EP1600516B1 - Bleifreie Automatenkupferlegierung - Google Patents

Bleifreie Automatenkupferlegierung Download PDF

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Publication number
EP1600516B1
EP1600516B1 EP05017190A EP05017190A EP1600516B1 EP 1600516 B1 EP1600516 B1 EP 1600516B1 EP 05017190 A EP05017190 A EP 05017190A EP 05017190 A EP05017190 A EP 05017190A EP 1600516 B1 EP1600516 B1 EP 1600516B1
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EP
European Patent Office
Prior art keywords
weight
percent
free
remainder
lead
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Expired - Lifetime
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EP05017190A
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English (en)
French (fr)
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EP1600516A3 (de
EP1600516A2 (de
Inventor
Keiichiro Oishi
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Sambo Copper Alloy Co Ltd
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Sambo Copper Alloy 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 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 vapour 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 are made of those alloys will dissolve out into drinking water.
  • the document GB-A-359 570 discloses a copper-silicon-zinc alloy with a content of 65 to 80 % of copper and 2 to 6 % of silicon.
  • US-A-1 954 003 discloses an alloy consisting of from 65 % and up to 94 % copper, from 2 % to 6 % silicon, from 3 % to 28 % zinc, and not more than 2 % aluminum.
  • the document GB-A-354 966 discloses copper-silicon-zinc alloys with up to 6 % silicon and up to 20 % zinc.
  • the document US-A-3 900 349 discloses a silicon brass alloy consisting of 3-21 weight % zinc, 2.5 to 7 weight % silicon, said amounts of zinc and silicon being sufficient to produce a structure consisting of alpha plus zeta phases in the brass, from 0.030 weight % up to the percentage by weight of solid solubility of one or more elements of the group consisting of arsenic, antimony and phosphorus, remainder being copper.
  • the document GB-A-1 443 090 discloses a silicon brass alloy consisting of 3-21 weight % zinc, 2.5 to 6 weight % silicon, said amounts of zinc and silicon being sufficient to produce a structure consisting of alpha plus zeta phases in the brass, from 0.030 weight % up to the percentage by weight of solid solubility of one or more elements of the group consisting of arsenic, antimony and phosphorus, remainder being copper.
  • 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 provides a lead-free, free-cutting copper alloy which comprises 70 to 80 percent, by weight, of copper; 1.8 to 3.5 percent, by weight, of silicon; 0.02 to 0.25 percent, by weight, of phosphorous and the remaining percent, by weight, of zinc and wherein the metal structure of the free cutting copper alloy has at least one phase selected from the ⁇ (gamma) phase and the ⁇ (kappa) phase.
  • Tin works the same way as silicon. That is, if tin is added to a Cu-Zn alloy, a gamma phase will be formed and the machinability of the Cu-Zn alloy will be improved. For example, the addition of tin in as amount of 1.8 to 4.0 percent by weight would bring about a high machinability in the Cu-Zn alloy containing 58 to 70 percent, by weight, of copper, even if silicon is not added. Therefore, the addition of tin to the Cu-Si-Zn alloy could facilitate the formation of a gamma phase and further improve the machinability of the Cu-Si-Zn alloy.
  • the gamma phase is formed with the addition of tin in an amount of 1.0 or more percent by weight and the formation reaches the saturation point at 3.5 percent, by weight, of tin. If tin exceeds 3.5 percent by weight, the ductility will drop instead. With the addition of tin in less than 1.0 percent by weight, on the other hand, no gamma phase will be formed. If the addition is 0.3 percent or more by weight, then tin will be effective in uniformly dispersing the gamma phase formed by silicon. Through that effect of dispersing the gamma phase, too, the machinability is improved. In other words, the addition of tin in not smaller than 0.3 percent by weight improves the machinability.
  • Aluminum is, too, effective in promoting the formation of the gamma phase.
  • the addition of aluminum together with tin or in place of tin could further improve the machinability of the Cu-Si-Zn.
  • Aluminum is also effective in improving the strength, wear resistance and high temperature oxidation resistance as well as the machinability and also in keeping down the specific gravity. If the machinability is to be improved at all, aluminum will have to be added in at least 1.0 percent by weight But the addition of more than 3.5 percent by weight could not produce the proportional results. Instead, that could affect the ductility as is the case with aluminum.
  • phosphorus As to phosphorus, it has no property of forming the gamma phase as tin and aluminum. But phosphorus works to uniformly disperse and distribute the gamma phase formed as a result of the addition of silicon alone or with tin or aluminum or both of them. That way, the machinability improvement through the formation of gamma phase is further enhanced.
  • phosphorus helps refine the crystal grains in the alpha phase in the matrix, improving hot workability and also strength and resistance to stress corrosion cracking.
  • phosphorous substantially increases the flow of molten metal in casting. To produce such results, phosphorus will have to be added in an amount not smaller than 0.02 percent by weight. But if the addition exceeds 0.25 percent by weight, no proportional effect can be obtained. Instead, there would be a fall in hot forging property and extrudability.
  • the alloy of the present invention has improved machinability by adding to the Cu-Si-Zn-P alloy at least one element selected from 0.3 to 3.5 percent, by weight, of tin and from 1.0 to 3.5 percent, by weight, of aluminum.
  • tin, aluminum and phosphorus are to improve the machinability by forming a gamma phase or dispersing that phase, and work closely with silicon in promoting the improvement in machinability through the gamma phase.
  • machinability is improved by not only silicon, but by tin or aluminum. Even if the addition of silicon is less than 2.0 percent by weight, silicon along with tin or aluminum will be able to enhance the machinability to an industrially satisfactory level as long as the percentage of silicon is 1.8 or more percent by weight.
  • the addition of silicon is not larger than 4.0 percent by weight, the addition of tin or aluminum will saturate the effect of silicon in improving the machinability, when the silicon content exceeds 3.5 percent by weight.
  • the addition of silicon is set at 1.8 to 3;.5 percent by weight in the alloy of the present invention.
  • the alloy of the present invention may additionally comprise 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.
  • the alloy of the present invention may further comprise at least one element selected from bismuth, tellurium and selenium 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 present invention also provides a method of forming a lead-free, free cutting alloy having a metal structure which has at least one phase selected from the ⁇ (gamma) phase and the ⁇ (kappa) phase which comprises alloying copper, silicon, phosphorous and zinc in an amount of 70 to 80 percent, by weight, of copper, 1.8 to 3.5 percent, by weight, of silicon; 0.02 to 0.25 percent, by weight, of phosphorus and the remaining percent by weight of zinc.
  • the method of the present invention may also further comprise subjecting said lead free, free cutting alloy to a heat treatment for 30 minutes to 5 hours at 400°C 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 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” 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.
  • Fig. 1 shows perspective views of cuttings formed in cutting a round bar of copper alloy by lathe.
  • cylindrical ingots with compositions given in Tables 1 to 4 each 100 mm in outside diameter and 150 mm in length, were hot extruded into a round bar 15 mm in outside diameter at 750°C to produce the following test pieces: invention alloys Nos 3004 to 3007 and 3010 to 3012, and 4022 to 4049.
  • 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 Table 6 to Table 10.
  • 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 an arc with a half winding to a spiral with two about windings as shown in (C), Fig. 1 do not cause such serious trouble as the chips in the form of a spiral with three or more windings yet are not easy to remove and could get tangled with the tool or damage 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 (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. Those taken into account, it is appropriate to consider the chips in (B) are the best, and the second best are the chips in (A). Those in (C) and (D) are not good. In Table 6 to Table 10, the chips judged to be shown in (B), (A), (C) and (D) are indicated by the symbols " ⁇ ", "o", " ⁇ " and "x" respectively.
  • the surface condition of the cut metal surface was checked after cutting work.
  • the results are shown in Table 6 to Table 10.
  • 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 the 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 invention alloys 3004 to 3007 and 3010 to 3012 are all equal to the conventional lead- contained alloys Nos. 14001 to 14003 in machinability. Especially with regard to formation of the chips, 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 alloys of the present invention were examined in comparison with the conventional alloys in hot workability and mechanical properties.
  • hot compression and tensile tests were conducted the following way.
  • 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 was visually evaluated.
  • the results are given in Table 6 to Table 10.
  • the evaluation of deformability was made by visually checking for cracks on the side of the test piece. In Table 6 to Table 10, the test pieces with not cracks found are marked "o", those with small cracks are indicated in " ⁇ " and those with large cracks are represented by symbol "x".
  • the second test pieces were put to a tensile test by the commonly practiced test method to determine the tensile strength, N/mm 2 and elongation, %.
  • alloys of the present invention 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 alloys of the present invention are excellent in corrosion resistance and favourable comparable with the conventional alloys Nos. 14001 to 14003 containing great amounts of lead.
  • 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 12.5% 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 sulphuric acid solution 10% and examined for cracks under a magnifier of 10 magnifications.
  • the results are given in Table 6 to Table 10.
  • 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 least 24 hours are given a symbol "o.”
  • machinability corrosion resistance hot work ability mechanical properties stress resistance corrosion cracking resistance high-temperature oxidation form of chipings condition of cut surface cutting force (N) maximum depth of corrosion ( ⁇ m) 700°C deforma bility tensile strength (N/mm 2 ) elongation (%) increase in weight by oxidation (mg/10cm 2 ) 14001 ⁇ ⁇ 103 1100 ⁇ 408 37 xx 1.8 14002 ⁇ ⁇ 101 1000 x 387 39 xx 1.7.

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  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Claims (6)

  1. Bleifreie Kupfer-Automatenlegierung, welche 70 bis 80 Gewichtsprozent an Kupfer, 1,8 bis 3,5 Gewichtsprozent an Silikon, 0,02 bis 0,25 Gewichtsprozent an Phosphor, optional mindestens ein Element, welches ausgewählt ist aus 0,3 bis 3,5 Gewichtsprozent an Zinn und 1,0 bis 3,5 Gewichtsprozent an Aluminium, und/oder optional mindestens ein Element, welches ausgewählt ist aus 0,02 bis 0,4 Gewichtsprozent an Wismut, 0,02 bis 0,4 Gewichtsprozent an Tellurium und 0,02 bis 0,4 Gewichtsprozent an Selen, und die restlichen Gewichtsprozentanteile an Zink umfasst, wobei die Metallstruktur der Kupfer-Automatenlegierung mindestens eine Phase aufweist, die ausgewählt ist aus der γ (gamma)-Phase und der κ (kappa)-Phase.
  2. Bleifreie Kupfer-Automatenlegierung nach Anspruch 1, wobei, wenn diese auf einer umlaufenden Oberfläche mit einem Drehmeißel, der als gerades Werkzeug mit scharfer Spitze bereitgestellt ist, mit einem Spanwinkel von -8 (minus 8) und einer Schnittrate von 50 m/min, einer Schnitttiefe von 1,5 mm und einer Vorschubrate von 0,11 mm/U geschnitten wird, sich Späne ergeben, welche eine oder mehrere Formen aufweisen, die ausgewählt sind aus der Gruppe, die aus einer Bogenform und einer feinen Nadelform besteht.
  3. Bleifreie Kupfer-Automatenlegierung nach einem der vorhergehenden Ansprüche, welche für 30 Minuten bis zu 5 Stunden einer Hitzebehandlung bei 400 bis 600 °C unterzogen ist.
  4. Verfahren zur Bildung einer bleifreien Automatenlegierung mit einer Metallstruktur, welche mindestens eine Phase aufweist, die aus der γ (gamma)-Phase und der κ (kappa)-Phase ausgewählt ist, welche Legierungen aus Kupfer, Silikon, Phosphor und Zink in einer Menge von 70 bis 80 Gewichtsprozent an Kupfer, 1,8 bis 3,5 Gewichtsprozent an Silikon, 0,02 bis 0,25 Gewichtsprozent an Phosphor, optional Legierungen mit mindestens einem Element, welches ausgewählt ist aus Zinn und Aluminium in einer Menge von 0,3 bis 3,5 Gewichtsprozent an Zinn und 1,0 bis 3,5 Gewichtsprozent an Aluminium, und/oder optional Legierungen mit mindestens einem Element, welches ausgewählt ist aus Wismut, Tellurium und Selen in einer Menge von 0,02 bis 0,4 Gewichtsprozent an Wismut, 0,02 bis 0,4 Gewichtsprozent an Tellurium und 0,02 bis 0,4 Gewichtsprozent an Selen und den restlichen Gewichtsprozentanteil an Zink umfasst.
  5. Verfahren nach Anspruch 4, wobei das Silikon als eine Cu-Si-Legierung bereitgestellt ist.
  6. Verfahren nach einem der Ansprüche 4 bis 5, wobei die bleifreie Automatenlegierung für 30 Minuten bis zu 5 Stunden einer Hitzebehandlung bei 400 bis 600 °C unterzogen ist.
EP05017190A 1998-10-12 1998-11-16 Bleifreie Automatenkupferlegierung Expired - Lifetime EP1600516B1 (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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EP98953071A Division EP1045041B1 (de) 1998-10-12 1998-11-16 Bleifreie automatenkupferlegierung

Publications (3)

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EP1600516A2 EP1600516A2 (de) 2005-11-30
EP1600516A3 EP1600516A3 (de) 2005-12-14
EP1600516B1 true EP1600516B1 (de) 2007-07-18

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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

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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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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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JP5326114B2 (ja) 2009-04-24 2013-10-30 サンエツ金属株式会社 高強度銅合金
EP2290114A1 (de) 2009-08-04 2011-03-02 Gebr. Kemper GmbH + Co. KG Metallwerke Wasserführendes Bauteil
TWI398532B (zh) 2010-01-22 2013-06-11 Modern Islands Co Ltd Lead-free brass alloy
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JP2011214095A (ja) * 2010-03-31 2011-10-27 Joetsu Bronz1 Corp 鋳造用無鉛快削黄銅合金
JP2011214094A (ja) * 2010-03-31 2011-10-27 Joetsu Bronz1 Corp 無鉛快削黄銅合金
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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
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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