EP1508626A1 - Alliage de décolletage à base de cuivre. - Google Patents

Alliage de décolletage à base de cuivre. Download PDF

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EP1508626A1
EP1508626A1 EP04077561A EP04077561A EP1508626A1 EP 1508626 A1 EP1508626 A1 EP 1508626A1 EP 04077561 A EP04077561 A EP 04077561A EP 04077561 A EP04077561 A EP 04077561A EP 1508626 A1 EP1508626 A1 EP 1508626A1
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weight
percent
remainder
alloy
silicon
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EP1508626B1 (fr
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Keiichiro Sambo Copper Alloy Co. Ltd. Oishi
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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

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  • the present invention relates to 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 so enhanced in machinability with the addition of 1.0 to 6.0 percent, by weight, of lead as to give industrially satisfactory results as easy-to-work copper alloy.
  • 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 does not form a solid solution in the matrix but disperses in granular form, thereby improving the machinability of those alloys.
  • lead has to be added in as much as 2.0 or more percent by weight. If the addition of lead is less than 1.0 percent by weight, chippings will be spiral in form as (D) in Fig. 1. Spiral chippings cause various troubles such as, for example, tangling with the tool. If, on the other hand, the content of lead is 1.0 or more percent by weight and not larger than 2.0 percent by weight, the cut surface will be rough, though that will produce some results such as reduction of the cutting resistance. It is usual, therefore, that lead is added in not smaller than 2.0 percent by weight.
  • Some expanded copper alloys in which a high degree of cutting property is required are mixed with some 3.0 or more percent, by weight, of lead. Further, some bronze castings have a lead content of as much as some 5.0 percent, by weight.
  • lead-mixed alloys have been greatly limited in recent years, because lead contained therein is harmful to humans as an environment pollutant. That is, the lead-contained alloys pose a threat to human health and environmental hygiene because lead finds its way in metallic vapor that generates in the steps of processing those alloys at high temperatures such as melting and casting and there is also danger that lead contained in the water system metal fittings, valves and others made of those alloys will dissolve out into drinking water.
  • 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.
  • a free-cutting copper alloy with an excellent easy-to-cut feature which is composed of 69 to 79 percent, by weight, of copper, 2.0 to 4.0 percent, by weight, of silicon, 0.02 to 0.4 percent, by weight, of lead and the remaining percent, by weight, of zinc.
  • this copper alloy will be hereinafter called the "first invention alloy”.
  • 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 the same 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 so as to bring about a high level of machinability meeting the industrial requirements, while making it possible to reduce greatly the lead content. 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 the 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 first invention alloy is composed of 69 to 79 percent, by weight, of copper and 2.0 to 4.0 percent, by weight, of silicon respectively.
  • 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 dezincing corrosion resistance will be improved to some extent.
  • the addition of lead is set at 0.02 to 0.4 percent by weight on this ground.
  • a sufficient level of machinability is obtained by adding silicon that has the aforesaid effect even if the addition of lead is reduced.
  • lead has to be added in the amount not smaller than 0.02 percent by weight if the alloy is to be superior to the conventional free-cutting copper alloy in machinability, while the addition of lead exceeding 0.4 percent would have adverse effects, resulting in a rough surface condition, poor hot workability such as poor forging behaviour and low cold ductility. Meanwhile, it is expected that such a small content of not higher than 0.4 percent by weight will be able to clear the lead-related regulations however strictly they are to be stipulated in the advanced nations including Japan in the future.
  • the addition range of lead is set at 0.02 to 0.4 percent by weight in the first and also second to eleventh invention alloys which will be described later.
  • Another embodiment of the present invention is a free-cutting copper alloy also with an excellent easy-to-cut feature which is composed of 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; one 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.
  • This second copper alloy will be hereinafter called the "second invention alloy”.
  • the second invention alloy is composed of the first invention alloy and, in addition, one selected element 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.
  • Bismuth, tellurium and selenium as well as lead do not form a solid solution with the matrix but disperse in granular form to enhance the machinability. That makes up for the reduction of the lead content.
  • the addition of any one of those elements along with silicon and lead could further improve the machinability beyond the level hoped from the addition of silicon and lead.
  • the second invention alloy is worked out in which one element selected from among bismuth, tellurium and selenium is mixed.
  • the addition of bismuth, tellurium or selenium as well as silicon and lead could make the copper alloy so machinable that complicated forms could be freely cut out at a high speed.
  • the second invention alloy is prepared with the addition of bismuth, tellurium or selenium kept to 0.02 to 0.4 percent by weight.
  • the addition of bismuth, tellurium or selenium which improves the machinability of the copper alloy though a mechanism different from that of silicon as mentioned above, would not affect the proper contents of copper and silicon. On this ground, the contents of copper and silicon in the second invention alloy are set at the same level as those in the first invention alloy.
  • Another embodiment of the present invention is a free-cutting copper alloy also with an excellent easy-to-cut feature which is composed of 70 to 80 percent, by weight, of copper; 1.8 to 3.5 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; at least one selected from among 0.3 to 3.5 percent, by weight, of tin, 1.0 to 3.5 percent, by weight, of aluminum, and 0.02 to 0.25 percent, by weight, of phosphorus; and the remaining percent, by weight, of zinc.
  • This third copper alloy will be hereinafter called the "third invention alloy”.
  • Tin works the same way as silicon. That is, if tin is added, a gamma phase will be formed and the machinability of the Cu-Zn alloy will be improved. For example, the addition of tin in the 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 present. 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 the 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 the amount less than 1.0 percent by weight, on the other hand, an insufficient gamma phase will be formed. If the addition is 0.3 or more percent 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 the amount not smaller than 0.3 percent by weight improves the machinability.
  • Aluminum is, too, effective in facilitating the formation'of the gamma phase.
  • the addition of aluminum together with or in place of tin could further improve the machinability of the Cu-Si-Zn alloy.
  • 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 the amount of 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 lower the ductility as is the case with tin.
  • 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. Furthermore, phosphorus substantially increases the flow of molten metal in casting. To produce such results, phosphorus will have to be added in the 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 third invention alloy is improved in machinability by adding to the Cu-Si-Pb-Zn alloy (first invention alloy) at least one selected from among 0.3 to 3.5 percent, by weight, of tin, 1.0 to 3.5 percent, by weight, of aluminum, and 0.02 to 0.25 percent, by weight, of phosphorus.
  • 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.
  • the addition of silicon is smaller than that in the second invention alloy to which is added bismuth, tellurium or selenium which replaces silicon of the first invention in improving machinability. That is, those elements bismuth, tellurium and selenium contribute to improving the machinability, not acting on the gamma phase but dispersing in the form of grains in the matrix.
  • a free-cutting copper alloy also with an excellent easy-to-cut feature which is composed of 70 to 80 percent, by weight, of copper; 1.8 to 3.5 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; at least one element selected from among 0.3 to 3.5 percent, by weight, of tin, 1.0 to 3.5 percent, by weight, of aluminum, and 0.02 to 0.25 percent, by weight, of phosphorus; 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.
  • This fourth copper alloy will be hereinafter called the "fourth invention alloy”.
  • the fourth invention alloy has any one 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 in addition to the components in the third invention alloy.
  • the grounds for mixing those additional elements and setting those amounts to be added are the same as given for the second invention alloy.
  • a free-cutting copper alloy with an excellent easy-to-cut feature and with a high corrosion resistance which is composed of 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; 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.
  • This fifth copper alloy will be hereinafter called the "fifth invention alloy"
  • the fifth invention alloy has, in addition to the first invention alloy, 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.
  • Tin is effective in improving not only the machinability but also corrosion resistance properties (dezincification 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 fifth invention alloy is thus improved in corrosion resistance by the property of tin and in machinability mainly by adding silicon. Therefore, the contents of silicon and copper in this alloy are set at the same as those in the first invention alloy.
  • tin would have to be added in the 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 amount added 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 corrosion), forgeability, stress corrosion cracking resistance and mechanical strength.
  • the fifth invention alloy is thus improved in corrosion resistance and others through the action 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 more than 0.25 percent by weight would not be so effective as hoped from the quantity added. Rather, that would reduce the hot forgeability and extrudability.
  • the fifth invention alloy 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 (which improve corrosion resistance) in quantities within the aforesaid limits in addition to the same quantities of copper and silicon as in the first invention copper alloy.
  • 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 - the same level as in the first invention alloy in which any other machinability improver than silicon and a small amount of lead is not added - because tin and phosphorus work mainly as corrosion resistance improver like antimony and arsenic.
  • a free-cutting copper alloy also with an excellent easy-to-cut feature and with a high corrosion resistance which is composed of 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; 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; 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.
  • This sixth copper alloy will be hereinafter called the "sixth invention alloy”.
  • the sixth invention alloy has any 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 in addition to the components in the fifth invention alloy.
  • the machinability is improved by adding, in addition to silicon and lead, any one element selected from among bismuth, tellurium and selenium as in the second invention alloy and the corrosion resistance and other properties are raised by adding at least one selected from among tin, phosphorus, antimony and arsenic as in the fifth invention alloy.
  • the additions of copper, silicon, bismuth, tellurium and selenium are set at the same levels as those in the second invention alloy, while the additions of tin, phosphorus, antimony and arsenic are adjusted to those in the fifth invention alloy.
  • a free-cutting copper alloy also with an excellent easy-to-cut feature and with an excellent high strength feature and high corrosion resistance which is composed of 62 to 78 percent, by weight, of copper; 2.5 to 4.5 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; at least one element selected from among 0.3 to 3.0 percent, by weight, of tin, 0.2 to 2.5 percent, by weight, of aluminum, and 0.02 to 0.25 percent, by weight, of phosphorus; and at least one element selected from among 0.7 to 3.5 percent, by weight, of manganese and 0.7 to 3.5 percent, by weight, of nickel; and the remaining percent, by weight, of zinc.
  • the seventh copper alloy will be hereinafter called the "seventh invention alloy”.
  • Manganese and nickel combine with silicon to form intermetallic compounds represented by MnxSiy or NixSiy which are evenly precipitated in the matrix, thereby raising the wear resistance and strength. Therefore, the addition of manganese and nickel or either of the two would improve the high strength feature and wear resistance. Such effects will be exhibited if manganese and nickel are added in the amount of not less than 0.7 percent by weight respectively. But the saturation state is reached at 3.5 percent by weight, and even if the addition is increased beyond that, no proportional results will be obtained.
  • the addition of silicon is set at 2.5 to 4.5 percent by weight to match the addition of manganese or nickel, taking into consideration the consumption to form intermetallic compounds with those elements.
  • tin, aluminum and phosphorus help to reinforce the alpha phase in the matrix, thereby improving the machinability.
  • Tin and phosphorus disperse the alpha and gamma phases, by which the strength, wear resistance and also machinability are improved.
  • Tin in the amount of 0.3 or more percent by weight is effective in improving the strength and machinability. But if the addition exceeds 3.0 percent by weight, the ductility will fall. For this reason, the addition of tin is set at 0.3 to 3.0 percent by weight to raise the high strength feature and wear resistance in the seventh invention alloy and also to enhance the machinability.
  • Aluminum also contributes to improving the wear resistance and exhibits its effect of reinforcing the matrix when added in the amount of 0.2 or more percent by weight.
  • the addition of aluminum is set at 0.2 to 2.5 in consideration of improvement of machinability.
  • the addition of phosphorus disperses the gamma phase and at the same time pulverizes the crystal grains in the alpha phase in the matrix, thereby improving the hot workability and also the strength and wear resistance. Furthermore, it is very effective in improving the flow of molten metal in casting. Such results will be produced when phosphorus is added in the amount of 0.02 to 0.25 percent by weight.
  • the content of copper is set at 62 to 78 percent by weight in the light of the addition of silicon and the property of manganese and nickel of combining with silicon.
  • a free-cutting copper alloy also with an excellent easy-to-cut feature and with an excellent high-temperature oxidation resistance which comprises 69 to 79 percent, by weight, of copper, 2.0 to 4.0 percent, by weight, of silicon, 0.02 to 0.4 percent, by weight, of lead, 0.1 to 1.5 percent, by weight, of aluminum, and 0.02 to 0.25 percent, by weight, of phosphorus, and the remaining percent, by weight, of zinc.
  • the eighth copper alloy will be hereinafter called the "eighth invention alloy”.
  • Aluminum is an element which improves the strength, machinability, wear resistance and also high-temperature oxidation resistance. Silicon, too, has a property of enhancing the machinability, strength, wear resistance, resistance to stress corrosion cracking and also high-temperature oxidation resistance. Aluminum works to raise the high-temperature oxidation resistance when it is used together with silicon and that in not smaller than 0.1 percent by weight. But even if the addition of aluminum increases beyond 1.5 percent by weight, no proportional results can be expected. For this reason, the addition of aluminum is set at 0.1 to 1.5 percent by weight.
  • Phosphorus is added to enhance the flow of molten metal in casting. Phosphorus also works for improvement of the aforesaid machinability, dezincification corrosion resistance and also high-temperature oxidation resistance in addition to the flow of molten metal. Those effects are exhibited when phosphorus is added in the amount not smaller than 0.02 percent by weight. But even if phosphorus is used in more than 0.25 percent by weight, it will not result in a proportional increase in effect rather weakening the alloy. For this consideration, the addition of phosphorus settles down on 0.02 to 0.25 percent by weight.
  • silicon is added to improve the machinability as mentioned above, it is also capable of improving the flow of molten metal like phosphorus.
  • the effect of silicon in improving the flow of molten metal is exhibited when it is added in the amount of not smaller than 2.0 percent by weight.
  • the range of the addition for the flow improvement overlaps that for improvement of the machinability. These taken into consideration, the addition of silicon is set to 2.0 to 4.0 percent by weight.
  • a free-cutting copper alloy also with excellent easy-to-cut feature coupled with a good high-temperature oxidation resistance which is composed of 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; 0.1 to 1.5 percent, by weight, of aluminum; 0.02 to 0.25 percent, by weight, of phosphorus; 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 ninth copper alloy will be hereinafter called the "ninth invention alloy”.
  • the ninth invention alloy contains 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 in addition to the components of the eighth invention alloy. While a high-temperature oxidation resistance as good as in the eighth invention alloy is secured, the machinability is further improved by adding one element selected from among bismuth and other elements which are as effective as lead in raising the machinability.
  • a free-cutting copper alloy also with excellent easy-to-cut feature and a good high-temperature oxidation resistance which is composed of 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; 0.1 to 1.5 percent, by weight, of aluminum; 0.02 to 0.25 percent, by weight, of phosphorus; at least one selected from among 0.02 to 0.4 percent, by weight, of chromium and 0.02 to 0.4 percent, by weight, of titanium; and the remaining percent, by weight, of zinc.
  • the tenth copper alloy will be hereinafter called the "tenth invention alloy”.
  • Chromium and titanium are intended for improving the high-temperature oxidation resistance. Good results can be expected especially when they are added together with aluminum to produce a synergistic effect. Those effects are exhibited when the addition is no less than 0.02 percent by weight, whether they are added alone or in combination. The saturation point is 0.4 percent by weight.
  • the tenth invention alloy has at least one element selected from among 0.02 to 0.4 percent by weight of chromium and 0.02 to 0.4 percent by weight of titanium in addition to the components of the eighth invention alloy and thus further improved over the eighth invention alloy with regard to the high-temperature oxidation resistance.
  • a free-cutting copper alloy also with excellent easy-to-cut feature and a good high-temperature oxidation resistance which is composed of 69 to 79 percent, by weight, of copper; 2.0 to 4.0 percent, by weight, of silicon; 0.02 to 0.4 percent, by weight, of lead; 0.1 to 1.5 percent, by weight, of aluminum; 0.02 to 0.25 percent, by weight, of phosphorus; at least one element selected from among 0.02 to 0.4 percent, by weight, of chromium and 0.02 to 0.4 percent, by weight, of titanium; 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 eleventh copper alloy will be hereinafter called the "eleventh invention alloy”.
  • the eleventh invention alloy contains any one 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 in addition to the components of the tenth invention alloy. While as high a high-temperature oxidation resistance as in the tenth invention alloy is secured, the eleventh invention alloy is further improved in machinability by adding one element selected from among bismuth and other elements which are as effective as lead in raising the machinability.
  • a free-cutting copper alloy also with further improved easy-to-cut feature obtained by subjecting any one of the preceding respective invention alloys to a heat treatment for 30 minutes to 5 hours at 400 to 600°C.
  • the twelfth copper alloy will be hereinafter called the "twelfth invention alloy”.
  • the first to eleventh invention alloys contain machinability improving elements such as silicon and have an excellent machinability because of the addition of such elements.
  • the effect of those machinability improving elements could be further enhanced by heat treatment.
  • the first to eleventh invention alloys 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.
  • the alloys with a low content of copper in particular 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.
  • first invention alloys Nos. 1001 to 1007 As the first series of examples of the present invention, cylindrical ingots with compositions given in Tables 1 to 15, 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: first invention alloys Nos. 1001 to 1007, second invention alloys Nos. 2001 to 2006, third invention alloys Nos. 3001 to 3010, fourth invention alloys Nos. 4001 to 4021, fifth invention alloys Nos. 5001 to 5020, sixth invention alloys Nos. 6001 to 6045, seventh invention alloys Nos. 7001 to 7029, eighth invention alloys Nos. 8001 to 8008, ninth invention alloys Nos. 9001 to 9006, tenth invention alloys Nos.
  • 12003 is an alloy test piece obtained by heat-treating an extruded test piece with the same composition as first invention alloy No. 1007 under the same conditions as for No. 12001 - for 30 minutes at 580°C.
  • No. 12004 is an alloy test piece obtained by heat-treating an extruded test piece with the same composition as No. 1007 under the same conditions as for No. 12002 - for two hours at 450°C.
  • This aluminum bronze is the most excellent of the expanded copper alloys under the JIS designations with regard to strength and wear resistance.
  • No. 13006 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 18 to Table 33.
  • the chippings 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.
  • chippings in the form of a fine needle as (A) in Fig. 1 or in the form of arc shaped pieces as (B) will not present such problems as mentioned above and are not bulky as the chippings in (C) and (D) and easy to process.
  • fine chippings as (A) still could creep in on the slide table 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 18 to Table 33.
  • 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 invention alloys are all equal to the conventional lead-contained alloys Nos. 13001 to 13003 in machinability: first invention alloys Nos. 1001 to 1007, second invention alloys Nos. 2001 to 2006, third invention alloys Nos. 3001 to 3010, fourth invention alloys Nos. 4001 to 4021, fifth invention alloys Nos. 5001 to 5020, sixth invention alloys Nos. 6001 to 6045, seventh invention alloys Nos. 7001 to 7029, eighth invention alloys Nos. 8001 to 8008, ninth invention alloys Nos. 9001 to 9006, tenth invention alloys Nos. 10001 to 10008, eleventh invention alloys Nos.
  • those invention alloys are favorably compared not only with the conventional alloys Nos. 13004 to 13006 with a lead content of not higher than 0.1 percent by weight but also Nos. 13001 to 13003 which contain large quantities of lead.
  • the twelfth invention alloys Nos. 12001 to 12004 which are obtained by heat-treating the first invention alloys Nos. 1006 and 1007, are improved over the first invention alloys in machinability. It is understood that a proper heat treatment could further enhance the machinability of the first to eleventh invention alloys, depending upon the alloy compositions and other conditions.
  • 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 at the compression rate of 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 were given in Table 18 to Table 33.
  • the evaluation of deformability was made by visually checking for cracks on the side of the test piece. In Table 18 to Table 33, the test pieces with no cracks found are marked " ⁇ "; those with small cracks are indicated by " ⁇ " 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 twelfth invention alloys are equal to or superior to the conventional alloys Nos. 13001 to 13004 and No. 13006 in hot workability and mechanical properties and are suitable for industrial use.
  • the seventh invention alloys in particular have the same level of mechanical properties as the conventional alloy No. 13005, i.e. 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 to six and eighth to twelfth invention alloys were put to dezincification corrosion 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 test piece taken from each extruded test piece was imbedded laid in a phenolic resin material in such a way that the exposed test piece surface is perpendicular to the extrusion direction of the extruded test piece.
  • the surface of the test piece was polished with emery paper No. 1200, and then ultrasonic-washed in pure water and dried.
  • the test piece thus prepared was dipped in a 12.7 g/l aqueous solution of cupric chloride dihydrate (CuCl 2 .2H 2 O) 1.0% and left standing for 24 hours at 75°C.
  • the test piece was taken out of the aqueous solution and the maximum depth of dezincing corrosion was determined.
  • the measurements of the maximum dezincification corrosion depth are given in Table 18 to Table 25 and Table 28 to Table 33.
  • the first to fourth invention alloys and the eighth to twelfth invention alloys are excellent in corrosion resistance in comparison with the conventional alloys Nos. 13001 to 13003 which contain great amount of lead. And it was confirmed that especially the fifth and sixth invention alloys whose improvement in both machinability and corrosion resistance has been intended are very high in corrosion resistance in comparison with the conventional alloy No. 13006, a naval brass which is the most resistant to corrosion of all the expanded alloys under the JIS designations.
  • test piece In the stress corrosion cracking tests in accordance with the test method described in "JIS H 3250", a 150-mm-long test piece was cut out from each extruded material. The test piece was bent with the center placed on an arc-shaped tester with a radius of 40 mm in such a way that one end forms an angle of 45 degrees with respect the other end. The test piece 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 piece was held some 80 mm above the surface of aqueous ammonia in the desiccator.
  • test piece After the test piece was left standing in the ammonia environment for 2 hours, 8 hours and 24 hours, the test piece 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 18 to Table 25 and Table 28 to Table 33.
  • the alloys which developed clear cracks when held in the ammonia environment for two hours are marked "xx.”
  • the test pieces which had no cracks at two hours but were found clearly cracked in 8 hours are indicated in "x.”
  • the test pieces which had no cracks in 8 hours, but were found clearly to have cracks in 28 hours are identified by the symbol " ⁇ ".
  • the test pieces which were found to have no cracks at all in 24 hours are given a symbol " ⁇ ".
  • Test' pieces 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 were prepared from each of the following extruded materials: No. 8001 to No. 8008, No. 9001 to No. 9006, No. 10001 to No. 10008, No. 11001 to No. 11011 and No. 13001 to No. 13006.
  • 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 the passage of 100 hours, the test piece was taken out of the electric furnace and was 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 adds to the weight. It can be said, therefore, that the alloys which are smaller in weight increase by oxidation are more excellent in high-temperature oxidation resistance.
  • Table 28 to Table 31 and Table 33 The results obtained are shown in Table 28 to Table 31 and Table 33.
  • the eighth to eleventh invention alloys are equal, in regard to weight increase by oxidation to the conventional alloy No. 13005, 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 eighth to eleventh invention alloys are very excellent in machinability and resistance to high-temperature oxidation as well.
  • test piece thus obtained was cut on the circumferential surface, holed and cut down into a ringshaped test piece 32 mm in outside diameter and 10 mm in thickness (that is, the length in the axial direction).
  • the test piece was then fitted and clamped on a rotatable shaft, and a roll 48 mm in diameter placed in parallel with the axis of the shaft was thrusted against the test piece under a load of 50 kg.
  • the roll was made of stainless steel under the JIS designation SUS 304.
  • alloy composition (wt%) Cu Si Pb Zn 1001 74.8 2.9 0.03 remainder 1002 74.1 2.7 0.21 remainder 1003 78.1 3.6 0.10 remainder 1004 70.6 2.1 0.36 remainder 1005 74.9 3.1 0.11 remainder 1006 69.3 2.3 0.05 remainder 1007 78.5 2.9 0.05 remainder No. alloy composition (wt%) Cu Si Pb Bi Te Se Zn 2001 73.8 2.7 0.05 0.03 remainder 2002 69.9 2.0 0.33 0.27 remainder 2003 74.5 2.8 0.03 0.31 remainder 2004 78.0 3.6 0.12 0.05 remainder 2005 76.2 3.2 0.05 0.33 remainder 2006 72.9 2.6 0.24 0.06 remainder No.
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 7001 o ⁇ ⁇ 132 ⁇ 755 17 7002 o ⁇ ⁇ 127 ⁇ 776 19 7003 o ⁇ ⁇ 135 ⁇ 620 15 7004 o ⁇ ⁇ 130 ⁇ 714 18 7005 o ⁇ ⁇ 128 ⁇ 708 19 7006 o ⁇ ⁇ 130 ⁇ 685 16 7007 o ⁇ ⁇ 132 ⁇ 717 18 7008 o ⁇ ⁇ 130 ⁇ 811 18 7009 o ⁇ ⁇ 130 ⁇ 790 15 7010 o ⁇ ⁇ 131 ⁇ 708 18 7011 o ⁇ ⁇ 128 ⁇ 810 17 7012 o ⁇ ⁇ 128 ⁇ 694 17 7013 o ⁇ ⁇ 132 ⁇ 742 16 7014 o ⁇ ⁇ 128 ⁇ 809 17 7015
  • machinability hot workability mechanical properties form of chippings condition of cut surface cutting force (N) 700°C deformability tensile strength (N/mm 2 ) elongation (%) 7021 o ⁇ ⁇ 126 ⁇ 792 19 7022 o ⁇ ⁇ 128 ⁇ 762 20 7023 o ⁇ ⁇ 129 ⁇ 725 17 7024 o ⁇ ⁇ 128 ⁇ 744 21 7025 o ⁇ ⁇ 130 ⁇ 750 20 7026 ⁇ ⁇ 132 ⁇ 671 23 7027 o ⁇ ⁇ 128 ⁇ 740 23 7028 o ⁇ ⁇ 133 ⁇ 763 22 7029 ⁇ ⁇ 129 ⁇ 647 24 No.
  • wear resistance weight loss by wear 7001a 0.7 7002a 1.4 7003a 2.0 7004a 1.4 7005a 1.2 7006a 1.8 7007a 2.3 7008a 0.7 7009a 0.6 7010a 1.3 7011a 0.8 7012a 1.7 7013a 1.1 7014a 0.8 7015a 1.1 7016a 1.0 7017a 1.6 7018a 1.9 7019a 1.1 7020a 1.4 No. wear resistance weight loss by wear (mg/100000rot.) 7021a 1.5 7022a 1.4 7023a 0.9 7024a 2.0 7025a 1.2 7026a 1.2 7027a 1.1 7028a 2.1 7029a 1.5 No. wear resistance weight loss by wear (mg/100000rot.) 13001a 500 13002a 620 13003a 520 13004a 450 13005a 25 13006a 600

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EP04077561A 1998-10-09 1998-11-16 Alliage de décolletage à base de cuivre. Expired - Lifetime EP1508626B1 (fr)

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EP3498873B1 (fr) 2016-08-15 2022-05-11 Mitsubishi Materials Corporation Alliage de cuivre facilement usinable et procédé de fabrication de celui-ci
WO2019035224A1 (fr) * 2017-08-15 2019-02-21 三菱伸銅株式会社 Alliage de cuivre de décolletage, et procédé de fabrication de celui-ci
JP6448168B1 (ja) * 2017-08-15 2019-01-09 三菱伸銅株式会社 快削性銅合金、及び、快削性銅合金の製造方法
JP6448166B1 (ja) * 2017-08-15 2019-01-09 三菱伸銅株式会社 快削性銅合金、及び、快削性銅合金の製造方法
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
KR101969010B1 (ko) 2018-12-19 2019-04-15 주식회사 풍산 납과 비스무트가 첨가되지 않은 쾌삭성 무연 구리합금
JP7180488B2 (ja) * 2019-03-25 2022-11-30 三菱マテリアル株式会社 銅合金丸棒材
WO2020261666A1 (fr) 2019-06-25 2020-12-30 三菱マテリアル株式会社 Alliage de cuivre à décolletage et procédé de production d'alliage de cuivre à décolletage
CN113348261B (zh) 2019-06-25 2022-09-16 三菱综合材料株式会社 易切削铜合金及易切削铜合金的制造方法
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DE102020127317A1 (de) 2020-10-16 2022-04-21 Diehl Metall Stiftung & Co. Kg Bleifreie Kupferlegierung sowie Verwendung der bleifreien Kupferlegierung

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EP1038981A1 (fr) 2000-09-27
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EP1038981A4 (fr) 2003-02-19
TW577931B (en) 2004-03-01
DE69835912T2 (de) 2007-03-08
KR20010033101A (ko) 2001-04-25
EP1508626B1 (fr) 2006-09-13
DE69828818D1 (de) 2005-03-03
JP3917304B2 (ja) 2007-05-23
EP1038981B1 (fr) 2005-01-26
DE69828818T2 (de) 2006-01-05
EP1502964A1 (fr) 2005-02-02
KR100375426B1 (ko) 2003-03-10
WO2000022181A1 (fr) 2000-04-20
JP2000119774A (ja) 2000-04-25
AU738301B2 (en) 2001-09-13
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CA2303512A1 (fr) 2000-04-20
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