EP1559802B1 - Bleifrei Automatenkupferlegierung - Google Patents

Bleifrei Automatenkupferlegierung Download PDF

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Publication number
EP1559802B1
EP1559802B1 EP05075421.7A EP05075421A EP1559802B1 EP 1559802 B1 EP1559802 B1 EP 1559802B1 EP 05075421 A EP05075421 A EP 05075421A EP 1559802 B1 EP1559802 B1 EP 1559802B1
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EP
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Prior art keywords
remainder
alloy
machinability
alloys
resistance
Prior art date
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Expired - Lifetime
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EP05075421.7A
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English (en)
French (fr)
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EP1559802A1 (de
Inventor
Keiichiro Sambo Copper Alloy Co. Ltd OISHI
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Mitsubishi Shindoh Co Ltd
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Mitsubishi Shindoh Co Ltd
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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 wt% 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.
  • DE 1558470 discloses copper zinc alloys with 0.5 to 2.5% silicon which are suitable for forming guides for valves in combustion engines.
  • US 3,900,349 discloses corrosion-resistant silicon brasses which are quenched from a high annealing temperature to form an alpha plus zeta microstructure.
  • 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.
  • lead-free copper alloys in accordance with claim 1.
  • Silicon in an amount of 2.0 to 4.0 percent is an additive to a lead-free copper alloy composition which comprises 69 to 79 wt% copper and the remaining wt% zinc, to improve the machinability of the alloy by producing in the metal structure ⁇ (gamma) phase, as set out in claim 1 hereinafter.
  • the invention is carried out in the manufacture of the following alloys:
  • the alloys listed above 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 (hereinafter referred to as the "high copper content alloy") 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-alr-cooled or water cooled depending on the forging conditions, productivity after hot working (hot extrusion, hot forging etc.), working environment and other factors.
  • the low copper content alloy those with a low content of copper (hereinafter called 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.
  • No. 13004 is an alloy test piece obtained by heat-treating an extruded test piece with the same composition as No. 13007 under the same conditions as for 13002 - for two hours at 450°C.
  • No. 13005 is an alloy test piece obtained by heat-treating an extruded test piece with the same composition as first alloy No. 1008 under the same conditions as for No. 13001 - for 30 minutes at 580°C.
  • No. 13006 is an alloy test piece obtained by heat-treating an extruded test piece with the same composition as No. 1008 and heat-treated under the same conditions as for 13002 - for two hours at 450°C.
  • 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.
  • 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 Table 38 to Table 66.
  • the commonly used basis for indication of the surface roughness is the maximum roughness (Rmax). While requirements are different depending on the application field of brass articles, the alloys with Rmax ⁇ 10 microns are generally considered excellent in machinability. The alloys with 10 microns ⁇ Rmax ⁇ 15 microns are judged as industrially acceptable, while those with Rmax ⁇ 15 microns are taken as poor in machinability.
  • the following alloys are all equal to the conventional lead- contained alloys Nos. 14001 to 14003 in machinability: first alloys Nos. 1001 to 1008, second alloys Nos. 2001 to 2011, fifth alloys Nos. 5001 to 5020, sixth alloys Nos. 6001 to 6105, ninth alloys Nos. 9001 to 9005, tenth alloys Nos. 10001 to 10008, eleventh alloys Nos. 11001 to 11007, twelfth alloys Nos. 12001 to 12021.
  • those alloys are favourably compared not only with the conventional alloys Nos. 14004 to 14006 with a lead content of not higher than 0.1 wt% but also Nos. 14001 to 14003 which contain large quantities of lead.
  • test pieces two test pieces, first and second test pieces, in the same shape 15 mm in outside diameter and 25 mm in length were cut out of each extruded test piece obtained as described above.
  • the first test piece was held for 30 minutes at 700°C, and then compressed 70 percent in the direction of axis to reduce the length from 25 mm to 7.5 mm.
  • the surface condition after the compression 700°C deformability
  • the results are given in Table 38 to Table 66.
  • the evaluation of deformability was made by visually checking for cracks on the side of the test piece. In Table 38 to Table 66, the test pieces with no cracks found are marked "o", those with small cracks are indicated in "_” and those with large cracks are represented by a symbol "x".
  • 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, %.
  • the first to thirteenth alloys are equal to or superior to the conventional alloys Nos. 14001 to 14004 and No. 14006 in hot workability and mechanical properties and are suitable for industrial use.
  • the seventh and eighth alloys in particular have the same level of mechanical properties as the conventional alloy No. 14005, the aluminum bronze which is the most excellent in strength of the expanded copper alloys under the JIS designations, and thus have understandably a prominent high strength feature.
  • first second, fifth, six and ninth to thirteenth 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 first and second alloys and the ninth to thirteenth alloys are excellent in corrosion resistance and favourablycomparable with the conventional alloys Nos.14001 to 14003 containing great amounts of lead. And it was confirmed that especially the fifth and sixth 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 In the stress corrosion cracking tests in accordance with the test method described in "JIS H 3250," a 150-mm-long 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 2.5% aqueous ammonia (ammonia diluted in the equivalent of pure water). To be exact, the test sample was held some 80 mm above the surface of aqueous ammonia in the desiccator.
  • test sample After the 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 Table 38 to Table 50 and Table 61 to Table 66.
  • the alloys which have developed clear cracks when held in the ammonia environment for two hours are marked "xx.”
  • the test samples which had no cracks at passage of two hours but were found to have clear cracks at 8 hours are indicated by "x.”
  • the test samples which had no cracks at 8 hours, but were found to have clear cracks at 24 hours were indicated by "_”.
  • the test samples which were found to have no cracks at all at 24 hours are given a symbol "o.”
  • test piece in the shape of a round bar with the surface cut to a outside diameter of 14 mm and the length cut to 30 mm was prepared from each of the following extruded test pieces: No. 9001 to No. 9005, No. 10001 to No. 10008, No. 11001 to No. 11007, No. 12001 to No. 12021 and No. 14001 to No. 14006.
  • Each test piece was then weighed to measure the weight before oxidation. After that, the test piece was placed In a porcelain crucible and held in an electric furnace maintained at 500°C. At passage of 100 hours, the test piece was taken out of the electric furnace and weighed to measure the weight after oxidation. From the measurements before and after oxidation was calculated the increase In weight by oxidation.
  • the weight of each test piece increased after oxidation.
  • the increase was brought about by high-temperature oxidation. Subjected to a high temperature, oxygen combines with copper, zinc and silicon to form Cu 2 O, ZnO, SiO 2 . That Is, oxygen increase contributes to the weight gain. It can be said, therefore, that the alloys which are the smaller in weight increase by oxidation are the more excellent in high-temperature oxidation resistance.
  • Table 61 to Table 64 and Table 66 The results obtained are shown In Table 61 to Table 64 and Table 66.
  • the ninth to twelfth alloys are equal to the conventional alloy No. 14005, an aluminum bronze ranking high in resistance to high-temperature oxidation among the expanded copper alloys under the JIS designations and are far smaller than any other conventional copper alloy.
  • the ninth to twelfth alloys are very excellent in machinability and resistance to high-temperature oxidation as well.
  • alloy composition (wt%) Cu Si Se P Sb As Zn 6101 76.1 3.0 0.04 0.05 0.02 remainder 6102 74.5 2.8 0.03 0.04 0.02 0.03 remainder 6103 74.3 2.6 0.31 0.04 remainder 6104 75.0 3.3 0.06 0.02 0.05 remainder 6105 73.9 2.9 0.10 0.11 remainder [Table 32] No. alloy composition (wt%) Cu Si Al P Zn 9001 72.6 2.3 0.8 0.03 remainder 9002 74.8 2.8 1.3 0.09 remainder 9003 77.2 3.6 0.2 0.21 remainder 9004 75.7 3.0 1.1 0.07 remainder 9005 78.0 3.8 0.7 0.12 remainder [Table 33] No.
  • machinability corrosion resistance hot workability mechanical properties stress resistance corrosion cracking resistance form of chippings condition of cut surface cutting force (N) maximum depth of corrosion ( ⁇ m) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 6061 ⁇ ⁇ 123 30 ⁇ 530 22 ⁇ 6062 ⁇ ⁇ 119 10 ⁇ 538 33 ⁇ 6063 ⁇ ⁇ 118 ⁇ 5 ⁇ 504 37 ⁇ 6064 ⁇ ⁇ 121 ⁇ 5 ⁇ 526 30 ⁇ 6065 ⁇ ⁇ 123 ⁇ 5 ⁇ 565 35 ⁇ No.
  • machinability corrosion resistance hot workabllity mechanical properties stress resistance corrosion cracking resistance form of chippings condition of cut surface cutting force (N) maximum depth of corrosion ( ⁇ m) 700°C deformabllity tensile strength (N/mm 2 ) elongation (%) 6066 ⁇ ⁇ 120 ⁇ 5 ⁇ 501 25 ⁇ 6067 ⁇ ⁇ 119 ⁇ 5 ⁇ 526 26 ⁇ 6068 ⁇ ⁇ 122 ⁇ 5 ⁇ 502 30 ⁇ 6069 ⁇ ⁇ 124 ⁇ 5 ⁇ 484 28 ⁇ 6070 ⁇ ⁇ 115 ⁇ 5 ⁇ 548 37 ⁇ 6071 ⁇ ⁇ 118 ⁇ 5 ⁇ 530 34 ⁇ 6072 ⁇ ⁇ 119 ⁇ 5 ⁇ 515 30 ⁇ 6073 ⁇ ⁇ 121 ⁇ 5 ⁇ 579 35 ⁇ 6074 ⁇ ⁇ 117 ⁇ 5 ⁇ 517 32 ⁇ 6075 ⁇ ⁇ 117 ⁇ 5 ⁇ 513 38 ⁇ 6076 ⁇ ⁇ 122 40

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Powder Metallurgy (AREA)
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Claims (1)

  1. Bleifreie Kupferlegierung, die 2.0 bis 4.0 Gew.% Silizium, 69 bis 79 Gew.% Kupfer umfasst und deren verbleibende Gew.% Zink sind, und die eine Gammaschicht in der Legierung bildet, und wobei die Legierung gegebenenfalls beinhaltet:
    a) mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Bismut, 0.02 bis 0.4 Gew.% Tellur und 0.02 bis 0.4 Gew.% Selen; oder
    b) mindestens ein Element, ausgewählt aus 0.02 bis 0.25 Gew.% Phosphor, 0.02 bis 0.15 Gew.% Antimon und 0.02 bis 0.15 Gew.% Arsen; oder
    c) mindestens ein Element, ausgewählt aus 0.3 bis 3.5 Gew.% Zinn, 0.02 bis 0.25 Gew.% Phosphor, 0.02 bis 0.15 Gew.% Antimon und 0.02 bis 0.15 Gew.% Arsen; mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Bismut, 0.02 bis 0.4 Gew.% Tellur und 0.02 bis 0.4 Gew.% Selen; oder
    d) 0.1 bis 1.5 Gew.% Aluminium; und 0.02 bis 0.25 Gew.% Phosphor; oder
    e) 0.1 bis 1.5 Gew.% Aluminium; 0.02 bis 0.25 Gew.% Phosphor; mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Chrom und 0.02 bis 0.4 Gew.% Titan; oder
    f) 0.1 bis 1.5 Gew.% Aluminium; 0.02 bis 0.25 Gew.% Phosphor; mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Bismut, 0.02 bis 0.4 Gew.% Tellur und 0.02 bis 0.4 Gew.% Selen; oder
    g) 0.1 bis 1.5 Gew.% Aluminium; 0.02 bis 0.25 Gew.% Phosphor; mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Chrom, und 0.02 bis 0.4 Gew.% Titan; mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Bismut, 0.02 bis 0.4 Gew.% Titan; mindestens ein Element, ausgewählt aus 0.02 bis 0.4 Gew.% Bismut, 0.02 bis 0.4 Gew.% Tellur und 0.02 bis 0.4 Gew.% Selen.
EP05075421.7A 1998-10-12 1998-11-16 Bleifrei Automatenkupferlegierung Expired - Lifetime EP1559802B1 (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

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EP1559802A1 EP1559802A1 (de) 2005-08-03
EP1559802B1 true EP1559802B1 (de) 2014-01-15

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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
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

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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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EP1600515B1 (de) 2008-07-30
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WO2000022182A1 (en) 2000-04-20
CA2314144C (en) 2006-08-22
EP1600515A2 (de) 2005-11-30
EP1600517B1 (de) 2009-02-18
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
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
EP1600516A2 (de) 2005-11-30

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