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EP0274586A1 - Copper alloy and its applications - Google Patents

Copper alloy and its applications Download PDF

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Publication number
EP0274586A1
EP0274586A1 EP87115880A EP87115880A EP0274586A1 EP 0274586 A1 EP0274586 A1 EP 0274586A1 EP 87115880 A EP87115880 A EP 87115880A EP 87115880 A EP87115880 A EP 87115880A EP 0274586 A1 EP0274586 A1 EP 0274586A1
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EP
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Prior art keywords
alloy
copper
copper alloy
zirconium
cold
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Application number
EP87115880A
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German (de)
French (fr)
Inventor
Hans Joachim Dr. Wallbaum
Meinhard Dipl.-Ing. Hecht
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KM Kabelmetal AG
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KM Kabelmetal AG
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Filing date
Publication date
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Publication of EP0274586A1 publication Critical patent/EP0274586A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/04Alloys based on copper with zinc as the next major constituent

Definitions

  • the invention relates to a copper alloy consisting of 75.0 to 80.0% copper, 1.5 to 2.5% aluminum, 0.02 to 0.060% arsenic remainder copper and production-related impurities.
  • a generic alloy with 70 to 85% copper, 0.5 to 6% aluminum, 0.005 to 0.5% arsenic, balance zinc is known from US Pat. No. 2,003,685. This alloy shows a high corrosion resistance. With this alloy, the arsenic counteracts dezincification.
  • the known alloy is used in addition to the aluminum bronzes, the copper-nickel alloys and the so-called admiralty alloy as a material for condenser tubes and the like. It is referred to as special brass 76 or as Cu Zn 20 Al 2.
  • degassing is to anneal the thermoformed workpiece for a sufficiently long time at higher temperatures (e.g. 650 ° C / 3 hours or 750 ° C / 2 hours). This method is carried out in practice, but there is a certain risk that the critical temperature range for pore chain formation is run through when heating to the annealing temperature and damage is already caused (pore chain formation with the resulting embrittlement).
  • the present invention has for its object to improve the known alloy so that the disadvantages described, ie pore chain formation and resulting brittleness are avoided.
  • the mechanical and technological properties such as warm plasticity, softening behavior and creep resistance, especially at temperatures between 250 ° and 450 ° C, are to be improved.
  • This object is achieved according to the invention in that 0.02 to 0.20% zirconium and / or titanium is added to the alloy.
  • zirconium or titanium avoids the formation of pore chains and the embrittlement associated therewith without the material being subjected to stronger preforms that weaken the formation of pore chains.
  • the addition of zirconium and / or titanium is particularly advantageously between 0.05 and 0.10%.
  • the alloy according to the invention can advantageously be used as a material for objects which are produced by hot and / or cold kneading, such as, for. B. plates and sheets for condenser construction or seawater-resistant pipes, in particular seamless pipes with large dimensions, d. H. thick-walled pipes or pipes of large diameter.
  • DE-OS 2 604 262 discloses a process for producing a copper alloy which has a high elongation in the annealed state, in which an alloy with 2 to 4.5% aluminum 15 to 31% zinc and a grain-fine addition of 0.001 to 3% of one or more of the elements iron, chromium, zirconium or cobalt are alternately subjected to annealing and cold working.
  • the processing steps prevent uneven grain growth.
  • the alloy treated according to the claimed process (CDA alloy 688) is free from arsenic and therefore tends to dezincify.
  • the zircon was added to the melt in the form of a copper-zircon master alloy with 30% zirconium content.
  • a sample of this alloy was first pressed into a tube at 800 ° C. and a degree of deformation of 80%.
  • the press tube was then cold worked on a drawing bench by 40%. After annealing at 500 ° C for one hour, the tube was cold-worked again on a drawing bench by 40% and the tube was finally annealed at 500 ° C for one hour.
  • a second sample was deformed by rolling by 70% at 800 ° and then cold-rolled, the stitch reduction being 50%.
  • the rolled strip was then annealed at 500 ° C for one hour.
  • the determined values are compared with the values of an otherwise identical alloy without zircon.

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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)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A copper alloy consisting of 75.0 to 80.0 % of copper, 1.5 to 2.5 % of aluminium and 0.02 to 0.060 % of arsenic, the remainder being zinc and impurities resulting from manufacture, with 0.02 to 0.2 % of added zirconium and/or titanium is used as material for articles produced by hot- and/or cold-working.

Description

Die Erfindung betrifft eine Kupferlegierung, bestehend aus 75,0 bis 80,0 % Kupfer, 1,5 bis 2,5 % Aluminium, 0,02 bis 0,060 % Arsen Rest Kupfer und herstellungsbedingte Verun­reinigungen.The invention relates to a copper alloy consisting of 75.0 to 80.0% copper, 1.5 to 2.5% aluminum, 0.02 to 0.060% arsenic remainder copper and production-related impurities.

Eine gattungsgemäße Legierung mit 70 bis 85 % Kupfer, 0,5 bis 6 % Aluminium, 0,005 bis 0,5 % Arsen, Rest Zink, ist aus der US-PS 2 003 685 bekannt. Diese Legierung zeigt eine hohe Korrosionsbeständigkeit. Der Arsengehalt wirkt bei dieser Legierung einer Entzinkung entgegen.A generic alloy with 70 to 85% copper, 0.5 to 6% aluminum, 0.005 to 0.5% arsenic, balance zinc is known from US Pat. No. 2,003,685. This alloy shows a high corrosion resistance. With this alloy, the arsenic counteracts dezincification.

Die bekannte Legierung wird neben den Aluminiumbronzen den Kupfer-Nickel-Legierungen und der sogenannten Admiralitäts­legierung eingesetzt als Werkstoff für Kondensatorrohre und dergl. und wird als Sondermessing 76 bzw. als Cu Zn 20 Al 2 bezeichnet.The known alloy is used in addition to the aluminum bronzes, the copper-nickel alloys and the so-called admiralty alloy as a material for condenser tubes and the like. It is referred to as special brass 76 or as Cu Zn 20 Al 2.

Bei niedrigen Glühtemperaturen - der kurzzeitige Durchlauf dieses Temperaturbereichs beim Aufheizen auf hohe Tempera­turen ist ebenfalls ausreichend - kommt es zu einer Poren­kettenbildung, welche die Ursache für eine Versprödung des Werkstoffes ist. Diese Erscheinung wird beobachtet bei einer Wärmebehandlung des warmgekneteten Werkstoffes ohne voraus­gegangene Kaltverformung. Sie wird ebenfalls beobachtet bei vorausgegangener Kaltverformung des Knetgefüges. Bei einer geringen Kaltverformung (z. B. 5 bis 30 %) tritt eine Ver­stärkung bei einer hohen Kaltverformung (z. B. 35 bis 50 %) tritt eine Abschwächung des Effektes ein. Bei Kaltverformungen über 50 % wird eine Porenkettenbildung nicht beobachtet. Als Ursache für die Porenkettenbildung wurden hohe Wasserstoffge­halte des Gußmaterials ermittelt, die über das Ausgangsmate­rial beim Erschmelzen eingebracht bzw. während des Schmelzens und Gießens aufgenommen werden.At low annealing temperatures - the brief passage through this temperature range when heating to high temperatures is also sufficient - pore chains form, which cause the embrittlement of the Material. This phenomenon is observed during heat treatment of the hot-kneaded material without previous cold working. It is also observed when the kneading structure has been cold worked beforehand. With a low cold deformation (e.g. 5 to 30%) there is an intensification with a high cold deformation (e.g. 35 to 50%) the effect is weakened. Pore chain formation is not observed with cold working over 50%. The cause of the pore chain formation was determined to be high hydrogen contents in the casting material, which were introduced via the starting material during melting or taken up during melting and casting.

Man kann daher die oben beschriebene Erscheinung unter­drücken, in dem z. B. das Gußmaterial sehr lange geglüht wird mit dem Ziel, eine Entgasung des Materials zu erreichen. Da wegen der langen Diffusionswege lange Glühzeiten erforder­lich sind, ist diese Vorgehensweise nicht anwendbar bzw. unwirtschaftlich.One can therefore suppress the phenomenon described above, in which, for. B. the casting material is annealed for a very long time with the aim of achieving degassing of the material. Since long annealing times are required due to the long diffusion paths, this procedure cannot be used or is uneconomical.

Eine andere Möglichkeit der Entgasung besteht darin, das warm­geformte Werkstück bei höheren Temperaturen genügend lange zu Glühen (z. B. 650° C/ 3 Stunden bzw. 750° C/ 2 Stunden). Dieses Verfahren wird in der Praxis durchgeführt, wobei je­doch ein gewisses Risiko darin besteht, daß beim Aufheizen auf die Glühtemperatur der kritische Temperaturbereich für die Porenkettenbildung durchlaufen wird und dabei bereits eine Schädigung (Porenkettenbildung mit daraus resultierender Versprödung) verursacht wird.Another option for degassing is to anneal the thermoformed workpiece for a sufficiently long time at higher temperatures (e.g. 650 ° C / 3 hours or 750 ° C / 2 hours). This method is carried out in practice, but there is a certain risk that the critical temperature range for pore chain formation is run through when heating to the annealing temperature and damage is already caused (pore chain formation with the resulting embrittlement).

Der vorliegenden Erfindung liegt die Aufgabe zugrunde, die bekannte Legierung dahingehend zu verbessern, daß die ge­schilderten Nachteile, d. h. Porenkettenbildung und daraus resultierende Sprödigkeit vermieden werden. Darüberhinaus sollen die mechanischen bzw. technologischen Eigenschaften wie Warmplastizität, Erweichungsverhalten sowie die Zeit­standfestigkeit insbesondere bei Temperaturen zwischen 250° und 450° C verbessert werden.The present invention has for its object to improve the known alloy so that the disadvantages described, ie pore chain formation and resulting brittleness are avoided. In addition, the mechanical and technological properties such as warm plasticity, softening behavior and creep resistance, especially at temperatures between 250 ° and 450 ° C, are to be improved.

Diese Aufgabe wird gemäß der Erfindung dadurch gelöst, daß man der Legierung 0,02 bis 0,20 % Zirkon und/oder Titan zusetzt.This object is achieved according to the invention in that 0.02 to 0.20% zirconium and / or titanium is added to the alloy.

Durch den Zirkon- bzw. Titanzusatz zu der bekannten Kupfer­legierung wird die Porenkettenbildung und die damit ver­bundene Versprödung vermieden, ohne daß der Werkstoff stärkeren, die Porenkettenbildung abschwächenden Vorformungen unterworfen wird. Mit besonderem Vorteil beträgt der Zirkon- ­und/oder Titanzusatz zwischen 0,05 und 0,10 %. Die erfin­dungsgemäße Legierung läßt sich vorteilhaft anwenden als Werkstoff für Gegenstände, die durch Warm- und/oder Kalt­knetung hergestellt werden, wie z. B. Platten und Bleche für den Kondensatorbau bzw. seewasserbeständige Rohre insbe­sondere nahtlose Rohre mit großen Abmessungen, d. h. dick­wandige Rohre bzw. Rohre großen Durchmessers.The addition of zirconium or titanium to the known copper alloy avoids the formation of pore chains and the embrittlement associated therewith without the material being subjected to stronger preforms that weaken the formation of pore chains. The addition of zirconium and / or titanium is particularly advantageously between 0.05 and 0.10%. The alloy according to the invention can advantageously be used as a material for objects which are produced by hot and / or cold kneading, such as, for. B. plates and sheets for condenser construction or seawater-resistant pipes, in particular seamless pipes with large dimensions, d. H. thick-walled pipes or pipes of large diameter.

Es ist zwar aus der DE-OS 1 558 697 bekannt, die Warmwalz­barkeit bleihaltiger Kupgerlegierungen dadurch zu verbessern, daß man der Kupferlegierung Zirkon in einer Menge zusetzt, die dem 0,2 bis 5-fachen des Bleigehaltes entspricht. Hin­weise darauf, welche Wirkung ein Zirkonzusatz bei bleifreien Kupferlegierungen hat, sind dieser Entgegenhaltung jedoch nicht zu entnehmen.It is known from DE-OS 1 558 697 to improve the hot rolling ability of copper alloys containing lead by adding zirconium to the copper alloy in an amount which corresponds to 0.2 to 5 times the lead content. However, this document does not give any indication of the effect of a zirconium additive on lead-free copper alloys.

Aus der DE-OS 2 405 496 ist es weiterhin bekannt, einer zweiphasigen Messinglegierung zwischen 0,005 und 0,3 % Zirkon zuzusetzen, um die Warmbrüchigkeit zu vermeiden. Die dort behandelten Legierungen bestehen aus 56,5 bis 65 % Kupfer, Rest Zink, denen u. a. auch Aluminium bis zu 0,8 % zugeführt werden kann. Bei diesem Werkstoff handelt es sich um einen Gußwerkstoff, der zur Herstellung von Armaturen mittels Kokillenguß Anwendung findet.From DE-OS 2 405 496 it is also known to add between two 0.005 and 0.3% zirconium to a two-phase brass alloy in order to avoid hot brittleness. The alloys treated there consist of 56.5 to 65% copper, the rest zinc, which u. a. aluminum can also be fed up to 0.8%. This material is a cast material that is used for the manufacture of fittings using permanent mold casting.

Es ist weiterhin aus der DE-OS 2 604 262 ein Verfahren zur Herstellung einer Kupferlegierung bekannt, die im geglühten Zustand eine hohe Dehnung aufweist, bei dem eine Legierung mit 2 bis 4,5 % Aluminium 15 bis 31 % Zink sowie einem kornfeinenden Zusatz von 0,001 bis 3 % eines oder mehrerer der Elemente Eisen, Chrom, Zirkon oder Kobalt wechselweise einem Glühen und einer Kaltverformung unterworfen wird. Durch die Bearbeitungsschritte wird ein ungleichmäßiges Kornwachstum unterbunden. Die nach dem beanspruchten Ver­fahren behandelte Legierung (CDA-Legierung 688) ist frei von Arsen und neigt daher zur Entzinkung.Furthermore, DE-OS 2 604 262 discloses a process for producing a copper alloy which has a high elongation in the annealed state, in which an alloy with 2 to 4.5% aluminum 15 to 31% zinc and a grain-fine addition of 0.001 to 3% of one or more of the elements iron, chromium, zirconium or cobalt are alternately subjected to annealing and cold working. The processing steps prevent uneven grain growth. The alloy treated according to the claimed process (CDA alloy 688) is free from arsenic and therefore tends to dezincify.

Die Erfindung ist an Hand eines Ausführungsbeispiels näher erläutert. Es wurde eine Legierung mit folgender Zusammen­setzung erschmolzen:

      Kupfer      77,6   %
      Aluminium    2,1   %
      Arsen        0,025 %
      Zirkon       0,10  %
(bzw. Titan        0,1   %)
      Zink         Rest
      sowie herstellungsbedingte Verunreinigungen.
The invention is explained in more detail using an exemplary embodiment. An alloy with the following composition was melted:

Copper 77.6%
Aluminum 2.1%
Arsenic 0.025%
Zircon 0.10%
(or titanium 0.1%)
Zinc rest
and manufacturing-related impurities.

Das Zirkon wurde der Schmelze in Form einer Kupfer-Zirkon-­Vorlegierung mit 30 % Zirkongehalt zugefügt.The zircon was added to the melt in the form of a copper-zircon master alloy with 30% zirconium content.

Eine Probe dieser Legierung wurde zunächst bei 800° C und einem Umformgrad von 80 % zu einem Rohr gepreßt. Das Preß­rohr wurde dann auf einer Ziehbank um 40 % kaltverformt. Nach einem einstündigen Glühen bei 500° C wurde das Rohr nochmals auf einer Ziehbank um 40 % kaltverformt und das Rohr abschließend bei 500° C eine Stunde geglüht.A sample of this alloy was first pressed into a tube at 800 ° C. and a degree of deformation of 80%. The press tube was then cold worked on a drawing bench by 40%. After annealing at 500 ° C for one hour, the tube was cold-worked again on a drawing bench by 40% and the tube was finally annealed at 500 ° C for one hour.

Eine zweite Probe wurde bei 800° durch Walzen um 70 % ver­formt und daran anschließend kaltgewalzt, wobei die Stich­abnahme 50 % betrug. Das gewalzte Band wurde dann einer einstündigen Glühung bei 500° C unterzogen.A second sample was deformed by rolling by 70% at 800 ° and then cold-rolled, the stitch reduction being 50%. The rolled strip was then annealed at 500 ° C for one hour.

In der Tabelle sind die ermittelten Werte den Werten einer sonst gleichen Legierung ohne Zirkon gegenübergestellt.

Figure imgb0001
In the table, the determined values are compared with the values of an otherwise identical alloy without zircon.
Figure imgb0001

Claims (3)

1. Kupferlegierung bestehend aus 75,0 bis 80,0 % Kupfer, 1,5 bis 2,5 % Aluminium, 0,02 bis 0,060 % Arsen Rest Zink und herstellungsbedingte Verunreinigungen, ge­kennzeichnet durch einen Zusatz von 0,02 bis 0,2 % Zirkon und/oder Titan.1. Copper alloy consisting of 75.0 to 80.0% copper, 1.5 to 2.5% aluminum, 0.02 to 0.060% arsenic remainder zinc and manufacturing-related impurities, characterized by an addition of 0.02 to 0.2 % Zircon and / or titanium. 2. Kupferlegierung nach Anspruch 1, gekennzeichnet durch einen Zusatz von 0,05 bis 0,10 % Zirkon und/oder Titan2. Copper alloy according to claim 1, characterized by an addition of 0.05 to 0.10% zirconium and / or titanium 3. Verwendung einer Kupferlegierung nach Anspruch 1 oder 2 als Werkstoff für durch Warm- und/oder Kaltknetung her­gestellte Gegenstände.3. Use of a copper alloy according to claim 1 or 2 as a material for objects produced by hot and / or cold kneading.
EP87115880A 1986-11-12 1987-10-29 Copper alloy and its applications Withdrawn EP0274586A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863638663 DE3638663A1 (en) 1986-11-12 1986-11-12 COPPER ALLOY AND THEIR USE
DE3638663 1986-11-12

Publications (1)

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EP0274586A1 true EP0274586A1 (en) 1988-07-20

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT504088B1 (en) * 2006-09-01 2008-11-15 Miba Gleitlager Gmbh BEARINGS
US11427891B2 (en) * 2019-07-24 2022-08-30 Nibco Inc. Low silicon copper alloy piping components and articles

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2003685A (en) * 1934-10-30 1935-06-04 American Brass Co Aluminum brass alloy
GB841086A (en) * 1957-11-13 1960-07-13 Ici Ltd Copper alloys
GB1040884A (en) * 1962-05-03 1966-09-01 Yorkshire Imp Metals Ltd Improvements in or relating to copper rich alloys
FR1512931A (en) * 1966-03-01 1968-02-09 Olin Mathieson Copper-based alloys and in particular titanium
GB1144334A (en) * 1966-03-18 1969-03-05 Yorkshire Imp Metals Ltd Improvements in or relating to copper nickel alloys
DE3031336A1 (en) * 1980-08-20 1982-04-01 Kurt Dr.-Ing. 6380 Bad Homburg Dies Martensitic copper alloys, esp. brasses or bronzes - where quenched metastable martensitic phase is cold worked and then heated so structural change produces alteration in dimensions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2003685A (en) * 1934-10-30 1935-06-04 American Brass Co Aluminum brass alloy
GB841086A (en) * 1957-11-13 1960-07-13 Ici Ltd Copper alloys
GB1040884A (en) * 1962-05-03 1966-09-01 Yorkshire Imp Metals Ltd Improvements in or relating to copper rich alloys
FR1512931A (en) * 1966-03-01 1968-02-09 Olin Mathieson Copper-based alloys and in particular titanium
GB1144334A (en) * 1966-03-18 1969-03-05 Yorkshire Imp Metals Ltd Improvements in or relating to copper nickel alloys
DE3031336A1 (en) * 1980-08-20 1982-04-01 Kurt Dr.-Ing. 6380 Bad Homburg Dies Martensitic copper alloys, esp. brasses or bronzes - where quenched metastable martensitic phase is cold worked and then heated so structural change produces alteration in dimensions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT504088B1 (en) * 2006-09-01 2008-11-15 Miba Gleitlager Gmbh BEARINGS
US11427891B2 (en) * 2019-07-24 2022-08-30 Nibco Inc. Low silicon copper alloy piping components and articles

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DE3638663A1 (en) 1988-05-19

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