EP1600517B1 - Bleifreie Automatenkupferlegierung - Google Patents

Bleifreie Automatenkupferlegierung Download PDF

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Publication number
EP1600517B1
EP1600517B1 EP05017191A EP05017191A EP1600517B1 EP 1600517 B1 EP1600517 B1 EP 1600517B1 EP 05017191 A EP05017191 A EP 05017191A EP 05017191 A EP05017191 A EP 05017191A EP 1600517 B1 EP1600517 B1 EP 1600517B1
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Prior art keywords
percent
weight
free
alloy
lead
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Expired - Lifetime
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EP05017191A
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English (en)
French (fr)
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EP1600517A2 (de
EP1600517A3 (de
Inventor
Keiichiro Oishi
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Mitsubishi Shindoh Co Ltd
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Mitsubishi Shindoh Co Ltd
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Publication of EP1600517A3 publication Critical patent/EP1600517A3/de
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    • 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
    • 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

Definitions

  • the present invention relates to lead-free, free-cutting copper alloys.
  • bronze alloys such as the one under JIS designation H5111 BC6 and brass alloys such as the ones under JIS designations H3250-C3604 and C3771.
  • Those alloys are enhanced in machinability by the addition of 1.0 to 6.0 percent, by weight, of lead and provide an industrially satisfactory machinability. Because of their excellent machinability, those lead-contained copper alloys have been an important basic material for a variety of articles such as city water faucets, water supply/drainage metal fittings and valves.
  • lead contained therein is an environment pollutant harmful to humans. That is, the lead-containing alloys pose a threat to human health and environmental hygiene because lead is contained in metallic vapor that is generated in the steps of processing those alloys at high temperatures such as melting and casting and there is also concern that lead contained in the water system metal fittings, valves and others made of those alloys will dissolve out into drinking water.
  • CH 148824 provides a method of producing particles of coquille and die casting through the use of a silicon containing alloy.
  • the alloy comprises copper and silicon and from 0.2 to 28% zinc.
  • GB 1443090 discloses a silicon-brass alloy which is resistant to parting corrosion consisting of 3-21% by weight of zinc, and an amount of silicon being sufficient to produce a structure consisting of alpha plus zeta phases in the brass and the remainder of the alloy comprising copper.
  • the alloy may also comprise 0.030% by weight of solid solubility of one or more elements of the group consisting of arsenic, antimony and phosphorus.
  • US 359570 discloses a bearing metal comprising a copper-silicon-zinc alloy having a content of 65-80% of copper and 2-6% of silicon. The alloy may further comprise 0.1 to 3% of tin.
  • US 1954003 discloses a copper alloy for chill and die casting having 65-94 wt% copper, 6-2 wt% silicon and 28-3 wt% zinc.
  • the alloy may also comprise up to 2% of lead, antimony, bismuth, cadmium, tin, nickel, cobalt, manganese, iron, chromium, aluminium, titanium, tungsten, molybdenum or zircon.
  • DE 1558470 provides the use of a copper alloy of 0.5-2.5% silicon, 29-35% zinc and the remainder of copper and up to 30% of a Beta joining portion for the production of an extruded valve guide for burning power engines.
  • the alloy may further comprise lead, iron, manganese with traces of aluminium.
  • US 354966 discloses a bell manufactured from a copper-silicon alloy having up to 6% silicon and up to 20% zinc.
  • US 3900349 discloses a silicon brass alloy which is resistant to parting corrosion comprising 3-20% zinc, 2.5-6% silicon, and from 0.03% up to the percentage of solid solubility of one or more elements of the group consisting of arsenic, antimony and phosphorous and the remainder copper.
  • the alloy includes substantial quantities of alpha and zeta phases.
  • the cutting works, forgings, castings and others include city water faucets, water supply/drainage metal fittings, valves, stems, hot water supply pipe fittings, shaft and heat exchanger parts.
  • the present invention also provides the method of forming a lead-fee, free cutting alloy having metal structure which has at least one phase selected form the ⁇ (gamma) phase and the ⁇ (kappa) phase which comprises 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; at least one element selected from among 0.02 to 0.25 percent, by weight, of phosphorous and/or 0.02 to 0.15 percent, by weight, of antimony; optionally at least one element selected from among 0.3 to 3.5 percent, by weight, of tin, and 0.02 to 0.15 percent, by weight, of arsenic, and/or; optionally at least one element selected from among 0.02 to 0.4 percent, by weight, of bismuth, 0.02 to 0.4 percent, by weight, of tellurium, and 0.02 to 0.4 percent, by weight, of selenium, and the remaining percent, by weight, of zinc and wherein the metal structure of the free cutting copper alloy at least one phase selected from the ⁇ (gamma) phase and
  • Silicon raises the easy-to-cut property by producing a gamma phase (in some cases, a kappa phase) in the structure of metal. That way, both are common in that they are effective in improving the machinability, though they are quite different in contribution to the properties of the alloy.
  • silicon is added to the first invention alloy in place of lead so as to bring about a high level of machinability meeting the industrial requirements. That is, the first invention alloy is improved in machinability through formation of a gamma phase with the addition of silicon.
  • silicon is usually added in the form of a Cu-Si alloy, which boosts the production cost.
  • An experiment showed that when silicon is added in an amount of 2.0 to 4.0 percent, by weight, it is desirable to hold the content of copper at 69 to 79 percent, by weight, in consideration of its relation to the content of zinc in order to maintain the intrinsic properties of the Cu-Zn alloy.
  • the alloy of the present invention is composed of 69 to 79 percent by weight, of copper and 2.0 to 4.0 percent, by weight, of silicon.
  • silicon improves not only the machinability but also the flow of the molten metal in casting, strength, wear resistance, resistance to stress corrosion cracking, high-temperature oxidation resistance. Also, the ductility and dezincification resistance will be improved to some extent.
  • the alloy of the present invention comprises at least one element selected from among 0.02 to 0.4 percent, by weight, of bismuth, 0.02 to 0.4 percent, by weight, of tellurium, and 0.02 to 0.4 percent, by weight, of selenium; and the remaining percent, by weight, of zinc.
  • the alloy of the present invention is provided in which at least one element selected from bismuth, tellurium and selenium is mixed to improve further the machinability obtained by the first invention alloy.
  • the addition of bismuth, tellurium or selenium in addition to silicon produces a high machinability such that complicated forms could be freely cut at a high speed.
  • the alloy of the present invention is prepared with the addition of bismuth, tellurium or selenium kept to 0.02 to 0.4 percent by weight.
  • the alloy of the present invention comprises at least one element selected from among 0.3 to 3.5 percent, by weight, of tin, 0.02 to 0.25 percent, by weight, of phosphorus, 0.02 to 0.15 percent, by weight, of antimony, and 0.02 to 0.15 percent, by weight of arsenic, and the remaining percent, by weight, of zinc.
  • Tin is effective in improving not only the machinability but also corrosion resistance properties (dezincification resistance and erosion corrosion resistance) and forgeability.
  • tin improves the corrosion resistance in the alpha phase matrix and, by dispersing the gamma phase, the corrosion resistance, forgeability and stress corrosion cracking resistance.
  • the alloy of the present invention is thus improved in corrosion resistance by such property of tin and in machinability mainly by adding silicon.
  • tin would have to be added in an amount of at least 0.3 percent by weight. But even if the addition of tin exceeds 3.5 percent by weight, the corrosion resistance and forgeability will not improve in proportion to the added amount of tin. It is no good economy.
  • phosphorus disperses the gamma phase uniformly and at the same time refines the crystal grains in the alpha phase in the matrix, thereby improving the machinability and also the corrosion resistance properties (dezincification resistance and erosion corrosion resistance), forgeability, stress corrosion cracking resistance and mechanical strength.
  • the alloy of the present invention is thus improved in corrosion resistance and others by such properties of phosphorus and in machinability mainly by adding silicon.
  • the addition of phosphorus in a very small quantity, that is, 0.02 or more percent by weight could produce results. But the addition in an amount of more than 0.25 percent by weight would not produce proportional results. Instead, that would reduce the hot forgeability and extrudability.
  • the alloy of the present invention is improved in machinability and also corrosion resistance and other properties by adding at least one element selected from among tin, phosphorus, antimony and arsenic in quantities as described above.
  • the additions of copper and silicon are set at 69 to 79 percent by weight and 2.0 to 4.0 percent by weight respectively because tin and phosphorus work mainly as corrosion resistance improver like antimony and arsenic.
  • the present invention also provides lead-free, free-cutting copper alloy with further improved machinability obtained by subjecting any one of the preceding invention alloys to a heat treatment for 30 minutes to 5 hours at 4000C to 600° C.
  • the alloys of the present invention contain machinability improving elements such as silicon and have an excellent machinability because of the addition of such elements.
  • the alloys with a high copper content which have great amounts of other phases, mainly kappa phase, than alpha, beta, gamma and delta phases can further improve in machinability in a heat treatment.
  • the kappa phase turns to a gamma phase.
  • the gamma phase finely disperses and precipitates to further enhance the machinability.
  • the alloys with a high content of copper are high in ductility of the matrix and low in absolute quantity of gamma phase, and therefore are excellent in cold workability.
  • the aforesaid heat treatment is very useful.
  • those which are high in copper content with gamma phase in small quantities and kappa phase in large quantities undergo a change in phase from the kappa phase to the gamma phase in a heat treatment.
  • the gamma phase is finely dispersed and precipitated, and the machinability is improved.
  • the materials are often force-air-cooled or water cooled depending on the forging conditions, productivity after hot working (hot extrusion, hot forging etc.), working environment and other factors.
  • those with a low content of copper hereinafter called the low copper content alloy
  • the low copper content alloy are rather low in the content of the gamma phase and contain beta phase.
  • the beta phase changes into gamma phase, and the gamma phase is finely dispersed and precipitated, whereby the machinability is improved.
  • 14005 corresponds to the alloy "JIS C 6191.” This aluminum bronze is the most excellent of the expanded copper alloys under the JIS designations with regard to strength and wear resistance.
  • No. 14006 corresponds to the naval brass alloy "JIS C 4622" and is the most excellent of the expanded copper alloys under the JIS designations with regard to corrosion resistance.
  • the chips from the cutting work were examined and classified into four forms (A) to (D) as shown in Fig. 1 .
  • the results are enumerated in Tables 14-17, 19-26, 29.
  • the chips in the form of a spiral with three or more windings as (D) in Fig. 1 are difficult to process, that is, recover or recycle, and could cause trouble in cutting work as, for example, getting tangled with the tool and damaging the cut metal surface.
  • chips in the form of a fine needle as (A) in Fig. 1 or in the form of an arc as (B) will not present such problems as mentioned above and are not bulky as the chips in (C) and (D) and easy to process. But fine chips as (A) still could creep into the sliding surfaces of a machine tool such as a lathe and cause mechanical trouble, or could be dangerous because they could stick into the worker's finger, eye or other body parts.
  • the surface condition of the cut metal surface was checked after cutting work.
  • the results are shown in Tables 14-17, 19-26, 29.
  • the following invention alloys are all equal to the conventional lead-contained alloys Nos. 14001 to 14003 in machinability: third invention alloys Nos. 3004 to 3005 and 3010 to 3012, 4022 to 4035, 5002, 5003, 5005, 5006, 5008 to 5018, 5020, 6002, 6003, 6005, 6010, 6012 to 6015, 6017, 6018, 6020 to 6029, 6032, 6033, 6035 to 6044, 6047, 6048, 6050 to 6059, 6062, 6063, 6065 to 6073, 6075, 6077, 6078, 6080 to 6089, 6092, 6093, 6095 to 6104.
  • those invention alloys are favourably compared not only with the conventional alloys Nos. 14004 to 14006 with a lead content of not higher than 0.1 percent by weight but also Nos. 14001 to 14003 which contain large quantities of lead.
  • the invention alloys were examined in comparison with the conventional alloys in hot workability and mechanical properties.
  • hot compression and tensile tests were conducted the following way.
  • the second test pieces were put to a tensile test by the commonly practised test method to determine the tensile strength, N/mm 2 and elongation, %.
  • invention alloys were put to dezincification and stress corrosion cracking tests in accordance with the test methods specified under "ISO 6509” and “JIS H 3250" respectively to examine the corrosion resistance and resistance to stress corrosion cracking in comparison with the conventional alloys.
  • the invention alloys and the ninth to thirteenth invention alloys are excellent in corrosion resistance and favourably comparable with the conventional alloys Nos. 14001 to 14003 containing great amounts of lead. And it was confirmed that especially the invention alloys which seek improvement in both machinability and corrosion resistance are very high in corrosion resistance and superior in corrosion resistance to the conventional alloy No. 14006, a naval brass which is the most resistant to corrosion of all the expanded alloys under the JIS designations.
  • test sample was cut out from each extruded test piece.
  • the sample was bent with its centre placed on an arc-shaped tester with a radius of 40 mm in such a way that one end and the other end subtend an angle of 45 degrees.
  • the test sample thus subjected to a tensile residual stress was degreased and dried, and then placed in an ammonia environment in the desiccator with a 12.5% aqueous ammonia (ammonia diluted in the equivalent of pure water).
  • the test sample was held some 80 mm above the surface of aqueous ammonia in the desiccator.
  • test sample was left standing in the ammonia environment for two hours, 8 hours and 24 hours, the test sample was taken out from the desiccator, washed in sulfuric acid solution 10% and examined for cracks under a magnifier of 10 magnifications.
  • the results are given in Tables 14-17, 19-25.

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  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Claims (6)

  1. Bleifreie Automatenkupferlegierung, umfassend 69 bis 79 Gew.-% Kupfer; 2,0 bis 4,0 Gew.-% Silicium; wenigstens ein Element, das ausgewählt ist unter 0,02 bis 0,25 Gew.-% Phosphor und/oder 0,02 bis 0,15 Gew.-% Antimon; wahlweise wenigstens ein Element, das ausgewählt ist unter 0,3 bis 3,5 Ges.-% Zinn und 0,02 bis 0,15 Gew.-% Arsen; und/oder wahlweise wenigstens ein Element, das ausgewählt ist unter 0,02 bis 0,4 Gew.-% Wismut, 0,02 bis 0,4 Gew.-% Tellur und 0,02 bis 0,4 Gew.-% Selen, wobei die restlichen Gew.-% Zink sind, und wobei die Metallstruktur der Automatenkupferlegierung mindestens eine Phase umfasst, die ausgewählt ist aus der χ-(Gamma)Phase und der κ-(Kappa)Phase.
  2. Bleifreie Automatenkupferlegierung nach Anspruch 1, wobei beim Spanen auf einer umlaufenden Fläche mit einer Drehmaschine, die mit einem geraden Drehspitzmeißel mit einem Spanwinkel von -8 (minus 8) und einer Spanungsgeschwindigkeit von 50m/min, einer Spanungstiefe von 1,5mm und einer Vorschubgeschwindigkeit von 0,11mm/U versehen ist, Späne mit einer oder mehreren Formen entstehen, die ausgewählt sind aus der Gruppe bestehend aus einer Bogenform und einer feinen Nadelform.
  3. Bleifreie Automatenkupferlegierung nach einem der vorhergehenden Ansprüche, die 30 Minuten bis 5 Stunden lang einer Wärmebehandlung bei 400 bis 600°C unterworfen wird.
  4. Verfahren zur Herstellung einer bleifreien Automatenkupferlegierung mit einer metallischen Struktur, die wenigstens eine Phase aufweist, die ausgewählt ist aus der χ-(Gamma)Phase und der κ-(Kappa)Phase, umfassend das Legieren von Kupfer, Silicium und Zink in einer Menge von 69 bis 79 Gew.-% Kupfer; 2,0 bis 4,0 Gew.-% Silicium und 0,02 bis 0,25 Gew.-% Phosphor und/oder 0,02 bis 0,15 Gew.-% Antimon; wahlweise das Legieren wenigstens eines Elementes, das ausgewählt ist aus Zinn und Arsen in einer Menge von 0,3 bis 3,5 Gew.-% Zinn und 0,02 bis 0,15 Gew.-% Arsen; und/oder wahlweise das Legieren wenigstens eines Elementes, das ausgewählt ist aus Wismut, Tellur und Selen in einer Menge von 0,02 bis 0,4 Gew.-% Wismut, 0,02 bis 0,4 Gew.-% Tellur und 0,02 bis 0,4 Gew.-% Selen, wobei die restlichen Gew.-% Zink sind.
  5. Verfahren nach Anspruch 4, wobei das Silicium als eine Cu-Si-Legierung bereitgestellt ist.
  6. Verfahren nach Anspruch 4 oder 5,wobei die bleifreie Automatenkupferlegierung 30 Minuten bis 5 Stunden lang einer Wärmebehandlung bei 400 bis 600°C unterworfen wird.
EP05017191A 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung Expired - Lifetime EP1600517B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP28859098 1998-10-12
JP28859098A JP3734372B2 (ja) 1998-10-12 1998-10-12 無鉛快削性銅合金
EP98953071A EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung

Related Parent Applications (1)

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EP98953071A Division EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung

Publications (3)

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EP1600517A2 EP1600517A2 (de) 2005-11-30
EP1600517A3 EP1600517A3 (de) 2005-12-14
EP1600517B1 true EP1600517B1 (de) 2009-02-18

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EP05017189A Expired - Lifetime EP1600515B8 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP05017190A Expired - Lifetime EP1600516B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP05017191A Expired - Lifetime EP1600517B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP98953071A Expired - Lifetime EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung
EP05075421.7A Expired - Lifetime EP1559802B1 (de) 1998-10-12 1998-11-16 Bleifrei Automatenkupferlegierung

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EP05017189A Expired - Lifetime EP1600515B8 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung
EP05017190A Expired - Lifetime EP1600516B1 (de) 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung

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EP98953071A Expired - Lifetime EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung
EP05075421.7A Expired - Lifetime EP1559802B1 (de) 1998-10-12 1998-11-16 Bleifrei Automatenkupferlegierung

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EP (5) EP1600515B8 (de)
JP (1) JP3734372B2 (de)
KR (1) KR100352213B1 (de)
AU (1) AU744335B2 (de)
CA (1) CA2314144C (de)
DE (4) DE69832097T2 (de)
TW (1) TW421674B (de)
WO (1) WO2000022182A1 (de)

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US8991787B2 (en) 2012-10-02 2015-03-31 Nibco Inc. Lead-free high temperature/pressure piping components and methods of use

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EP1600515B1 (de) 2008-07-30
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CA2314144C (en) 2006-08-22
EP1600515A2 (de) 2005-11-30
AU744335B2 (en) 2002-02-21
DE69838115D1 (de) 2007-08-30
TW421674B (en) 2001-02-11
EP1600517A2 (de) 2005-11-30
EP1600515B8 (de) 2008-10-15
JP2000119775A (ja) 2000-04-25
EP1600516B1 (de) 2007-07-18
EP1045041B1 (de) 2005-10-26
EP1045041A1 (de) 2000-10-18
EP1600515A3 (de) 2005-12-14
DE69832097D1 (de) 2005-12-01
DE69832097T2 (de) 2006-07-06
EP1559802A1 (de) 2005-08-03
DE69839830D1 (de) 2008-09-11
DE69840585D1 (de) 2009-04-02
EP1559802B1 (de) 2014-01-15
JP3734372B2 (ja) 2006-01-11
EP1600517A3 (de) 2005-12-14
KR20010033073A (ko) 2001-04-25
AU1054199A (en) 2000-05-01
KR100352213B1 (ko) 2002-09-12
EP1045041A4 (de) 2003-05-07
CA2314144A1 (en) 2000-04-20
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