EP3985136A1 - Alliage de cuivre sans plomb et utilisage de l'alliage de cuivre sans plomb - Google Patents

Alliage de cuivre sans plomb et utilisage de l'alliage de cuivre sans plomb Download PDF

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Publication number
EP3985136A1
EP3985136A1 EP21201428.6A EP21201428A EP3985136A1 EP 3985136 A1 EP3985136 A1 EP 3985136A1 EP 21201428 A EP21201428 A EP 21201428A EP 3985136 A1 EP3985136 A1 EP 3985136A1
Authority
EP
European Patent Office
Prior art keywords
weight
copper alloy
free copper
lead
lead free
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.)
Pending
Application number
EP21201428.6A
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German (de)
English (en)
Inventor
Norbert Gaag
Florian Seuss
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.)
Diehl Brass Solutions Stiftung and Co KG
Original Assignee
Diehl Metall Stiftung 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 Diehl Metall Stiftung and Co KG filed Critical Diehl Metall Stiftung and Co KG
Publication of EP3985136A1 publication Critical patent/EP3985136A1/fr
Pending 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
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • 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 invention relates to a lead-free copper alloy.
  • copper alloys with Sn and Al are known. Zr must also be added to these for grain refinement.
  • Such copper alloys are, for example, in EP 1 777 305 B1 , EP 1 502 964 B1 as well as the EP 1 777 308 B1 described.
  • the DE 103 08 778 B3 discloses a lead-free copper alloy which can be used in the field of drinking water and sanitary installations.
  • the well-known copper alloy necessarily contains Fe and/or Co as well as Ni and Mn.
  • the EP 1 600 516 A2 , EP 1 559 802 A1 , EP 1 600 517 A2 , EP 1 045 041 A1 as well as the EP 1 508 626 A1 each disclose lead-free copper alloys in which the content of Sn is at least 0.3% by weight.
  • the Al content is at least 0.1%.
  • the aforementioned lead-free alloys do not always form a sufficiently corrosion-inhibiting top layer or oxide layer when they come into contact with drinking water. As a result, undesired corrosion occurs due to selective leaching of Zn from the alloy (so-called "dezincification").
  • the object of the invention is to overcome the disadvantages of the prior art.
  • a lead-free copper alloy is to be specified whose corrosion resistance is improved, particularly when used in the drinking water sector.
  • a lead-free copper alloy comprising 70.0 to 83.0% by weight of Cu, 2.0 to 2.9% by weight of Si, 0.05 to 0.10% by weight of P, 0.01 to less than 0.30% by weight of Sn, balance: Zn and unavoidable impurities.
  • the proposed lead-free copper alloy is characterized by improved corrosion resistance, especially when it comes into contact with drinking water.
  • the improved corrosion resistance is attributed to the formation of a top layer or oxide layer with improved adhesion.
  • the improved adhesion is already achieved with a Sn content of less than 0.30% by weight.
  • the corrosion resistance can surprisingly be increased by adding less than 0.1% by weight of Al.
  • the Cu content is advantageously 73.3 to 76.8% by weight.
  • the copper alloy according to the invention comprises 0.01 to less than 0.1% by weight of Al.
  • the proposed addition of Al improves the adhesion of the top layer.
  • the proportion of Si is 2.40 to 2.90% by weight, preferably 2.60 to 2.80% by weight, advantageously 2.60 to 2.78% by weight.
  • the proposed addition of Si helps to reduce the kappa phase to a maximum proportion of 25% by weight. It has been observed that reducing the level of kappa phase also contributes to improved corrosion resistance.
  • the proportion of kappa phase is preferably at most 25% by weight, in particular 5 to 20% by weight.
  • the proportion of Al is advantageously 0.01 to 0.05% by weight.
  • the proportion of P can be 0.08 to 0.10% by weight. The proposed proportions enable the production of a particularly corrosion-resistant alloy.
  • the proposed lead-free copper alloy is particularly suitable for the production of installation components for the drinking water sector, for example for the production of fittings, fittings, pipes and the like.
  • Table 1 shows the composition of experimental alloys.
  • Table 1 Alloy No. Alloying Elements (wt%) Cu si P sn Al 2737 76.43 3.35 0.091 0.003 0.002 2838 76.42 3.02 0.091 0.003 0.002 2839 76.45 2.72 0.091 0.003 0.001 2840 75.99 2.73 0.093 0.003 0.001 2841 76.44 2.75 0.052 0.002 0.001 2842 76.46 2.71 0.09 0.103 0.001 2843 76.52 2.71 0.093 0.287 0.001 2845 76.33 3.1 0.092 0.019 0 2846 76.16 3.4 0.048 0.005 0 2858 76.6 2.61 0.095 0.288 0.042
  • test specimens were produced as follows: A melt formed from the alloying elements was poured into sand molds with a diameter of 40 mm at a temperature of 1020°C to 1050°C. The solidified specimens were then turned to a diameter of 24 mm. The specimens were then reduced to a diameter of 8 mm at a temperature of 700 °C using an extrusion simulation. Finally, the specimens were annealed at 550°C to 580°C for 2 hours and then cooled in air.
  • alloy Nos. 2842, 2843 and 2858 correspond to alloys according to the invention.
  • the other alloys are comparison alloys.
  • Table 2 shows results of structural analysis.
  • Table 2 Alloy No. alloying elements structure Cu si P sn Al Kappa MK Gamma MK 2737 76.43 3.35 0.091 0.003 0.002 44% 1% 2838 76.42 3.02 0.091 0.003 0.002 31% 1% 2839 76.45 2.72 0.091 0.003 0.001 22% 1% 2840 75.99 2.73 0.093 0.003 0.001 24% 1% 2841 76.44 2.75 0.052 0.002 0.001 19% ⁇ 1% 2842 76.46 2.71 0.09 0.103 0.001 15% 1% 2843 76.52 2.71 0.093 0.287 0.001 16% 1% 2845 76.33 3.1 0.092 0.019 0 26% ⁇ 1% 2846 76.16 3.4 0.048 0.005 0 42% ⁇ 1% 2858 76.6 2.61 0.095 0.288 0.042 10% ⁇ 1%
  • the only figure shows the maximum depth of dezincification [ ⁇ m] for the 3 alloys Nos. 2842, 2843 and 2858 according to the invention in comparison to alloy No. 2846 (prior art).
  • the "maximum depth of dezincification” is the depth up to which Zn was detectable according to the following test protocol.
  • the samples were sawn.
  • the sawing surface was brought into contact with drinking water for a period of 8 weeks.
  • the drinking water was changed twice a week.
  • the hardness of the drinking water was adjusted to a value of 25°dH by adding NaCl and MgSO 4 .
  • the chloride content was 250 mg/l
  • the sulfate content was also 250 mg/l.
  • the exposure test took place under room conditions.
  • the sample was cut perpendicular to the surface, polished and then optically analyzed using a reflected light microscope. The depth of the dezincification was evident from the characteristic color of the zinc-free sponge copper.
  • alloys Nos. 2842, 2843 and 2858 according to the invention exhibit a drastically reduced maximum depth of dezincification compared to alloy No. 2846 (prior art). In particular, no dezincification could be observed with alloy no. 2843 according to the invention.
  • the alloy according to the invention is characterized by a drastically improved corrosion resistance when in contact with drinking water.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Conductive Materials (AREA)
  • Domestic Plumbing Installations (AREA)
  • Table Devices Or Equipment (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP21201428.6A 2020-10-16 2021-10-07 Alliage de cuivre sans plomb et utilisage de l'alliage de cuivre sans plomb Pending EP3985136A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102020127317.7A DE102020127317A1 (de) 2020-10-16 2020-10-16 Bleifreie Kupferlegierung sowie Verwendung der bleifreien Kupferlegierung

Publications (1)

Publication Number Publication Date
EP3985136A1 true EP3985136A1 (fr) 2022-04-20

Family

ID=78085853

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21201428.6A Pending EP3985136A1 (fr) 2020-10-16 2021-10-07 Alliage de cuivre sans plomb et utilisage de l'alliage de cuivre sans plomb

Country Status (6)

Country Link
US (1) US20220119920A1 (fr)
EP (1) EP3985136A1 (fr)
JP (1) JP2022066187A (fr)
CN (1) CN114369743A (fr)
DE (1) DE102020127317A1 (fr)
MX (1) MX2021012641A (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1045041A1 (fr) 1998-10-12 2000-10-18 Sambo Copper Alloy Co., Ltd Alliage de cuivre de decolletage sans plomb
DE10308778B3 (de) 2003-02-28 2004-08-12 Wieland-Werke Ag Bleifreie Kupferlegierung und deren Verwendung
EP1508626A1 (fr) 1998-10-09 2005-02-23 Sambo Copper Alloy Co., Ltd Alliage de décolletage à base de cuivre.
US20070062615A1 (en) 2005-09-22 2007-03-22 Sanbo Shindo Kogyo Kabushiki Kaisha Free-cutting copper alloy containing very low lead
EP1777305B1 (fr) 2004-08-10 2010-09-22 Mitsubishi Shindoh Co., Ltd. Moulage d'alliage de cuivre avec des granules de cristal raffiné
EP2634275A1 (fr) * 2010-10-25 2013-09-04 Mitsubishi Shindoh Co., Ltd. Alliage de cuivre résistant à la pression et à la corrosion, structure brasée et procédé pour la production de la structure brasée
CN105603250A (zh) * 2016-03-28 2016-05-25 上海理工大学 一种耐海水腐蚀的铜合金及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101633987A (zh) 2009-06-19 2010-01-27 浙江天申铜业有限公司 一种无铅环保的硅黄铜合金棒或合金锭及其制备方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1508626A1 (fr) 1998-10-09 2005-02-23 Sambo Copper Alloy Co., Ltd Alliage de décolletage à base de cuivre.
EP1502964B1 (fr) 1998-10-09 2006-03-01 Sambo Copper Alloy Co., Ltd Alliage de décolletage à base de cuivre.
EP1600517A2 (fr) 1998-10-12 2005-11-30 Sambo Copper Alloy Co., Ltd Alliage de cuivre de décolletage sans plomb
EP1559802A1 (fr) 1998-10-12 2005-08-03 Sambo Copper Alloy Co., Ltd Alliage de cuivre de décolletage sans plomb
EP1600516A2 (fr) 1998-10-12 2005-11-30 Sambo Copper Alloy Co., Ltd Alliage de cuivre de décolletage sans plomb
EP1600515A2 (fr) 1998-10-12 2005-11-30 Sambo Copper Alloy Co., Ltd Alliage de cuivre de décolletage sans plomb
EP1045041A1 (fr) 1998-10-12 2000-10-18 Sambo Copper Alloy Co., Ltd Alliage de cuivre de decolletage sans plomb
DE10308778B3 (de) 2003-02-28 2004-08-12 Wieland-Werke Ag Bleifreie Kupferlegierung und deren Verwendung
EP1777305B1 (fr) 2004-08-10 2010-09-22 Mitsubishi Shindoh Co., Ltd. Moulage d'alliage de cuivre avec des granules de cristal raffiné
EP1777308B1 (fr) 2004-08-10 2011-12-14 Mitsubishi Shindoh Co., Ltd. Alliage de cuivre
US20070062615A1 (en) 2005-09-22 2007-03-22 Sanbo Shindo Kogyo Kabushiki Kaisha Free-cutting copper alloy containing very low lead
EP2634275A1 (fr) * 2010-10-25 2013-09-04 Mitsubishi Shindoh Co., Ltd. Alliage de cuivre résistant à la pression et à la corrosion, structure brasée et procédé pour la production de la structure brasée
CN105603250A (zh) * 2016-03-28 2016-05-25 上海理工大学 一种耐海水腐蚀的铜合金及其制备方法

Also Published As

Publication number Publication date
MX2021012641A (es) 2022-04-18
CN114369743A (zh) 2022-04-19
DE102020127317A1 (de) 2022-04-21
JP2022066187A (ja) 2022-04-28
US20220119920A1 (en) 2022-04-21

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