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US20090214380A1 - Low-migration copper alloy - Google Patents

Low-migration copper alloy Download PDF

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Publication number
US20090214380A1
US20090214380A1 US12/095,615 US9561506A US2009214380A1 US 20090214380 A1 US20090214380 A1 US 20090214380A1 US 9561506 A US9561506 A US 9561506A US 2009214380 A1 US2009214380 A1 US 2009214380A1
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US
United States
Prior art keywords
weight
copper alloy
components
alloy
unavoidable impurities
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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.)
Abandoned
Application number
US12/095,615
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English (en)
Inventor
Katrin Müller
Patrik Zeiter
Frank Leistritz
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.)
JRG Gunzenhauser AG
R NUSSBAUM AG METALLGIESSEREI und ARMATURENFABRIK
Viega GmbH and Co KG
Gebr Kemper GmbH and Co KG
Original Assignee
JRG Gunzenhauser AG
R NUSSBAUM AG METALLGIESSEREI und ARMATURENFABRIK
Viega GmbH and Co KG
Gebr Kemper GmbH and Co KG
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=36499302&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20090214380(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by JRG Gunzenhauser AG, R NUSSBAUM AG METALLGIESSEREI und ARMATURENFABRIK, Viega GmbH and Co KG, Gebr Kemper GmbH and Co KG filed Critical JRG Gunzenhauser AG
Assigned to R. NUSSBAUM AG METALLGIESSEREI UND ARMATURENFABRIK, GEBR. KEMPER GMBH & CO. KG METALWERKE, VIEGA GMBH & CO. KG, JRG GUNZENHAUSER AG reassignment R. NUSSBAUM AG METALLGIESSEREI UND ARMATURENFABRIK ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MULLER, KATRIN, ZEITER, PATRIK, LEISTRITZ, FRANZ
Publication of US20090214380A1 publication Critical patent/US20090214380A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • C22C9/10—Alloys based on copper with silicon as the next major constituent

Definitions

  • the present invention relates to a copper alloy.
  • the present invention relates to a low-migration copper alloy for the manufacture of components for gas and sanitary installations, especially for components which are employed in drinking water installations and are in direct contact with the drinking water carried in the components, as a rule pipes, fittings and valves.
  • Materials for the manufacture of components for gas and water installations are subject to particular demands which are in particular placed on lines carrying drinking water as well as their elements.
  • the corrosion resistance of the components has to be mentioned, for the installed components must not corrode even if they are employed for several years.
  • particular demands are placed on the manufacturability and processability, where it must not only be possible to cast the alloys easily and economically but where it moreover is necessary for the cast components to be easily mechanically worked.
  • good machinability has to be paid attention to.
  • the components made of the copper alloy also have to withstand the mechanical strains required for the field of employment.
  • a tensile strength of more than 180 N/mm 2 at a 0.2% proof stress of 85 N/mm 2 is always considered to be necessary.
  • bronzes copper-tin alloys
  • the tensile strength should be 240 N/mm 2 and the 0.2% proof stress 130 N/mm 2 and more.
  • the behavior of the materials with respect to the emission of ions of the alloy components of the materials or of reaction products with water ingredients is of particular interest.
  • very narrow limits with respect to the allowed emission of metal ions from the components into the drinking water have to be observed for protecting the consumer.
  • nonferrous heavy metal alloys such as bronze or red bronze
  • bronze or red bronze are employed for the manufacture of the components of gas and water lines carrying media.
  • lead are added to these nonferrous heavy metal alloys.
  • nickel is to be preferred.
  • GB-1 443 090 discloses a copper alloy improved with respect to dezincification with between 80 and 90% by weight of copper, between 6.3 and 17.5% by weight of zinc, and between 2.8 and 4.75% by weight of silicon as essential alloy components with between 0.03 and 0.05% by weight of arsenic.
  • a heat treatment of the cast parts is suggested. In this heat treatment, the cast parts are annealed at temperatures of between 600° C. and 750° C. over a period of 5 to 10 days and subsequently quenched. This heat treatment is performed with the aim of obtaining the ⁇ and ⁇ -phases to be preferred with respect to corrosion. By quenching, in particular the formation of phases of which the corrosion resistance is low, e.g. the ⁇ - and ⁇ -phases, is to be avoided.
  • a copper alloy which has up to 10% by weight of aluminum and up to 5% by weight of iron and is employed for the manufacture of components of water installations carrying water.
  • This alloy however. has an insufficient corrosion behavior and in particular migration of metal ions into the water is too high.
  • the problem underlying the present invention is to provide a copper alloy improved with respect to the migration behavior which is in particular suited for the manufacture of gas and water lines carrying media and their parts and which has good corrosion resistance with respect to media, good strength and good workability and castability.
  • the machining properties of the copper alloy are very important.
  • the invention wants to provide corresponding medium-carrying components, in particular fittings or valves, as well as an advantageous use of the copper alloy according to the invention.
  • the same suggests a copper alloy with the features of claim 1 .
  • This copper alloy comprises between 2 and 4.5% by weight of silicon, between 1 and 15% by weight of zinc and between 0.05 and 2% by weight of manganese.
  • the copper alloy can contain between 0.05 and 0.5% by weight of aluminum and/or between 0.05 and 2% by weight of tin.
  • copper and unavoidable impurities are contained in the alloy. These impurities are preferably restricted to a proportion of 0.5% by weight. Particularly preferred, the upper limit for the impurities is 0.25%.
  • the alloy is preferably free from lead and/or nickel.
  • An alloy in which the proportion of lead is less than 0.25% is considered as lead-free alloy.
  • An alloy in which the proportion of nickel is less than 0.15% is considered as nickel-free alloy.
  • the alloy should contain between 0.01 and 0.05% by weight of zirconium.
  • the zirconium proportion should be between 0.01% by weight and 0.03% by weight; particularly preferred, the upper limit is determined to be 0.02% by weight. This interval applies for essentially all cast components, except for sand castings. Grain refining usually results only as of 0.01% by weight, above 0.02% by weight, the risk of zirconium formation in the grain boundary zone is increased.
  • Zirconium improves the solidification morphology and reduces the formation of heat cracks, mainly in permanent mold casting. In particular in castings which are made by means of sand casting, a deliberate addition of zirconium, however, can be dispensed with. In these components, the zirconium proportion can be below 0.01% by weight, preferably even below 5 ppm (0.0005%).
  • zirconium 0.02% should be observed to avoid zirconium formation in the grain boundary zone of the texture which leads to increased tool wear in the machining of the components cast from the alloy for water-carrying lines.
  • phosphorous should also be provided in certain proportions.
  • Phosphorous is preferably present with a proportion of 0.01% by weight to 0.2% by weight.
  • Phosphorous is controlled in stated limits in particular with respect to an improvement of castability (flowability and feeding behavior of the alloy).
  • phosphorous reduces the dezincification of the alloy and improves corrosion resistance.
  • the demands to be placed on components for medium-carrying gas or water lines can be met best.
  • the alloy shows good casting behavior.
  • the components made by casting can be easily machined.
  • Tests with test pieces showed that the strength corresponds to the demands to be placed.
  • the corrosion resistance of the alloy is high.
  • the degree of impurities for phosphorous is preferably controlled to a range of 0.01 to 0.05% by weight.
  • the aluminum content of the copper alloy according to the invention is determined with regard to the corrosion resistance of the same. At present, it is assumed that with an aluminum content of between 0.05 and 0.5% by weight, good corrosion resistance can be achieved. Without considerable quality losses, the upper limiting value for the aluminum content can be determined to 0.4% by weight.
  • the relevant components for medium-carrying lines can be easily made with the usual casting methods, for example sand casting. permanent mold casting, centrifugal casting or continuous casting.
  • the casting obtained in this manner can be easily machined.
  • the same can preferably be subjected to a heat treatment before machining.
  • the casting is preferably annealed at between 400° C. and 800° C. for at least half an hour.
  • the heat treatment is performed at a temperature interval of between 600° C. and 700° C.
  • the annealing time can be arbitrarily long. With respect to economic margin conditions, it is, however, determined to between 2 and 16 hours.
  • the heat up phase is not included in this annealing time.
  • Annealing is performed in particular with the aim of adjusting the ⁇ -phase in the cast component which permits the combination of various properties to be achieved according to the present idea of the inventors. It should be pointed out, however, that already the major part of the necessary alloy elements copper, zinc and silicon solidifies in the form of an ⁇ -solid solution with natural quenching from the melt without separate heat treatment.
  • silicon within the given intervals further favors chip breakage during working.
  • the tool wear in the machining of the components made from the alloy is also increased.
  • the upper limit for the silicon content is determined to 4.5% by weight, not least also in view of the mechanical workability of the alloy.
  • the zinc content is limited to 15% by weight.
  • a minimum content of 1% by weight of zinc in contrast guarantees a minimum of machinability.
  • Manganese is added to the alloy within the limits of 0.05 to 2% by weight to improve the texture. Manganese improves the texture and has a positive influence on the solidification behavior of the copper alloy. However, the manganese content is limited to 2% by weight with regard to the migration tendency of manganese.
  • the alloy according to the invention contains between 5 and 15% by weight of zinc. In this restricted interval, a best possible combination of corrosion resistance and machinability can be achieved.
  • the silicon content is determined to between 2.8% by weight and 4% by weight.
  • the alloy For further reducing the migration tendency of manganese, its content is preferably determined to 0.2 to 0.6% by weight.
  • the alloy preferably does not contain any nickel or lead, respectively.
  • the copper content in the alloy should be at least 80 and maximally 96.95% by weight.
  • the use of the copper alloy according to the invention is suggested for the manufacture of components for medium-carrying gas and water lines, respectively. These are in particular such components which form drinking water lines, such as in particular fittings and valves as well as parts thereof. Not least due to the good stress-strain properties of the copper alloy according to the invention.
  • a compression joint is to be made from the copper alloy according to the invention.
  • the compression joints can be either formed as separate components or be provided at the fitting or the valve with a substance- or form-fit.
  • the compression joints can be also realized as integral parts in the casting of the valve or the fitting from the copper alloy according to the invention.
  • the casting alloy according to the invention is in particular suited for the manufacture of an element of a compression joint arrangement, as they are known, for example, from EP 0 343 395 or DE 10 2004 031 247.
  • FIG. 1 shows a diagram with a comparison of the lead migration of an embodiment of the copper alloy according to the invention with respect to a conventional red-bronze alloy
  • FIG. 2 shows a diagram with a comparison of the nickel migration of an embodiment of the copper alloy according to the invention with respect to a conventional red-bronze alloy
  • FIG. 3 shows a diagram with a comparison of the copper migration of an embodiment of the copper alloy according to the invention with respect to a conventional red-bronze alloy
  • FIG. 4 shows a diagram with a comparison of the zinc migration of an embodiment of the copper alloy according to the invention with respect to a conventional red-bronze alloy.
  • FIGS. 1 to 4 show the time history of the emission of certain metal ions in a set-up of measuring instruments according to DIN 50931-1 over a time of altogether 26 weeks.
  • the DIN determines the test set-up and the test conditions by means of which the corrosion probability of materials for metallic components of a drinking water installation in case of a corrosion contamination of drinking water can be determined.
  • the results in the respective representations of FIGS. 1 to 4 are compared with those measured values that can be achieved in a conventional red-bronze alloy with the same test conditions.
  • the red-bronze alloy has the following composition:
  • the measuring results with the embodiment of the copper alloy according to the invention are marked with A.
  • the comparison measurement with the red-bronze alloy is marked with B.
  • FIGS. 1 to 3 also contain a limiting value according to the German Drinking Water Regulation (DrinkwR) for the emission of certain ions into water and the parameter value W( 15 ) to be observed in migration tests.
  • This parameter value W( 15 ) has to be observed if an excess of the value of the DrinkwR is to be avoided when the tested component is used.
  • the parameter value W( 15 ) results from the product of the limiting value according to the DrinkwR and the relation of the form factors A and B.
  • the form factor A results according to DIN 50931 -1 from the relation of the surface of the material contacted by water to the surface of the complete test arrangement contacted by water.
  • the form factor B is a scaling factor according to DIN 50930-6 which takes into consideration the type of the components.
  • FIG. 1 illustrates that the amount of lead emission of the red-bronze alloy falls within the first four test weeks nearly exponentially from a very high value, higher tan 50 ⁇ g/l, to a value which settles just above the limiting value of the German DrinkwR of 10 ⁇ g/l after 12 to 26 test weeks. It is assumed that this clear excess at the beginning of the tests is due to the fact that lead that has reached the surface of the component to be tested due to the working and manufacture migrates into the drinking water After the first weeks, the surface-near lead has migrated from the sample body and the amount of the emitted lead remains approximately constant.
  • the embodiment according to invention A emits nearly no lead to the drinking water.
  • An increased value at the beginning of the tests can neither be identified.
  • the measured values are at the boarder of discrimination of the measuring analysis, the fluctuations of the measured values are attributed to the measuring accuracy of the measuring instruments.
  • the measured value for the lead emission remains clearly below the limiting value of the DrinkwR of 10 ⁇ g/l in the sample according to the invention.
  • the comparison sample from the red-bronze alloy shows a typical course where the conventional alloy exceeds the limiting value according to the German DrinkwR after nine weeks and slowly falls back again towards the limiting value of the DrinkwR after a maximum approximately in the 18 th week. It is true that the increase of the nickel concentration in the drinking water by the red-bronze alloy B could yet not be exactly explained. However, the increase is reproducible. The limiting value given by the DrinkwR is not observed.
  • the copper alloy A according to the invention does not emit any mentionable nickel ions into the drinking water.
  • the measured values of approximately 2 ⁇ g/l are within the range of discrimination of the analysis used in the measuring devices.
  • the two compared alloys show essentially the same course.
  • the alloy A according to the invention takes lower values for the copper emission in ⁇ g/l within the timely significant test results.
  • the maximum for both alloys is the measured value after 18 test weeks.
  • the copper emission is reduced for both alloys.
  • the better migration values for the element copper with respect to conventional red bronze evidence the improved corrosion resistance of the alloy according to the invention and were first not to be expected as the alloy according to the invention has a higher copper proportion than conventional red bronze. It showed, however, that just this high copper proportion of 80% and more represents the essential cause for the improved migration behavior.
  • both alloys have a sufficient distance to the W( 15 -value) even when they have reached their maximum.
  • the alloy A according to the invention has a more favorable behavior with respect to the conventional alloy B with a difference amount of approx. 500 ⁇ g/l, corresponding to 20 to 25%.
  • FIG. 4 shows the amount of zinc emitted into the drinking water by the alloy.
  • the course for the zinc emission in the copper alloy A according to the invention differs considerably from the corresponding course for the comparison alloy B.
  • the migration of the embodiment A of the alloy of zinc according to the invention is at any time below 100 ⁇ g/l.
  • the conventional alloy B exceeds this value many times over.
  • FIGS. 1 to 4 illustrate the advantages of the copper alloy according to the invention, in particular the influence of the silicon for the suppression of undesired metal ion migration into the drinking water.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Domestic Plumbing Installations (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
US12/095,615 2005-12-14 2006-12-13 Low-migration copper alloy Abandoned US20090214380A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05027341.6A EP1798298B2 (fr) 2005-12-14 2005-12-14 Utilisation d'un alliage de cuivre à faible migration et pièces en cet alliage
EP05027341.6 2005-12-14
PCT/EP2006/012008 WO2007068470A1 (fr) 2005-12-14 2006-12-13 Alliage de cuivre peu sensible aux migrations

Publications (1)

Publication Number Publication Date
US20090214380A1 true US20090214380A1 (en) 2009-08-27

Family

ID=36499302

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Application Number Title Priority Date Filing Date
US12/095,615 Abandoned US20090214380A1 (en) 2005-12-14 2006-12-13 Low-migration copper alloy

Country Status (8)

Country Link
US (1) US20090214380A1 (fr)
EP (2) EP1798298B2 (fr)
JP (1) JP4838859B2 (fr)
AT (2) ATE380259T1 (fr)
DE (2) DE502005002181D1 (fr)
ES (2) ES2297598T5 (fr)
NO (1) NO20083081L (fr)
WO (1) WO2007068470A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023138974A1 (fr) 2022-01-18 2023-07-27 Conex Ipr Limited Composants pour tuyaux d'eau potable et leur procédé de fabrication

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1801250B1 (fr) * 2005-12-22 2017-11-08 Viega Technology GmbH & Co. KG Produits à faible migration pour le transport de fluides et de l'eau potable fabriqués à partir d'alliages de cuivre
DE102007059182B4 (de) 2007-12-06 2017-04-13 Viega Gmbh & Co. Kg Verfahren zum Herstellen einer unlösbaren Verbindung sowie unlösbare Verbindung zwischen einem Fitting und einem Rohr, Fitting für ein Rohr mit einem vorgegebenen Innendurchmesser und lösbare Verbindung zwischen mindestens einem Fitting und einem Fittinggrundkörper
EP2290114A1 (fr) 2009-08-04 2011-03-02 Gebr. Kemper GmbH + Co. KG Metallwerke Composant pour conduite d'eau
DE202009016240U1 (de) 2009-11-27 2010-04-29 Weihmann, Andreas, Dipl.-Designer Wassergewinnungssystemtechnologie
DE102010055055B3 (de) * 2010-12-17 2012-05-10 Wieland-Werke Ag Verwendung einer Kupfer-Zinn-Mehrstoffbronze
DE102012013817A1 (de) * 2012-07-12 2014-01-16 Wieland-Werke Ag Formteile aus korrosionsbeständigen Kupferlegierungen
DE102013012288B4 (de) 2013-07-24 2025-10-16 Wieland-Werke Ag Korngefeinte Kupfer-Gusslegierung
DE202016101661U1 (de) 2016-03-29 2017-06-30 Geberit International Ag Bauteil für medienführende Gas- oder Wasserleitungen
CN106011528A (zh) * 2016-05-18 2016-10-12 来安县赛华管业有限公司 用于饮用水管的环保合金管材
DE102018004702A1 (de) 2018-06-12 2019-12-12 Gebr. Kemper Gmbh + Co. Kg Metallwerke Formteile aus einer korrosionsbeständigen und zerspanbaren Kupferlegierung
DE202019101597U1 (de) * 2019-03-20 2019-04-23 Otto Fuchs - Kommanditgesellschaft - Cu-Zn-Legierung

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US20040234411A1 (en) * 2003-02-28 2004-11-25 Uwe Hofmann Lead-free copper alloy and a method of manufacture
WO2005093244A1 (fr) * 2004-03-17 2005-10-06 Federal-Mogul Nürnberg GmbH Piston pour moteur a combustion interne, procede pour produire un piston et utilisation d'un alliage de cuivre pour produire un piston

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JP3734372B2 (ja) 1998-10-12 2006-01-11 三宝伸銅工業株式会社 無鉛快削性銅合金
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Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US20040234411A1 (en) * 2003-02-28 2004-11-25 Uwe Hofmann Lead-free copper alloy and a method of manufacture
WO2005093244A1 (fr) * 2004-03-17 2005-10-06 Federal-Mogul Nürnberg GmbH Piston pour moteur a combustion interne, procede pour produire un piston et utilisation d'un alliage de cuivre pour produire un piston
US20080000444A1 (en) * 2004-03-17 2008-01-03 Federal-Mogul Nuernberg Gmbh Piston for an Internal Combustion Engine, Method for Producing Said Piston and Use of a Copper Alloy in the Production of a Piston

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023138974A1 (fr) 2022-01-18 2023-07-27 Conex Ipr Limited Composants pour tuyaux d'eau potable et leur procédé de fabrication
EP4650482A2 (fr) 2022-01-18 2025-11-19 Conex IPR Limited Composants pour tuyaux d'eau potable et leur procédé de fabrication

Also Published As

Publication number Publication date
EP1817438A1 (fr) 2007-08-15
EP1798298A1 (fr) 2007-06-20
JP4838859B2 (ja) 2011-12-14
DE502006001675D1 (de) 2008-11-13
ATE380259T1 (de) 2007-12-15
ES2297598T3 (es) 2008-05-01
EP1798298B2 (fr) 2016-05-04
JP2009519377A (ja) 2009-05-14
ATE409753T1 (de) 2008-10-15
WO2007068470A1 (fr) 2007-06-21
DE502005002181D1 (de) 2008-01-17
NO20083081L (no) 2008-07-09
ES2297598T5 (es) 2016-06-03
ES2314946T3 (es) 2009-03-16
EP1798298B1 (fr) 2007-12-05
EP1817438B1 (fr) 2008-10-01

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