EP1749897A1 - Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit - Google Patents

Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit Download PDF

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Publication number
EP1749897A1
EP1749897A1 EP05016381A EP05016381A EP1749897A1 EP 1749897 A1 EP1749897 A1 EP 1749897A1 EP 05016381 A EP05016381 A EP 05016381A EP 05016381 A EP05016381 A EP 05016381A EP 1749897 A1 EP1749897 A1 EP 1749897A1
Authority
EP
European Patent Office
Prior art keywords
copper
tin
weight
alloy
migration
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.)
Granted
Application number
EP05016381A
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German (de)
English (en)
Other versions
EP1749897B1 (fr
Inventor
Frank Leistritz
Katrin Dr.-Ing. Müller
Patrik Zeiter
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
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
Priority to EP05016381A priority Critical patent/EP1749897B1/fr
Priority to AT05016381T priority patent/ATE376076T1/de
Priority to DE502005001747T priority patent/DE502005001747D1/de
Priority to EP07008709A priority patent/EP1818423A3/fr
Priority to ES05016381T priority patent/ES2294604T3/es
Publication of EP1749897A1 publication Critical patent/EP1749897A1/fr
Application granted granted Critical
Publication of EP1749897B1 publication Critical patent/EP1749897B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • 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.
  • From the GB-1 385 411 is a copper alloy with up to 10 wt .-% aluminum and up to 5 wt .-% iron for the production of water-bearing components of water installations known.
  • this shows an insufficient corrosion behavior and in particular an excessive migration of metal ions into the drinking water.
  • 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 present invention provides a water-conducting component having the features of claim 12.
  • This component is produced as a casting from a copper-tin, copper-tin-zinc or copper-silicon-zinc alloy, in particular such an alloy of the kind specified above and according to the invention has significantly reduced migration values compared to the prior art ,
  • 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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  • 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)
  • Sliding-Contact Bearings (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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EP05016381A 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit Not-in-force EP1749897B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP05016381A EP1749897B1 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit
AT05016381T ATE376076T1 (de) 2005-07-28 2005-07-28 Verfahren zur herstellung von wasserführenden kupfer-gussteilen mit durch glühen verringerter migrationsneigung
DE502005001747T DE502005001747D1 (de) 2005-07-28 2005-07-28 Verfahren zur Herstellung von wasserführenden Kupfer-Gussteilen mit durch Glühen verringerter Migrationsneigung
EP07008709A EP1818423A3 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit
ES05016381T ES2294604T3 (es) 2005-07-28 2005-07-28 Procedimiento de fabricacion de piezas fundidas en cobre, con tendencia a la migracion reducida.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05016381A EP1749897B1 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit

Related Child Applications (1)

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EP07008709A Division EP1818423A3 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit

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EP1749897A1 true EP1749897A1 (fr) 2007-02-07
EP1749897B1 EP1749897B1 (fr) 2007-10-17

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EP07008709A Ceased EP1818423A3 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit
EP05016381A Not-in-force EP1749897B1 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit

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EP07008709A Ceased EP1818423A3 (fr) 2005-07-28 2005-07-28 Procédé de fabrication de pièces coulées en cuivre, dont la tendance de migration est réduite par recuit

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EP (2) EP1818423A3 (fr)
AT (1) ATE376076T1 (fr)
DE (1) DE502005001747D1 (fr)
ES (1) ES2294604T3 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1980633A1 (fr) 2007-04-02 2008-10-15 Ed. Fitscher GmbH & Co. KG Alliage de bronze destiné à la coulée
EP2014964A1 (fr) * 2007-06-05 2009-01-14 R. Nussbaum AG Armature
DE202007019373U1 (de) 2007-04-02 2012-02-06 Ed. Fitscher Gmbh & Co. Kg Verwendung einer Bronzelegierung für ein Schneckenzahnrad
CN114459850A (zh) * 2021-12-23 2022-05-10 广州海关技术中心 一种饰品镍释放量检测用标准样品的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1385411A (en) 1971-08-11 1975-02-26 Toyo Valve Co Ltd Aluminium-containing copper alloys
GB1443090A (en) 1974-03-25 1976-07-21 Anaconda Co Silicon brass resistant to partin corrosion-
EP1045041A1 (fr) 1998-10-12 2000-10-18 Sambo Copper Alloy Co., Ltd Alliage de cuivre de decolletage sans plomb

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2265812A1 (fr) * 1996-09-09 1998-03-12 Toto Ltd. Alliage de cuivre et procede de fabrication correspondant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1385411A (en) 1971-08-11 1975-02-26 Toyo Valve Co Ltd Aluminium-containing copper alloys
GB1443090A (en) 1974-03-25 1976-07-21 Anaconda Co Silicon brass resistant to partin corrosion-
EP1045041A1 (fr) 1998-10-12 2000-10-18 Sambo Copper Alloy Co., Ltd Alliage de cuivre de decolletage sans plomb

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1980633A1 (fr) 2007-04-02 2008-10-15 Ed. Fitscher GmbH & Co. KG Alliage de bronze destiné à la coulée
DE202007019373U1 (de) 2007-04-02 2012-02-06 Ed. Fitscher Gmbh & Co. Kg Verwendung einer Bronzelegierung für ein Schneckenzahnrad
EP2014964A1 (fr) * 2007-06-05 2009-01-14 R. Nussbaum AG Armature
CN114459850A (zh) * 2021-12-23 2022-05-10 广州海关技术中心 一种饰品镍释放量检测用标准样品的制备方法
CN114459850B (zh) * 2021-12-23 2023-10-03 广州海关技术中心 一种饰品镍释放量检测用标准样品的制备方法

Also Published As

Publication number Publication date
ATE376076T1 (de) 2007-11-15
DE502005001747D1 (de) 2007-11-29
ES2294604T3 (es) 2008-04-01
EP1818423A2 (fr) 2007-08-15
EP1749897B1 (fr) 2007-10-17
EP1818423A3 (fr) 2007-08-22

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