EP1452613A2 - Alliage de cuivre sans plomb et son utilisation - Google Patents

Alliage de cuivre sans plomb et son utilisation Download PDF

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Publication number
EP1452613A2
EP1452613A2 EP04002009A EP04002009A EP1452613A2 EP 1452613 A2 EP1452613 A2 EP 1452613A2 EP 04002009 A EP04002009 A EP 04002009A EP 04002009 A EP04002009 A EP 04002009A EP 1452613 A2 EP1452613 A2 EP 1452613A2
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EP
European Patent Office
Prior art keywords
copper alloy
alloy according
balance
unavoidable impurities
alloy
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
EP04002009A
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German (de)
English (en)
Other versions
EP1452613A3 (fr
EP1452613B1 (fr
Inventor
Uwe Dr. Hofmann
Wolfgang Dannenmann
Andreas Dr. Bögel
Monika Dr. Breu
Günter Schmid
Joerg Dr. Seeger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
Original Assignee
Wieland Werke AG
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Publication date
Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Publication of EP1452613A2 publication Critical patent/EP1452613A2/fr
Publication of EP1452613A3 publication Critical patent/EP1452613A3/fr
Application granted granted Critical
Publication of EP1452613B1 publication Critical patent/EP1452613B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 invention relates to a copper alloy based on Cu-Zn-Si and their Use.
  • Brass is used in different areas of mechanical engineering, electrical engineering and used in sanitary engineering.
  • brass containing Pb is predominantly used as the contact material used, namely as dormant contacts or fixed contacts to which for example, include clamp and plug connections or plug contacts.
  • the choice of materials focuses on easy processing.
  • the corresponding Assemblies can be machined from Pb-containing cutting brass high productivity.
  • the Pb deposits in the structure have disadvantages.
  • the storages act as chip breaker, but also set due to notch effect as well Reduction of the load-bearing cross-section, the strength or ductility of the material down. These disadvantages have to be dimensioned accordingly be compensated.
  • Pb-containing brasses also become components or containers for the Transport or storage of liquids is made.
  • An important area is the sanitary engineering. Metal casualness is particularly problematic here.
  • the materials used should therefore be less susceptible to any type be from corrosion.
  • the manufacture of components for transport or storage liquids are usually machined. Hot forming is often used upstream by drop forging.
  • Such lead-containing brass alloys are, for example, from the publication DE 43 18 377 C2 is known which is used as a wrought or cast alloy in the optical industry, the jewelry industry and in the field of drinking water and Sanitary installation takes place. This alloy also maintains its good machinability an addition of a significant amount of lead.
  • the invention has for its object a lead-free copper alloy to further improve their properties and to indicate their use.
  • the task is solved by a copper alloy based on copper, zinc and Silicon, consisting of: 70 to 83% Cu, 1 to 5% Si and the other matrix-active Elements: 0.01 to 2% Sn, 0.01 to 0.3% Fe and / or Co, 0.01 to 0.3% Ni, 0.01 up to 0.3% Mn, rest Zn and unavoidable impurities.
  • the copper alloy still contains up to 0.1% P and optionally each still up to 0.5% Ag, Al, As, Sb, Mg, Ti, Zr.
  • the copper alloy is also a Si-containing CuZn alloy (special brass) trained without toxic additives. Naturally, the requirements health and ecological compatibility fulfilled.
  • the Cu content of the alloy according to the invention is between 70 and 83%. Cu contents below 70% would lead to embrittlement, which is significant in a low elongation at break or impact strength. This would, for example, result in disadvantages in non-cutting shaping. If the Cu content exceeds 83%, this would result in machining uninterrupted cut long, bulky chips.
  • Sn, Mn and Ni are used to build the structure for a given copper content to influence specifically.
  • Sn and Mn increase the proportion of cubic space-centered beta phase, Ni stabilizes the proportion of surface-centered copper-zinc mixed crystal.
  • Mn below 0.01% would not be advantageous since the beta phase would then be too low Proportions would be present. Mn above 0.3% would increase formability and impair the resistance to stress corrosion cracking.
  • Ni below 0.01% would not be sufficient to make the copper mixed crystal sufficient to stabilize, in addition, the beneficial effect on the resistance against extensive corrosion attack. Ni above 0.3% would lead to more solidification lead in cold forming and would therefore not be advantageous.
  • Fe or Co is necessary to control the grain size of the alpha phase. Below the effect of 0.01% would not be sufficient. Above 0.3% there would also be a risk of coarse excretions together with Si. This would be disadvantageous for cold forming.
  • the characteristic of the new material is that it is determined according to EN 10045 Notched impact strength at room temperature between that of Pb-containing and Pb-free Brass can be classified while at temperatures above 600 ° C reaches the level of Pb-free brass grades.
  • P is included to form the initial cast structure and the To influence corrosion properties favorably.
  • Phosphorus increases fluidity of the melt and has a favorable effect against the susceptibility to stress corrosion cracking out.
  • aluminum can be added to prevent the formation of To enable tarnish layers.
  • This is particularly advantageous for decorative purposes. This effect is particularly significant from a share of 0.003%. contents over 0.5% would not be due to the promotion of beta phase formation more beneficial.
  • Semi-finished products made from the material according to the invention are preferably used over conventional ones Continuous casting, extrusion at temperatures between 600 ° C and 750 ° C and cold forming, for example by drawing.
  • the composition proves to be problem-free producible and surprisingly constant in properties.
  • Alloys Cu-Zn-Si as are usually treated in the literature, do not given. They lack the favorable properties in continuous casting and a stable, fluctuations in the operating parameters, for example in extrusion, less dependent structure formation. This affects both the smooth course of the technological parameters in the manufactured product itself, as well as unchanged Properties between different processed cast batches. It appears, that the fluctuation range of manufactured round bars in their properties in first approximation depends on the content of the matrix-active elements.
  • the copper alloy consists of 73 to 83% Cu and 2.5 to 4% Si, balance Zn and unavoidable impurities.
  • the copper alloy is made 73 to 78% Cu and 3 to 3.5% Si, balance Zn and unavoidable impurities.
  • the copper alloy is made 70 to 81% Cu and 1.5 to 2% Si, balance Zn and unavoidable impurities.
  • the copper alloy is made 73 to 83% Cu and 2 to 2.5% Si, balance Zn and unavoidable impurities.
  • phosphorus to be included in particular the formation of the initial cast structure and to influence the corrosion properties favorably.
  • alloy compositions with a share of 0.02 to 0.05% P are those of the material expectations met in a special way.
  • the copper alloy is advantageously used for contacts, pins or fastening elements in electrical engineering, for example as static contacts or Fixed contacts, including terminal and plug connections or plug contacts belong.
  • the alloy has a high corrosion resistance against fluid and gaseous media on. It is also resistant to dezincification and stress corrosion cracking extremely stable. As a result, the alloy is advantageously suitable for use in containers for transporting or storing liquids or gases, especially for containers in refrigeration technology or for pipes, Water fittings, tap extensions, pipe connectors and valves in sanitary engineering.
  • the low corrosion rates also ensure that the metal permeability, i.e. the Property due to the action of liquid or gaseous media to carry out is low in itself.
  • the material is suitable for areas of application, that require low pollution to protect the environment. advantageously, is therefore the use of the alloy according to the invention on the Area of recyclable components.
  • the alloy is insensitive to stress corrosion cracking for use in screw or clamp connections in which large elastic energies are stored for technical reasons.
  • the material according to the invention achieves higher yield strength values than CuZn alloys containing Pb. This means that larger tightening torques can be achieved in screw connections that must not deform plastically.
  • the yield point ratio R p0.2 / R m is smaller for the CuZnSi alloy than for machine brass. Screw connections that are only tightened once and consciously overstretched thereby achieve particularly high holding forces. Because of the higher strength level, miniaturization can save weight by at least 10%.
  • the alloy according to the invention shows a pronounced temperature dependence the impact strength. At temperatures above 600 ° C, the temperature drops Notched impact strength to values that correspond to those of some Pb-containing alloys and promise an advantageous use for drop forgings.
  • the copper alloy Possible uses of the copper alloy arise both for tubular as well as ribbon-shaped starting materials. Advantageously, they work well millable or punchable strips, sheets and plates, especially for keys, Engraving, decorative purposes or for lead frame applications. Leads to manufacture conventional continuous casting, hot rolling between 600 to 900 ° C with subsequent Forming, such as cold rolling and supplemented by others if required Annealing and forming steps, to the corresponding semi-finished strip.
  • the alloy is as Kneading, rolling or casting alloy can be used.
  • the alloy according to the invention proves to be particularly advantageous in its suitability for mass production in the semi-finished product plant in terms of robust production, ie production that is insensitive to fluctuating operating parameters.
  • Material properties by using the composition according to the invention in their variability, especially the foreground are the yield strength, the tensile strength, the elongation at break, the hardness, the grain size and the strengthening ability of the material.
  • the further course of processing by cold forming and annealing, possibly alternating, become corresponding observations made.
  • Bolt 1 had the composition 73.63% Cu, 23.37% Zn, 2.94% Si, 0.01% Sn, 0.02% Fe, 0.01% Ni, 0.01% Mn, 0.006% P.
  • Bolt 2 had the Composition 76.65% Cu, 20.04% Zn, 3.27% Si, 0.01% Sn, 0.01% Fe, 0.01 % Ni, 0.01% Mn, 0.003% P.
  • the bolts were extruded at 700 ° C Round bars, ⁇ 21.5 mm, formed. After a surface treatment Pickling in sulfuric acid and hydrogen peroxide was carried out by cold working Pull to the final dimension ⁇ 20 mm.
  • the table below shows an example of some usage properties of the Si-containing Special brass compared to semi-finished products made of CuZn37 and CuZn39Pb3, which was produced in a comparable way.
  • the example illustrates that a reduction in the Cu content leads to a significant embrittlement of the material.
  • the copper concentration is approx. 3% lower than in bolt 2. The consequence is a corresponding decrease in the elongation at break. If the Cu content is further reduced below a value of 70%, the properties of the alloy which are advantageous according to the invention are no longer achieved.
  • Bolt 1 Bolt 2 CuZn39Pb3 CuZn37 Status Round bar 7% pulled Round bar, 7% pulled Round bar, 7% pulled Round bar, 7% pulled Yield strength R p0.2 421 MPa 412 MPa 335 MPa 300 MPa
  • Elongation at break A 10 6% 26% 18% 32% SRK4 test according to DIN 50916T1 (on a turned part made from the rod - see Fig. 1) - no cracks cracks cracks Max.
  • the tensile strength of the round bars, which consist of the copper and silicon-rich bolts 2 was produced, is significantly higher than the comparison materials.
  • the Elongation at break lies between those of CuZn39Pb3 and CuZn37; the corrosion resistance is greatest in the Si-containing material; at the cutting Processing involves the same, inexpensive chip shapes as with those containing Pb Cutting brass.
  • the rods resulting from bolt 2 were used for impact tests. 2 shows the notched impact strength a K as a function of the temperature for alloys according to the invention and Pb-containing alloys of the prior art.
  • Fig. 2 also shows Pb-free and Pb-containing brass types for comparison.
  • the classic forged brass CuZn40Pb2 is the classic forged brass CuZn40Pb2.
  • the a k values are below those of the Pb-free CuZn alloys. This correlates with the comparatively favorable chip shapes of the alloy according to the invention.
  • the impact strength reaches the values of the Pb-free alloy. Accordingly, the Si-containing alloys are also suitable for the production of complex drop forgings.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Domestic Plumbing Installations (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
EP04002009A 2003-02-28 2004-01-30 Alliage de cuivre sans plomb et son utilisation Expired - Lifetime EP1452613B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10308778 2003-02-28
DE10308778A DE10308778B3 (de) 2003-02-28 2003-02-28 Bleifreie Kupferlegierung und deren Verwendung

Publications (3)

Publication Number Publication Date
EP1452613A2 true EP1452613A2 (fr) 2004-09-01
EP1452613A3 EP1452613A3 (fr) 2004-09-22
EP1452613B1 EP1452613B1 (fr) 2007-12-05

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Family Applications (1)

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EP04002009A Expired - Lifetime EP1452613B1 (fr) 2003-02-28 2004-01-30 Alliage de cuivre sans plomb et son utilisation

Country Status (9)

Country Link
US (1) US7354489B2 (fr)
EP (1) EP1452613B1 (fr)
JP (1) JP4537728B2 (fr)
CN (1) CN100430498C (fr)
AT (1) ATE380258T1 (fr)
AU (1) AU2004200784B2 (fr)
CA (1) CA2458723C (fr)
DE (2) DE10308778B3 (fr)
DK (1) DK1452613T3 (fr)

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EP1936388A1 (fr) 2006-12-22 2008-06-25 Wieland-Werke Ag Matériau électrique conducteur doté d'une résistance de mesure
WO2012104426A2 (fr) 2011-02-04 2012-08-09 Swissmetal Industries Ltd Alliage de cu-ni-zn-mn
CN104018047A (zh) * 2014-06-24 2014-09-03 长沙学院 一种用于无铅易切削铋黄铜的铋锰铝铈添加剂和制备方法
WO2023138974A1 (fr) * 2022-01-18 2023-07-27 Conex Ipr Limited Composants pour tuyaux d'eau potable et leur procédé de fabrication
GB2627162A (en) * 2022-01-18 2024-08-14 Conex Ipr Ltd Components for drinking water pipes, and method for manufacturing same

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CN103480987B (zh) * 2013-09-26 2015-08-19 郑州机械研究所 一种高脆性铜锌焊丝/焊片的制备方法
CN103757471B (zh) * 2013-12-31 2015-12-09 安徽瑞庆信息科技有限公司 一种无铅易切削镁黄铜合金材料及其制备方法
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CN104831114A (zh) * 2015-05-12 2015-08-12 苏州列治埃盟新材料技术转移有限公司 新型多组分环保无铅合金新材料合金棒及其制备方法
KR102021723B1 (ko) 2016-08-15 2019-09-16 미쓰비시 신도 가부시키가이샤 쾌삭성 구리 합금 주물, 및 쾌삭성 구리 합금 주물의 제조 방법
US11155909B2 (en) 2017-08-15 2021-10-26 Mitsubishi Materials Corporation High-strength free-cutting copper alloy and method for producing high-strength free-cutting copper alloy
CN107805738B (zh) * 2017-11-24 2020-01-07 江西勇骏实业有限公司 一种镍铝黄铜合金及其制备工艺
JP6713074B1 (ja) * 2019-04-16 2020-06-24 Ｄｏｗａメタルテック株式会社 銅合金板材およびその製造方法
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TWI731506B (zh) 2019-06-25 2021-06-21 日商三菱伸銅股份有限公司 快削性銅合金及快削性銅合金的製造方法
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1936388A1 (fr) 2006-12-22 2008-06-25 Wieland-Werke Ag Matériau électrique conducteur doté d'une résistance de mesure
WO2012104426A2 (fr) 2011-02-04 2012-08-09 Swissmetal Industries Ltd Alliage de cu-ni-zn-mn
CN104018047A (zh) * 2014-06-24 2014-09-03 长沙学院 一种用于无铅易切削铋黄铜的铋锰铝铈添加剂和制备方法
CN104018047B (zh) * 2014-06-24 2016-04-06 长沙学院 一种用于无铅易切削铋黄铜的铋锰铝铈添加剂和制备方法
WO2023138974A1 (fr) * 2022-01-18 2023-07-27 Conex Ipr Limited Composants pour tuyaux d'eau potable et leur procédé de fabrication
GB2614752B (en) * 2022-01-18 2024-07-31 Conex Ipr Ltd Components for drinking water pipes, and method for manufacturing same
GB2627162A (en) * 2022-01-18 2024-08-14 Conex Ipr Ltd Components for drinking water pipes, and method for manufacturing same
AU2023210036B2 (en) * 2022-01-18 2025-02-27 Conex Ipr Limited Components for drinking water pipes, and method for manufacturing same
GB2627162B (en) * 2022-01-18 2025-04-23 Conex Ipr Ltd Components for drinking water pipes, and method for manufacturing same
EP4650482A3 (fr) * 2022-01-18 2026-01-28 Conex IPR Limited Composants pour tuyaux d'eau potable et leur procédé de fabrication

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DK1452613T3 (da) 2008-04-14
JP4537728B2 (ja) 2010-09-08
US20040234411A1 (en) 2004-11-25
CA2458723A1 (fr) 2004-08-28
JP2004263301A (ja) 2004-09-24
EP1452613A3 (fr) 2004-09-22
CN1524970A (zh) 2004-09-01
CA2458723C (fr) 2009-10-06
DE10308778B3 (de) 2004-08-12
DE502004005634D1 (de) 2008-01-17
AU2004200784B2 (en) 2009-08-20
AU2004200784A1 (en) 2004-09-16
CN100430498C (zh) 2008-11-05
US7354489B2 (en) 2008-04-08
EP1452613B1 (fr) 2007-12-05
ATE380258T1 (de) 2007-12-15

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