellt. Andere metallische Werkstoffe kommen aufgrund der Korrosionsproblematik nicht ernsthaft in Betracht. Geläufig sind Kupferlegierungen zur Herstellung von Bauteilen in Trinkwasserinstallationen, insbesondere Messing und Rotguss. Diese Kupferlegierungen zeigen zwar hinreichend gute Korrosionsbeständigkeit bei einem dauerhaften Einsatz in Wasser-, insbesondere Trinkwasserleitungen. Sie werden aber nicht immer den heute erwarteten Anforderungen gerecht. Diese werden insbesondere durch die novellierte Trinkwasserverordnung vom 21. Mai 2001 gesetzt, welche deutlich verminderte Toleranzwerte für die Abgabe von Metallionen an das Trinkwasser vorschreibt. Die Trinkwasserverordnung limitiert die maximal zulässigen Metallionen im Trinkwasser, insbesondere in Bezug auf Kupfer-, Blei-, Nickel- und Arsen-lonen. Diese Ionen können originär im Trinkwasser enthalten sein. Zusätzlich kann eine Migration aus den metallischen Bauteilen in das Trinkwasser erfolgen. Je höher der Anteil der originär in dem Trinkwasser enthaltenen Ionen ist, desto höher sind die Anforderungen an die Bauteile der Trinkwasserleitung in Bezug auf Migration.Today piping systems with water-bearing pipes - if they are made of a metallic material - in particular drinking water pipes in buildings made of stainless steel or copper. Other metallic materials are not seriously considered due to the corrosion problem. Common are copper alloys for the production of components in drinking water installations, in particular brass and gunmetal. Although these copper alloys show sufficiently good corrosion resistance in a permanent use in water, especially drinking water pipes. However, they do not always meet the requirements expected today. These are set in particular by the amended Drinking Water Ordinance of May 21, 2001, which requires significantly reduced tolerance values for the delivery of metal ions to the drinking water. The Drinking Water Ordinance limits the maximum permissible metal ions in drinking water, in particular with regard to copper, lead, nickel and arsenic ions. These ions can be originally contained in drinking water. In addition, a migration from the metallic components into the drinking water can take place. The higher the proportion of the ions originally contained in the drinking water, the higher the requirements for the components of the drinking water pipeline with regard to migration.
Die DIN 50930-6 vom August 2001 regelt die Beeinflussung der Trinkwasserbeschaffenheit durch gelöste metallische Metall-lonen und schränkt die zulässigen Obergrenzen von Legierungselementen von Fittings und Armaturen aus Kupferlegierung ein, um deren Migration in das Trinkwasser zu minimieren. Dennoch weisen heutige Bauteile in Trinkwasserinstallationen, zu deren Herstellung Kupferlegierungen verwendet werden, eine gewisse Migration von Kupfer, Zink, Zinn, Blei, Nickel und Arsen auf und so bemüht sich die Fachwelt, geeignete Maßnahmen vorzuschlagen, mit denen die Migration von Metallionen in das Wasser weiter vermindert werden kann, ohne auf die Vorteile von metallischen Bauteilen für die Trinkwasserinstallation verzichten zu müssen.DIN 50930-6 of August 2001 regulates the influence of dissolved metallic metal ions on drinking water conditions and restricts the permissible upper limits of alloying elements of fittings and fittings made of copper alloy in order to minimize their migration into the drinking water. Nevertheless, today's components in drinking water installations, for the production of which copper alloys are used, exhibit a certain migration of copper, zinc, tin, lead, nickel and arsenic and so the experts endeavor to propose suitable measures with which the migration of metal ions into the water can be further reduced without the benefits of to dispense with metallic components for drinking water installation.
Übliche Vertreter von Bronze-Guss-Legierungen sind in DIN EN 1982 zusammengestellt. Beispielhaft soll hier die Rotguss-Legierung CuSn5Zn5Pb5 mit jeweils zwischen 4 bis 6 Gew.-% Zinn, Zink und Blei bei einem Gehalt von bis zu 2,0 Gew.-% Nickel und bis zu 0,1 Gew.-% Phosphor sowie als Beimengungen bis zu 0,3 Gew.-% Eisen und bis zu 0,25 Gew.-% Antimon genannt werden. Dieser Werkstoff zeichnet sich zwar durch eine gute Gießbarkeit sowie Korrosionsbeständigkeit auch gegenüber Meerwasser aus. Hinsichtlich der Abgabe von Metallionen in das Wasser muss dieser Werkstoff indes vor dem Hintergrund der künftig zu erwartenden Grenzwerte als nicht zufriedenstellend angesehen werden. Zu bemängeln ist insbesondere der hohe Bleigehalt von CuSn5Zn5Pb5.Conventional representatives of bronze casting alloys are compiled in DIN EN 1982. By way of example, the gun metal alloy CuSn5Zn5Pb5 with in each case between 4 to 6 wt .-% tin, zinc and lead at a level of up to 2.0 wt .-% nickel and up to 0.1 wt .-% phosphorus and as Admixtures up to 0.3 wt .-% iron and up to 0.25 wt .-% antimony are called. Although this material is characterized by good castability and corrosion resistance to seawater. With regard to the release of metal ions into the water, however, this material must be regarded as unsatisfactory against the background of the future expected limit values. In particular, the high lead content of CuSn5Zn5Pb5 is to be criticized.
Die
Die
Neben der aus der vorerwähnten Britischen Offenlegungsschrift bekannten Siliziumbronze ist bereits aus der
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von wasserführenden Bauteilen einer Trinkwasserinstallation anzugeben, welche eine verminderte Neigung zur Migration von Metallionen in das Trinkwasser zeigen. Mit der vorliegenden Erfindung wird ferner ein Bauteil einer Trinkwasserinstallation mit verbesserten Migrationswerten angegeben.The present invention has for its object to provide a method for producing water-bearing components of a drinking water installation, which show a reduced tendency to migrate metal ions in the drinking water. The present invention further specifies a component of a drinking water installation with improved migration values.
Zur Lösung des verfahrensmäßigen Problems wird mit der vorliegenden Erfindung ein Verfahren mit den Merkmalen von Anspruch 1 angegeben. Nach dem erfindungsgemäßen Verfahren wird das Gussteil, welches insbesondere eine Armatur oder ein Fitting ist, durch Vergießen einer Kupferlegierung hergestellt, die wenigstens 80 Gew.-% Kupfer enthält. Bei dieser Kupferlegierung kann es sich um eine Kupfer-Zinn-Gusslegierung (Zinnbronze), eine Kupfer-Zinn-Zink-Gusslegierung (Rotguss) oder eine Kupfer-Silizium-Zink-Gusslegierung (Siliziumbronze) handeln, wobei auch Mangan, Phosphor und/oder Arsen zulegiert sein können. Bevorzugt ist insbesondere Rotguss gemäß DIN 50930-6 mit einem Blei-Gehalt von nicht mehr als 3 Gew.-% und einem Nickel-Gehalt von nicht mehr als 0,6 Gew.-%, insbesondere mit einem Anteil von 3,8 bis 4,5 Gew.-% Zinn, 5,5 bis 6,5 Gew.-% Zink, 2,5 bis 3 Gew.-% Blei und 0,2 bis 0,6 Gew.-% Nickel und als Rest Kupfer und unvermeidbare Begleitelemente bzw. Verunreinigungen, wie Arsen, Eisen, Phosphor und Schwefel. Unter den Kupfer-Zinn-Gusslegierungen werden solche Legierungen bevorzugt, die bis zu 12 Gew.-% Zinn und bis zu 5 Gew.-% Blei haben. Letzteres wird zur Verbesserung der Bearbeitbarkeit, insbesondere der Zerspanbarkeit beigegeben. Unter den Silizium-Bronzen werden solche Werkstoffe bevorzugt, die einen Siliziumgehalt von nicht mehr als 4,5 Gew.-%, einen Zinngehalt von nicht mehr als 8 Gew.-% und einen Mangangehalt von nicht mehr als 1 Gew.-% haben.To solve the procedural problem, the present invention provides a method having the features of claim 1. According to the method of the invention, the casting, which is in particular a fitting or a fitting, is made by casting a copper alloy containing at least 80% by weight of copper. This copper alloy may be a copper-tin casting alloy (tin bronze), a copper-tin-zinc casting alloy (gunmetal) or a copper-silicon-zinc casting alloy (silicon bronze), wherein manganese, phosphorus and / or Arsenic can be added. In particular, red brass according to DIN 50930-6 with a lead content of not more than 3% by weight and a nickel content of not more than 0.6% by weight, in particular with a content of from 3.8 to 4, is preferred , 5% by weight of tin, 5.5 to 6.5% by weight of zinc, 2.5 to 3% by weight of lead and 0.2 to 0.6% by weight of nickel and the remainder being copper and unavoidable Accompanying elements or impurities, such as arsenic, iron, phosphorus and sulfur. Among the copper-tin casting alloys, those alloys having up to 12% by weight of tin and up to 5% by weight of lead are preferred. The latter is added to improve the workability, in particular the machinability. Among the silicon bronzes, preferred are those having a silicon content of not more than 4.5 wt%, a tin content of not more than 8 wt%, and a manganese content of not more than 1 wt%.
Diese allgemein bekannten Kupferlegierungen werden zur Ausbildung eines Gussteils gegossen, beispielsweise im Sand-, Kokillen- oder Schleuderguss. Danach erfolgt eine Wärmebehandlung des Gussteils bei zwischen 400°C und 800°C für mindestens eine halbe Stunde. Diese Wärmebehandlung wird in einem Temperaturintervall von zwischen 400 und 800°C, bevorzugt in einem Intervall von 650 bis 700°C durchgeführt. Aus wirtschaftlichen Gründen sollte die Glühzeit auf 36 Stunden begrenzt sein. Besonders bevorzugt sind Glühzeiten von zwischen 2 und 16 Stunden. Die Aufheizphase ist in diese Glühzeiten nicht einbezogen.These well-known copper alloys are cast to form a casting, for example in sand, mold or centrifugal casting. This is followed by a heat treatment of the casting at between 400 ° C and 800 ° C for at least one half a hour. This heat treatment is carried out at a temperature interval of between 400 and 800 ° C, preferably at an interval of 650 to 700 ° C. For economic reasons, the annealing time should be limited to 36 hours. Particularly preferred are annealing times of between 2 and 16 hours. The heating phase is not included in these annealing times.
Nach dieser Wärmebehandlung erfolgt in Abkehr von dem Lösungsvorschlag nach der
Sofern wasserführende Bauteile aus den genannten Kupferlegierungen mittels Umformen hergestellt werden, erfolgt die vorerwähnte Glühbehandlung nach dem Umformen. Sofern ein Warmumformverfahren hierbei zur Anwendung kommt, kann die verbleibende Wärme des umgeformten Bauteils als Anfangswärme der Glühbehandlung genutzt werden.If water-bearing components are produced from said copper alloys by means of forming, the aforementioned annealing treatment takes place after forming. If a hot forming process is used here, the remaining heat of the formed component can be used as the initial heat of the annealing treatment.
Im Hinblick auf eine möglichst saubere Materialoberfläche wird gemäß einer bevorzugten Ausgestaltung der vorliegenden Erfindung vorgeschlagen, die Glühbehandlung in einer Glühatmosphäre durchzuführen, die Stickstoff, Wasserstoff und/oder Argon enthält. Vorzugsweise wird eine Mischung aus den drei genannten Gasen verwendet.With regard to a surface of the material which is as clean as possible, it is proposed according to a preferred embodiment of the present invention to carry out the annealing treatment in an annealing atmosphere which contains nitrogen, hydrogen and / or argon. Preferably, a mixture of the three gases mentioned is used.
Die in dem Verfahren zur Anwendung kommenden Legierungen sind vorzugsweise hinsichtlich folgender Legierungsbestandteile auf die im einzelnen angegebenen Werte beschränkt: Pb ≤ 3,0 Gew.-%; Ni ≤ 2,0 Gew.-%, P ≤ 0,04 Gew.-%. Als unvermeidbare Verunreinigungen sind zugelassen: Fe ≤ 0,5 Gew.-%; S ≤ 0,05 Gew.-%; Sb ≤ 0,2 Gew.-%; As ≤ 0,03 Gew.-%.The alloys used in the process are preferably limited to the specific values given for the following alloy constituents: Pb ≤ 3.0% by weight; Ni ≤ 2.0 wt%, P ≤ 0.04 wt%. As unavoidable impurities are allowed: Fe ≤ 0.5 wt .-%; S ≤ 0.05 wt%; Sb ≤ 0.2 wt%; As ≦ 0.03 wt%.
Bei der Verwendung einer Kupfer-Zinn-Legierung, wie auch bei der Verwendung einer Kupfer-Zinn-Zink-Legierung sollten vorzugsweise für die nachfolgend angegebenen Elemente bzw. Verunreinigungen die im einzelnen angegebenen Obergrenzen eingehalten werden: Al ≤ 0,01 Gew.-%; Fe ≤ 0,5 Gew.-%, besonders bevorzugt Fe ≤ 0,15 Gew.-%; Mn ≤ 0,20 Gew.-%; Se ≤ 0,1 Gew.-%, besonders bevorzugt ≤ 0,05 Gew.-%; Sb ≤ 0,2 Gew.-%; Si ≤ 0,01 Gew.-%. Bei Verwendung einer Kupfer-Zinn-Legierung sollte der Zink-Gehalt < 0,5 Gew.-% sein; bei einer Kupfer-Zinn-Zink-Legierung ist Zink vorzugsweise mit einem Anteil von zwischen 7 und 10 Gew.-% vorgesehen.When using a copper-tin alloy, as well as when using a copper-tin-zinc alloy, the specified upper limits should preferably be observed for the following elements or impurities: Al ≦ 0.01 wt .-% ; Fe ≦ 0.5% by weight, more preferably Fe ≦ 0.15% by weight; Mn ≤ 0.20 wt%; Se ≤ 0.1 wt%, more preferably ≤ 0.05 wt%; Sb ≤ 0.2 wt%; Si ≤ 0.01 wt .-%. When using a copper-tin alloy, the zinc content should be <0.5 wt .-%; in a copper-tin-zinc alloy, zinc is preferably provided in a proportion of between 7 and 10% by weight.
Bei Verwendung einer Kupfer-Silizium-Zink-Legierung gelten die vorerwähnten bevorzugten Grenzwerte für Fe, Mn, S, Sb und Pb, vorzugsweise in gleicher Weise. Bei der Kupfer-Silizium-Zink-Legierung liegt der Silizium-Gehalt vorzugsweise zwischen 0,01 und 5,0 Gew.-%. Dieser Anteil an Silizium kann ganz oder teilweise durch einen Aluminium-Anteil ersetzt werden. Für die Kupfer-Silizium-Zink-Legierung werden weiter bevorzugt folgende Grenzwerte für die nachfolgend genannten Elemente angegeben.When using a copper-silicon-zinc alloy, the aforementioned preferred limits for Fe, Mn, S, Sb and Pb apply, preferably in the same way. In the case of the copper-silicon-zinc alloy, the silicon content is preferably between 0.01 and 5.0% by weight. This proportion of silicon can be replaced in whole or in part by an aluminum content. For the copper-silicon-zinc alloy, the following limit values are further preferably specified for the elements mentioned below.
Neben den vorstehend ausdrücklich genannten Elementen sind ansonsten nur die Legierungsbestandteile, mehr als 80 Gew.-% Kupfer und darüber hinaus unvermeidbare Verunreinigungen in Kupfer-Legierungen enthalten. Als unvermeidbare Verunreinigungen können folgende Elemente mit folgenden Obergrenzen (in Gew.-%) toleriert werden: Al: 0,01%; Sb: 0,1%; As: 0,03%; Bi: 0,02%; Cd: 0,02%; Cr:0,02%; Fe: 0,3%; Si:0,01%.Apart from the elements expressly mentioned above, only the alloy constituents, more than 80% by weight of copper and furthermore unavoidable impurities in copper alloys are otherwise contained. As unavoidable impurities, the following elements can be tolerated with the following upper limits (in% by weight): Al: 0.01%; Sb: 0.1%; As: 0.03%; Bi: 0.02%; Cd: 0.02%; Cr: 0.02%; Fe: 0.3%; Si: 0.01%.
Nachfolgend werden einige Kupfer-Legierungen angegeben, die sich besonders zur Durchführung des erfindungsgemäßen Verfahrens eignen. Zu diesen gehören zunächst die Kupfer-Zinn-Legierungen, beispielsweise CuSn12 mit nicht mehr als 2 Gew.-% Nickel, nicht mehr als 0,6 Gew.-% Phosphor, nicht mehr als 0,7 Gew.-% Blei und zwischen 11 und 13 Gew.-% Zinn als wesentliche Legierungselemente mit Kupfer zwischen 85 und 88,5 Gew.-%. Zusätzlich können als Verunreinigungen Aluminium und Silizium mit jeweils bis zu 0,01 Gew.-%, Eisen und Mangan mit bis zu 0,2 Gew.-%, Schwefel mit bis zu 0,05 Gew.-%, Antimon mit bis zu 0,15 Gew.-% und Zink mit bis zu 0,5 Gew.-% enthalten sein.Below are some copper alloys specified, which are particularly suitable for carrying out the method according to the invention. These include first the copper-tin alloys, for example CuSn12 with not more than 2 wt .-% nickel, not more than 0.6 wt .-% phosphorus, not more than 0.7 wt .-% lead and between 11 and 13 wt% tin as the major alloying elements with copper between 85 and 88.5 wt%. In addition, as impurities aluminum and silicon each with up to 0.01 wt .-%, iron and manganese with up to 0.2 wt .-%, sulfur with up to 0.05 wt .-%, antimony with up to 0 , 15% by weight and zinc containing up to 0.5% by weight.
Alternativ kann eine CuSn12Ni2-Legierung zum Einsatz kommen, die als wesentliche Legierungsbestandteile zwischen 1,5 und 2,5 Gew.-% Nickel, zwischen 11 und 13 Gew.-% Zinn und zwischen 84 und 87,5 Gew.-% Kupfer enthält. Phosphor kann mit bis zu 0,05 Gew.-% enthalten sein. Weitere mögliche unvermeidbare Verunreinigungen sind Aluminium und Silizium jeweils bis zu 0,01 Gew.-%, Eisen und Mangan mit jeweils 0,2 Gew.-%, Blei mit 0,3 Gew.-%, Schwefel mit 0,05 Gew.-%, Antimon mit 0,1 Gew.-% und Zink mit nicht mehr als 0,4 Gew.-% enthalten.Alternatively, a CuSn12Ni2 alloy can be used which contains as essential alloying constituents between 1.5 and 2.5% by weight of nickel, between 11 and 13% by weight of tin and between 84 and 87.5% by weight of copper , Phosphorus may be included at up to 0.05% by weight. Other possible unavoidable impurities are Aluminum and silicon in each case up to 0.01 wt .-%, iron and manganese with 0.2 wt .-%, lead with 0.3 wt .-%, sulfur with 0.05 wt .-%, antimony with 0 , 1 wt .-% and zinc containing not more than 0.4 wt .-%.
Als weiterer Vertreter einer Kupfer-Zinn-Blei-Legierung seien CuSn3Zn8Pb5 bzw. CuSn5Zn5Pb5 genannt. Die erstgenannte Legierung enthält als wesentliche Legierungsbestandteile Blei mit zwischen 2,5 und 6,0 Gew.-%, Zinn mit zwischen 2,0 und 3,5 Gew.-% und Zink mit zwischen 7,5 und 10,0 Gew.-%, wobei der Kupferanteil zwischen 81 und 86 Gew.-% liegt. Weiterhin kann Phosphor mit bis zu 0,05 Gew.-% enthalten sein. Weitere unvermeidbare Verunreinigungen sind Aluminium mit bis zu 0,01 Gew.-% bzw. Silizium mit bis zu 0,01 Gew.-%. Eisen kann mit bis zu 0,5 Gew.-% enthalten sein, Schwefel mit bis zu 0,1 Gew.-% und Antimon mit bis zu 0,3 Gew.-%.Another representative of a copper-tin-lead alloy is CuSn3Zn8Pb5 or CuSn5Zn5Pb5. The former alloy contains, as essential alloy constituents, lead with between 2.5 and 6.0% by weight, tin with between 2.0 and 3.5% by weight and zinc with between 7.5 and 10.0% by weight. %, wherein the copper content is between 81 and 86 wt .-%. Furthermore, phosphorus can be contained with up to 0.05 wt .-%. Further unavoidable impurities are aluminum with up to 0.01% by weight and silicon with up to 0.01% by weight. Iron may be present at up to 0.5% by weight, sulfur at up to 0.1% by weight, and antimony at up to 0.3% by weight.
Die CuSn5Zn5Pb5 Legierung enthält zwischen 4,0 und 6,0 Gew.-% Blei, 4,0 und 6,0 Gew.-% Zinn und 4,0 bis 6,5 Gew.-% Zink. Phosphor kann mit bis zu 0,1 Gew.-% enthalten sein. Der Nickelgehalt kann bis 2 Gew.-% betragen. Als mögliche weitere Verunreinigungen können Aluminium oder Silizium mit jeweils einem Gewichtsanteil von 0,1 Gew.-% enthalten sein. Eisen kann mit 0,3 Gew.-%, Schwefel mit 0,1 Gew.-% und Antimon mit bis zu 0,25 Gew.-% in der Legierung enthalten sein. Kupfer ist mit einem Gewichtsanteil von 83 bis 87% enthalten.The CuSn5Zn5Pb5 alloy contains between 4.0 and 6.0 wt% lead, 4.0 and 6.0 wt% tin, and 4.0 to 6.5 wt% zinc. Phosphorus may be included at up to 0.1% by weight. The nickel content can be up to 2 wt .-%. Possible further impurities may be aluminum or silicon, each with a weight fraction of 0.1% by weight. Iron may be contained in the alloy at 0.3% by weight, sulfur at 0.1% by weight and antimony at up to 0.25% by weight. Copper is contained in a proportion by weight of 83 to 87%.
Als weitere mögliche Legierung mit einem Kupferanteil von zwischen 85 und 89 Gew.-% wird die Legierung CuSn7Zn2Pb3 genannt. Diese enthält als weitere wesentliche Legierungsbestandteile zwischen 2,5 und 3,5 Gew.-% Blei, zwischen 6,0 und 8,0 Gew.-% Zinn und zwischen 1,5 und 3,2 Gew.-% Zink. Ferner können Nickel mit bis zu 2,0 Gew.-% und Phosphor mit bis zu 0,1 Gew.-% enthalten sein. Als Verunreinigungen können Aluminium und Silizium jeweils mit bis zu 0,01 Gew.-% enthalten sein, Eisen mit bis zu 0,2 Gew.-% , Antimon mit bis zu 0,25 Gew.-% und Schwefel mit bis zu 0,10 Gew.-%.As another possible alloy with a copper content of between 85 and 89 wt .-%, the alloy CuSn7Zn2Pb3 called. This contains as further essential alloy constituents between 2.5 and 3.5 wt .-% lead, between 6.0 and 8.0 wt .-% tin and between 1.5 and 3.2 wt .-% zinc. Further, nickel may be contained at up to 2.0% by weight and phosphorus at up to 0.1% by weight. As impurities, aluminum and silicon may each be contained at up to 0.01% by weight, iron at up to 0.2% by weight, antimony at up to 0.25% by weight and sulfur at up to 0, 10% by weight.
Als weitere Kupfer-Zinn-Bleilegierung, die mit dem erfindungsgemäßen Verfahren verarbeitet werden kann, ist CuSn7Zn4Pb7 zu nennen mit einem Kupfergehalt von zwischen 81 und 85 Gew.-% und zwischen 5,2 und 8,0 Gew.-% Blei, 6,0 und 8,0 Gew.-% Zinn und zwischen 2,0 und 5 Gew.-% Zink. Als weitere mögliche Legierungsbestandteile sind Nickel mit bis zu 2,0 Gew.-% und Phosphor mit bis zu 0,10 Gew.-% in der Legierung enthalten. Darüber hinaus können als Verunreinigungen jeweils Aluminium und Silizium mit 0,01 Gew.-% enthalten sein. Der Anteil an Eisen ist auf 0,2% beschränkt. Schwefel kann mit bis zu 0,1 Gew.-% enthalten sein, Antimon mit bis zu 0,3 Gew.-%.As a further copper-tin-lead alloy, which can be processed by the method according to the invention, CuSn7Zn4Pb7 is to be mentioned with a copper content of between 81 and 85 wt .-% and between 5.2 and 8.0 wt .-% lead, 6, 0 and 8.0 wt .-% tin and between 2.0 and 5 wt .-% zinc. As further possible alloying components are Nickel containing up to 2.0% by weight and phosphorus containing up to 0.10% by weight in the alloy. In addition, aluminum and silicon at 0.01% by weight may be contained as impurities, respectively. The amount of iron is limited to 0.2%. Sulfur may be present at up to 0.1% by weight, antimony at up to 0.3% by weight.
Anhand von Versuchen konnte ferner die Legierung CuSn6Zn4Pb2 als geeignet ermittelt werden, die zwischen 86 und 90 Gew.-% Kupfer, 1,0 und 2,0% Blei, 5,5 und 6,5 Gew.-% Zinn und 3,0 und 5,0 Gew.-% Zink enthält. Weitere Legierungsbestandteile können Nickel mit nicht mehr als 1,0 Gew.-% und Phosphor mit nicht mehr als 0,05 Gew.-% sein. Als unvermeidbare Verunreinigungen sind zugelassen: Aluminium mit nicht mehr als 0,01 Gew.-%,Eisen ist auf 0,25 Gew.-%, der Anteil an Schwefel auf 0,1 Gew.-% und der Anteil an Antimon auf 0,25 Gew.-% beschränkt. Silizium kann schließlich mit dem Anteil von Aluminium, d.h. mit bis zu 0,01 % enthalten sein.On the basis of experiments, the alloy CuSn6Zn4Pb2, which contained between 86 and 90% by weight of copper, 1.0 and 2.0% of lead, 5.5 and 6.5% by weight of tin and 3.0, was also found to be suitable and 5.0 wt% zinc. Other alloying constituents may be nickel at not more than 1.0% by weight and phosphorus at not more than 0.05% by weight. As unavoidable impurities are permitted: aluminum with not more than 0.01 wt .-%, iron is 0.25 wt .-%, the proportion of sulfur to 0.1 wt .-% and the proportion of antimony to 0, 25 wt .-% limited. Silicon may eventually interfere with the proportion of aluminum, i. containing up to 0.01%.
Als ebenfalls geeignet haben sich Kupfer-Zinn-Legierungen erwiesen, so beispielsweise CuSn10 mit zwischen 88,5 und 90,5 Gew.-% Kupfer und Zinn mit zwischen 9 und 11 Gew.-% als notwendige Legierungsbestandteile und mit bis zu 2 Gew.-% Nickel, mit bis zu 0,2 Gew.-% Phosphor und bis zu 1,0 Gew.-% Blei. Als Verunreinigung kann Aluminium mit bis zu 0,01 Gew.-% enthalten sein, Eisen mit bis zu 0,2 Gew.-%, Mangan mit bis zu 0,1 Gew.-%, Schwefel mit bis zu 0,05 Gew.-%, Antimon mit bis zu 0,2 Gew.-%, Silizium mit bis zu 0,02 Gew.-% und Zink mit bis zu 0,5 Gew.-%.Also suitable copper-tin alloys have been found, such as CuSn10 with between 88.5 and 90.5 wt .-% copper and tin with between 9 and 11 wt .-% as necessary alloying constituents and with up to 2 wt. -% nickel, with up to 0.2 wt .-% phosphorus and up to 1.0 wt .-% lead. As an impurity, aluminum may be contained at up to 0.01% by weight, iron at up to 0.2% by weight, manganese at up to 0.1% by weight, sulfur at up to 0.05% by weight. -%, antimony with up to 0.2 wt .-%, silicon with up to 0.02 wt .-% and zinc with up to 0.5 wt .-%.
Alternativ kann auch die Legierung CuSn11P zum Einsatz kommen, die zwischen 10 und 11,5 Gew.-% Zinn und zwischen 0,5 und 1,0 Gew.-% Phosphor und zwischen 87 Gew.-% und 89,5 Gew.-% Cu als notwendige Legierungsbestandteile enthält. Als Verunreinigungen können Aluminium und Silizium mit jeweils bis zu 0,01 Gew.-% enthalten sein,Eisen und Nickel mit jeweils bis zu 0,1 Gew.-%, Mangan, Schwefel und Antimon mit jeweils bis zu 0,05 Gew.-% und Blei mit bis zu 0,25 Gew.-%.Alternatively, it is also possible to use the alloy CuSn11P, which contains between 10 and 11.5% by weight of tin and between 0.5 and 1.0% by weight of phosphorus and between 87% by weight and 89.5% by weight. Contains% Cu as necessary alloying constituents. The impurities may be aluminum and silicon, each containing up to 0.01% by weight, iron and nickel each containing up to 0.1% by weight, manganese, sulfur and antimony each having up to 0.05% by weight. % and lead with up to 0.25 wt .-%.
Schließlich hat sich die Legierung CuSn11Pb2 als für die Durchführung des Verfahrens geeignetes Basismaterial erwiesen, die zwischen 83,5 und 87,0 Gew.-% Kupfer und zwischen 0,7 und 2,5 Gew.-% Blei sowie zwischen 10,5 und 12,5 Gew.-% Zinn als notwendige Legierungsbestandteile enthält. Nickel kann mit bis zu 2,0 Gew.-%, Phosphor mit bis zu 0,4 Gew.-% und Zink mit bis zu 2,0 Gew.-% vorhanden sein. Auch bei dieser Legierung sollte hinsichtlich der unvermeidbaren Verunreinigungen der Aluminiumgehalt auf einen Anteil von 0,01 Gew.-% begrenzt sein. Mit gleichem Wert sollte auch der Anteil des Siliziums in der Legierung begrenzt sein. Mangan und Antimon können mit jeweils 0,2 Gew.-% enthalten sein, ebenso wie Eisen. Schwefel wird bis zu 0,08 Gew.-% geduldet.Finally, the alloy CuSn11Pb2 has proven to be suitable for carrying out the process base material consisting of between 83.5 and 87.0 wt .-% copper and between 0.7 and 2.5 wt .-% lead and between 10.5 and Contains 12.5 wt .-% tin as necessary alloying constituents. Nickel can with up to 2.0 wt .-%, phosphorus with up to 0.4% by weight and zinc with up to 2.0% by weight. Also in this alloy, in view of unavoidable impurities, the aluminum content should be limited to a content of 0.01 wt%. Equally, the proportion of silicon in the alloy should also be limited. Manganese and antimony can each be contained at 0.2% by weight, as well as iron. Sulfur is tolerated up to 0.08% by weight.
Nachfolgend werden einige Versuchsergebnisse von Migrationsversuchen mit der Legierung CuSn10Pb diskutiert. Die Messkurve mit den quadratischen schwarzen Symbolen als Stützstellen wurde anhand einer nach dem erfindungsgemäßen Verfahren vorbereiteten gegossenen und nachfolgend geglühten Probe ermittelt. Bei den Stützstellen mit Dreieckssymbolen handelt es sich um die Messergebnisse einer konventionellen Gussprobe des gleichen Werkstoffs ohne Glühbehandlung. Die mit Rauten versehene Linie zeigt jeweils den Grenzwert nach der Trinkwasserverordnung (TrinkwV).Some experimental results of migration tests with the alloy CuSn10Pb are discussed below. The measurement curve with the square black symbols as support points was determined by means of a cast sample prepared according to the method according to the invention and subsequently annealed. Support points with triangular symbols are the measurement results of a conventional cast sample of the same material without annealing. The rhombus line shows the limit value according to the Drinking Water Ordinance (TrinkwV).
Figur 1 zeigt die Kupferabgabe in mg/l in dem Migrationsversuch. Nach einer Anlaufzeit zeigt sich bei der erfindungsgemäßen Probe eine Kupferabgabe von unter 1000 µg/l, die nach einer Versuchsdauer von mehr als 26 Wochen auf ein Niveau von unter 500 µg/l absinkt. Die Werte der konventionellen Probe sind etwa doppelt so hoch und liegen auch nach einer Versuchsdauer von 26 Wochen deutlich höher.FIG. 1 shows the copper release in mg / l in the migration test. After a start-up time, a copper release of less than 1000 μg / l appears in the sample according to the invention, which drops to a level of less than 500 μg / l after a test duration of more than 26 weeks. The values of the conventional sample are about twice as high and are significantly higher even after a test period of 26 weeks.
In Figur 2 ist die Bleiabgabe in µg/l dargestellt. Hier zeigt sich am Anfang des Versuchs eine sehr hohe Bleiabgabe, die aber nach einer Versuchsdauer von wenigen Wochen stark abnimmt. Nach etwa 26 Wochen liegt die Bleiabgabe der erfindungsgemäßen Probe unter 5 µg/l, wohingegen die konventionelle Probe eine Bleiabgabe von etwas über 5 µg/l zeigt.FIG. 2 shows the lead delivery in μg / l. Here, at the beginning of the experiment, a very high lead levy appears, which decreases sharply after a trial period of a few weeks. After about 26 weeks, the lead release of the sample according to the invention is below 5 μg / l, whereas the conventional sample shows a lead release of slightly above 5 μg / l.
In Figur 3 wird schließlich die Nickelabgabe derselben Probe dargestellt, und zwar in µg/l in Abhängigkeit von der Versuchsdauer. Auch hier zeigt sich nach einer Anfangsphase ein erheblicher Anstieg bei der konventionellen Probe auf ca. 15 µg/l. Zum gleichen Zeitpunkt (12 Wochen Versuchsdauer) liegt die Nickelabgabe der erfindungsgemäßen Probe bei etwa 5 µg/l und tritt nach einer Versuchsdauer von mehr als 18 Wochen in einen Bereich von weniger als 5 µg/l ein.Finally, FIG. 3 shows the nickel release of the same sample, specifically in μg / l as a function of the duration of the experiment. Again, after an initial phase, a significant increase in the conventional sample to about 15 ug / l. At the same time point (12 weeks test duration), the nickel release of the sample according to the invention is about 5 μg / l and, after a test duration of more than 18 weeks, enters a range of less than 5 μg / l.
Die obigen Versuchsergebnisse sind nur beispielhaft für die Wirkung der Glühbehandlung. Insbesondere die Bleiabgabe kann dadurch vermindert werden, dass der Gusslegierung ein geringerer Anteil an Blei zugegeben wird. Diese Maßnahme wird insbesondere dann ergriffen werden, wenn es auf Zerspanungseigenschaften nicht ankommt.The above test results are only examples of the effect of the annealing treatment. In particular, the lead output can be reduced by adding a smaller amount of lead to the cast alloy. This measure will be taken in particular when it does not depend on machining properties.
In Figur 4 wird ein typisches Gefüge eines gegossenen Bauteils aus einer Rotgusslegierung nach dem Gießen (Figur 4.1) sowie nach der Glühbehandlung bei 700°C über die Dauer von 5 Stunden an zwei verschiedenen Stellen der Probe anhand von jeweils zwei Darstellungen unterschiedlicher Vergrößerung gezeigt (Figur 4.2 und 4.3).FIG. 4 shows a typical structure of a cast component made from a gunmetal alloy after casting (FIG. 4.1) and after the annealing treatment at 700 ° C. over the duration of 5 hours at two different points of the sample on the basis of two representations of different magnifications (FIG 4.2 and 4.3).
Figur 5 zeigt entsprechende Schliffe einer Rotgussprobe nach einer Glühbehandlung bei 700°C über 13 Stunden. Bei sämtlichen Schnittansichten zeigt sich gegenüber dem gegossenen Gefüge (linke Darstellungen) eine klare gekömte Struktur, wobei innerhalb der Korngrenzen noch mitunter noch die dendritische Ausbildung des Gussgefüges zu erkennen ist.FIG. 5 shows corresponding sections of a gunmetal sample after an annealing treatment at 700 ° C. for 13 hours. In all sectional views, a clear, combed structure is shown in relation to the cast structure (left representations), whereby the dendritic formation of the cast structure can still occasionally be recognized within the grain boundaries.
Claims (11)
- Process for the production of water-conducting castings of a water-supply line with reduced migration propensity, wherein a copper-zinc, copper-tin-zinc or copper-silicon-zinc alloy containing at least 80 %wt of copper is cast and, to reduce its migration propensity, the casting thus obtained is annealed at between 400°C and 800°C for at least 0.5 h and the heat-treated component is gradually cooled at 10 to 100 K/h.
- Process according to Claim 1, characterized in that the cooling is effected at a cooling rate of 20 to 60 K/h.
- Process according to Claim 1 or Claim 2, characterized in that the annealing is performed in an annealing atmosphere containing nitrogen, hydrogen and/or argon.
- Process according to Claim 1 or Claim 2, characterized in that the annealing is effected in vacuo and the subsequent cooling is performed with nitrogen.
- Process according to any one of Claims 1 to 4, characterized in that the cast alloy has the following composition in %wt: 2.6 ≤ Sn ≤ 6; 4 ≤ Zn ≤ 7; 2.0 ≤ Pb ≤ 3; 0.1 ≤ Ni ≤ 0.6; and as remainder Cu ≥ 80 and unavoidable impurities.
- Process according to Claim 5, characterized in that the cast alloy has the following composition in %wt: 3.8 ≤ Sn ≤ 6; 5.5 ≤ Zn ≤ 6.5; 2.5 ≤ Pb ≤ 3; 0.2 ≤ Ni ≤ 0.6; and as remainder Cu ≥ 80 and unavoidable impurities.
- Process according to Claim 5, characterized in that the cast alloy has the following composition in %wt: 3.9 ≤ Sn ≤ 4.1; 5.9 ≤ Zn ≤ 6.1; 2.8 ≤ Pb ≤ 3.0; 0.5 ≤ Ni ≤ 0.6; and as remainder Cu ≥ 80 and unavoidable impurities.
- Process according to any one of Claims 1 to 7, characterized in that the unavoidable impurities, for the elements listed below, are limited to the following maximum values in %wt: Al: 0.01, Sb: 0.1, As: 0.03, Bi: 0.02, Cd: 0.02, Cr: 0.02, Fe: 0.3, Si: 0.02.
- Process according to any one of Claims 1 to 8, characterized in that the cast alloy has the following composition in %wt: 0.1 ≤ Ni ≤ 2.0; 0.01 ≤ P ≤ 0.6; 0.1 ≤ Pb ≤ 0.7; 11 ≤ Sn ≤ 13; 85 ≤ Cu ≤ 88.5; and the unavoidable impurities are limited as follows, in %wt: Al ≤ 0.01, Fe ≤ 0.20; Mn ≤ 0.2; S ≤ 0.05; Sb ≤ 0.15; Si ≤ 0.01; Zn ≤ 0.05.
- Process according to any one of Claims 1 to 4, characterized in that the cast alloy has the following composition in %wt: 0.1 ≤ Si ≤ 5.0; 0.1 ≤ Zn ≤ 5.0; 0.1 ≤ Mn ≤ 1.0; 0.1 ≤ Sn ≤ 3.0; 0.5 < Pb < 3.0; 83 ≤ Cu ≤ 85; and unavoidable impurities.
- Process according to Claim 10, characterized in that the cast alloy has a silicon content in %wt of 2.0 ≤ Si ≤ 3.5.
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EP05016381A EP1749897B1 (en) | 2005-07-28 | 2005-07-28 | Process including annealing for producing water-bearing copper cast parts with lowered tendency of migration |
EP07008709A EP1818423A3 (en) | 2005-07-28 | 2005-07-28 | Process for producing water-bearing copper cast parts with lowered tendency of migration by annealing |
ES05016381T ES2294604T3 (en) | 2005-07-28 | 2005-07-28 | PROCEDURE OF MANUFACTURE OF FUNDED PARTS IN COPPER, WITH TREND TO REDUCED MIGRATION. |
AT05016381T ATE376076T1 (en) | 2005-07-28 | 2005-07-28 | METHOD FOR PRODUCING WATER-CONDUCTING COPPER CASTINGS WITH REDUCED MIGRATION TENDENCE THROUGH ANNEALING |
DE502005001747T DE502005001747D1 (en) | 2005-07-28 | 2005-07-28 | Process for the preparation of water-bearing copper castings with annealing-reduced migration tendency |
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DE (1) | DE502005001747D1 (en) |
ES (1) | ES2294604T3 (en) |
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DE202007019373U1 (en) | 2007-04-02 | 2012-02-06 | Ed. Fitscher Gmbh & Co. Kg | Use of a bronze alloy for a worm gear |
ES2373121T3 (en) | 2007-04-02 | 2012-01-31 | Ed. Fitscher Gmbh & Co. Kg | USE OF A BRONZE ALLOY FOR A WHEELED TOOL WITH ENDLESS SCREW. |
EP2014964B1 (en) * | 2007-06-05 | 2011-11-23 | R. Nussbaum AG | Valve |
CN114459850B (en) * | 2021-12-23 | 2023-10-03 | 广州海关技术中心 | Preparation method of standard sample for detecting nickel release amount of ornaments |
Family Cites Families (4)
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AU465605B2 (en) | 1971-08-11 | 1975-10-02 | Toyo Valve Co., Ltd | Copper rase alloy |
GB1443090A (en) * | 1974-03-25 | 1976-07-21 | Anaconda Co | Silicon brass resistant to partin corrosion- |
EP0947592B1 (en) * | 1996-09-09 | 2003-03-26 | Toto Ltd. | Copper alloy and method of manufacturing same |
JP3734372B2 (en) | 1998-10-12 | 2006-01-11 | 三宝伸銅工業株式会社 | Lead-free free-cutting copper alloy |
-
2005
- 2005-07-28 EP EP05016381A patent/EP1749897B1/en not_active Not-in-force
- 2005-07-28 AT AT05016381T patent/ATE376076T1/en active
- 2005-07-28 ES ES05016381T patent/ES2294604T3/en active Active
- 2005-07-28 EP EP07008709A patent/EP1818423A3/en not_active Ceased
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Also Published As
Publication number | Publication date |
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DE502005001747D1 (en) | 2007-11-29 |
ATE376076T1 (en) | 2007-11-15 |
EP1818423A2 (en) | 2007-08-15 |
ES2294604T3 (en) | 2008-04-01 |
EP1818423A3 (en) | 2007-08-22 |
EP1749897A1 (en) | 2007-02-07 |
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