WO2007013428A1 - 銅合金押出材およびその製造方法 - Google Patents
銅合金押出材およびその製造方法 Download PDFInfo
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- WO2007013428A1 WO2007013428A1 PCT/JP2006/314628 JP2006314628W WO2007013428A1 WO 2007013428 A1 WO2007013428 A1 WO 2007013428A1 JP 2006314628 W JP2006314628 W JP 2006314628W WO 2007013428 A1 WO2007013428 A1 WO 2007013428A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
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- 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
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
- B22F2009/046—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling by cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
- B23B2222/21—Copper
Definitions
- the present invention relates to a high strength copper alloy extruded material having free machinability, and more preferably relates to a copper alloy extruded material which does not contain lead or cadmium which is harmful to the environment or human body.
- Copper alloys are widely used in automotive parts, electronic parts, piping members (water faucet 'valves), etc., but in view of future expansion of the applicable products and expansion of the market, the machinability ( It is important to improve and improve both machinability and strength. It is important to improve the machinability of copper alloys, especially in light of productivity and low cost.
- a copper alloy containing such lead for example, a bronze-based alloy such as JIS H5111 BC6 or a brass-based alloy such as JIS H3250-C3604 or C3771 can be used.
- lead-free machinable copper alloy having no lead or cadmium at all for example, JP-A-2000
- a machinability improving element to replace lead or cadmium which may adversely affect the environment or human body is selected, and when the element is added, the element is uniformly dispersed in the alloy and stable high efficiency It is desirable to develop a copper alloy that can achieve machinability and excellent mechanical properties (especially high strength). In particular, in order to achieve both the machinability and high strength of the copper alloy, it is important to uniformly disperse the element in the alloy when adding the machinability improving element to the copper alloy. .
- An object of the present invention is to provide a copper alloy extruded material having high machinability.
- Another object of the present invention is to provide a copper alloy extruded material in which a suitable amount of a machinability improving element is uniformly dispersed.
- Still another object of the present invention is to provide a copper alloy extruded material in which stable high free chipping properties and excellent mechanical properties are compatible.
- Still another object of the present invention is to provide a copper alloy member obtained by drawing or hot forging the above-mentioned extruded copper alloy material.
- Still another object of the present invention is to provide a method for producing a copper alloy extruded material having high machinability.
- the extruded copper alloy material according to the present invention is obtained by extruding a billet of a solidified copper alloy powder, and is characterized in that old powder grain boundaries are left inside.
- the copper alloy extruded material when the copper alloy extruded material is 100 wt% of the entire copper alloy extruded material, in the matrix, graphite, boron nitride, molybdenum disulfide, copper sulfide and calcium fluoride force are used. It contains 0.1% to 3% by weight of at least one selected powder particle. More preferably, the extruded material of the copper alloy is selected from the group consisting of graphite, boron nitride, molybdenum disulfide, copper sulfide and fluoride, in the matrix, assuming that the entire extruded copper alloy is 100% by weight. It contains 0.3% to 1% by weight of at least one powder particle.
- the copper alloy constituting the matrix is 77 to 88% of copper by weight
- aluminum is 8.5% to 12%, nickel 0.5% to 5.5%, iron 2% to 5%, manganese 0.5% to 2%, and the balance having an alloy composition of zinc .
- the copper alloy constituting the matrix is 69-80% of copper by weight and silicon Containing 1. 8 to 3.5%, and further selected from 0.3 to 3.5% tin, 1 to 3.5% aluminum, 0.20 to 0.25% phosphorus group power It has an alloy composition that contains one or more elements, and the balance also has zinc power.
- the copper alloy constituting the matrix when the entire copper alloy constituting the matrix is 100% by weight, the copper alloy constituting the matrix is zinc in an amount of 26 to 32% by weight, An alloy composition containing 0.5-5. 5% silicon, 3-45% aluminum, 0.5-5. 5% iron, 2-45% nickel and the balance being copper Have.
- the copper alloy constituting the matrix when the total amount of copper alloy constituting the matrix is 100% by weight, the copper alloy constituting the matrix is 55 to 65% of copper on a weight basis, It has an alloy composition that contains 0.2 to 7.5% of aluminum, 0.1 to 4% of iron, 0.5 to 5% of manganese, and the balance of zinc.
- the copper alloy constituting the matrix when the total amount of copper alloy constituting the matrix is 100% by weight, the copper alloy constituting the matrix is 55 to 64% of copper on a weight basis, It has an alloy composition containing 0.1% to 0.7% iron, 0.2% to 2.5% tin, and the balance zinc.
- the copper alloy constituting the matrix further comprises, on a weight basis, 0.1 to 1.5% of titanium, 0.1 to 1.5% of chromium, and 0.1 to 1.5% of cobalt.
- Group Force May contain one or more selected elements.
- the copper alloy constituting the matrix further contains 0.2 to 4% of bismuth, 0.20% by weight.
- It may also contain one or more elements selected from the group consisting of: .4% tellurium, 0.20 to 0. 4% selenium, 0.20 to 0. 15% antimony. .
- the particle diameter of the above-mentioned powder particle is, for example, 5 ⁇ m or more and 300 ⁇ m or less.
- the powder particles are distributed along the old powder grain boundaries.
- the extruded copper alloy according to still another embodiment contains 0.3 to 4% of lead on a weight basis, assuming that the entire extruded copper alloy is 100% by weight.
- the billet for a copper alloy extruded material according to the present invention is a billet for obtaining the copper alloy extruded material described in any of the above, and is formed by compacting a copper alloy powder. ing.
- a copper alloy member according to the present invention is obtained by drawing or hot forging a copper alloy extruded material as described in any of the above.
- the method for producing a copper alloy extruded material according to the present invention comprises the steps of: compacting the copper alloy powder to produce a billet of the solidified copper alloy powder; and extruding the billet to press the billet. And obtaining a material.
- the extrusion ratio of the extrusion force is, for example, 20 or more and 500 or less.
- the copper alloy powder is And a step of adding at least one powder particle selected from lead, boron nitride, molybdenum disulfide, copper sulfide and calcium fluoride, and mixing them.
- the addition amount of powder particles is 0.1 to 3 parts by weight with respect to 100 parts by weight of the copper alloy powder.
- the particle size of the powder particles to be added is, for example, 5 ⁇ m or more and 300 ⁇ m or less.
- the billet is heated to a range of 400 ° C to 800 ° C to perform the above-mentioned extrusion.
- FIG. 1 is a photograph showing the shapes of various chips.
- FIG. 2 is a drawing depicting a part of the photograph of the chip of FIG.
- FIG. 3 A photograph of the structure of a solidified billet of copper alloy powder and a billet made of copper alloy.
- FIG. 4 This is a structure photograph obtained by adding a line indicating the old powder grain boundary to the structure photograph of Fig. 3.
- FIG. 5 is a view schematically showing a drilling machine.
- the present inventors propose a high strength copper alloy extruded material excellent in machinability and a method for producing the same. Specifically, graphite, boron nitride, sulfur dioxide molybdenum, copper sulfide and calcium fluoride are selected as machinability improving elements to replace lead, and at least one kind of powder particles having a medium strength of a predetermined alloy composition is selected.
- the above object is to be achieved by adding and mixing an appropriate amount of copper alloy powder having the above and forming and solidifying the mixed powder.
- the powder particles of both are melted together.
- the machinability improving element particles are uniformly dispersed in the copper alloy base by extruding and solidifying and extruding, as a result, a copper alloy extruded material having excellent machinability and high strength and toughness is provided. be able to.
- the copper alloy powder constituting the base of the copper alloy extruded material according to the present invention has a machinability modified to be described later. After mixing with the good element particles, pressure is maintained while being filled in a mold or mold to produce a billet of a solidified copper alloy powder for extrusion. The billet is subsequently heated and then immediately solidified by extrusion. As a result, in the inside of the obtained copper alloy extruded material, a structure with the old powder grain boundaries corresponding to the copper alloy powder which is the input material remaining appears. The present inventors have found that such a structural structure can be realized and controlled by hot plastic working of a solidified copper alloy powder billet at an appropriate extrusion ratio.
- FIG. 1 is a photograph showing the shape of chips (cutting chips) obtained when cutting various types of extruded copper alloy.
- FIG. 2 is a drawing depicting a part of the photograph of the chip of FIG. 1, and (a), (b), (c) and (d) of FIG. 2 respectively represent (a) of FIG. , (b), (c), (d).
- extruding and solidifying the billet of the solidified copper alloy powder at an appropriate extrusion ratio is a new method of improving machinability for extruded copper alloy, which has not been seen so far. Since such old powder grain boundaries can not exist inside the extruded material obtained by using the melt-blown billet of the prior art, even if melt-blown billets of the same composition are used, as described above There is no noticeable improvement in machinability.
- the frictional resistance (cutting resistance) between the tool and the copper alloy material at the time of cutting can be determined.
- the size of chips can be further reduced as shown in Fig. 1 (a) and Fig. 2 (a). Therefore, if the tool life is increased and the cutting time is shortened, the effect of further improving the machinability can be realized.
- the particle diameter of the copper alloy powder is not particularly restricted! /, But in consideration of the moldability to molds and molds, the particle diameter is about 10 m to 10 mm. What desirable.
- the particle size of the copper alloy powder is less than 10 / z m, the powder particles enter into the gaps of the mold to cause seizing between the molds, or the problem that the filling property is lowered, and the relative surface area is Due to the increase of the friction resistance between the copper alloy powders to increase the powder formability is lowered, and problems such as cracking and breakage occur in the powder solidified billet.
- the particle size of the copper alloy powder exceeds 10 mm, the filling rate into the mold or the mold is reduced and the compactability is reduced.
- a method of producing a copper alloy powder a method of producing a copper alloy powder by a spraying method (atomization method) or a copper alloy ingot having a predetermined alloy composition by a melting method is fabricated and cut.
- a method that produces relatively coarse copper alloy powder and chips by grinding machining is effective.
- general cutting chips can also be formed.
- At least one powder particle selected from graphite, boron nitride, molybdenum disulfide, copper sulfide, and a group force which is also a calcium fluoride force is selected as the machinability improving element particle replacing lead.
- the mixture is mixed with the above-mentioned copper alloy powder, and then compacted to prepare a billet of the solidified powder.
- the machinability improving element particles are present between the copper alloy powders, the machinability improving element particles added in the base material of the extruded material using such a powder solidified billet are copper. It exists along the former powder grain boundary inside the alloy extrusion material.
- the above-mentioned machinability improving element particles do not form a solid solution in the copper alloy base but improve and improve the machinability of the copper alloy by forming particles and dispersing them. Have an effect.
- graphite powder particles are inexpensive and advantageous in terms of economy.
- the graphite powder may be natural graphite or artificial graphite, and may be in the form of particles, flakes or lumps in terms of shape.
- the content of the machinability improving element particles in that is 0.1% to 3% on a weight basis. It is desirable that 0.1 Adding 1% or more of weight can reduce the above-mentioned cutting resistance and extend the tool life, and can shorten the cutting process. At the same time, cutting chips are further reduced, so cutting at the time of cutting. Processing of powder discharge is facilitated. However, even if it is added in excess of 3% by weight, the above-mentioned effect corresponding to the addition amount can not be obtained. Rather, problems arise such as a decrease in the strength and toughness of the copper alloy extruded material. In particular, the addition of machinability improving element particles By setting the addition amount to 0.3% to 1% on a weight basis, the effect of improving the machinability can be exhibited while maintaining high strength and high toughness.
- the particle diameter of the above-mentioned machinability improving element particles By setting the particle diameter of the above-mentioned machinability improving element particles to 5 ⁇ m or more and 300 ⁇ m or less, it is possible to achieve both the above-mentioned excellent mechanical properties and free machinability in the extruded material of copper alloy. it can .
- fine particles are aggregated by electrostatic attraction or the like to form coarse secondary particles, and the presence of such particles in the copper alloy leads to a decrease in strength or toughness. If it exceeds 300 m, the strength and toughness decrease. From the viewpoint of the mixing property with the copper alloy powder and the compactability, it is more preferable to set the particle size of the machinability improving element particle to 20 m or more and 150 m or less.
- the copper alloy component constituting the base of the copper alloy extruded material of the present invention will be described.
- the extruded copper alloy according to the first embodiment based on 100% by weight of the entire copper alloy constituting the matrix, 77 to 88% of copper, 8.5 to 12% of aluminum, and nickel are on a weight basis. It has an alloy composition containing 0.5 to 5.5% of iron, 2-5% of iron, 0.5 to 2% of manganese, and the balance being zinc power.
- the addition of aluminum can improve the strength, hardness and high temperature oxidation resistance of the copper alloy. Within the copper content range of this alloy, if less than 8.5% of aluminum, these effects are sufficient, and even if it is contained over 12%, these further improvement effects are not observed, and the toughness of the copper alloy is When it falls, it causes problems.
- addition of aluminum exceeding 4% by weight causes the Cu-A1 intermetallic compound to be coarsened, resulting in a reduction in toughness of the copper alloy extruded material.
- the Cu-A1 intermetallic compound is fine even if it is added in excess of 4% by weight because aluminum is forced to form a solid solution in the substrate.
- the particles are uniformly dispersed in the base material, and as a result, they contribute to the improvement of strength without any decrease in toughness.
- crystal grains of the ⁇ phase that forms the base are recrystallized due to the processing strain accumulated in the powder base, and in the process, the Cu-Al based intermetallic compound Is a fine granular composite, so the strength is improved without causing a decrease in toughness.
- nickel can improve the strength and hardness of the copper alloy.
- iron also forms an Fe—Al based intermetallic compound by being present together with aluminum, thereby improving the strength, hardness and heat resistance of the copper alloy.
- this alloy component range if the amount of added carbon is less than 2% by weight, sufficient improvement effect disappears, and if it is added more than 5% by weight, the toughness of the copper alloy extruded material may be lowered, or the surface of the extruded material. With the occurrence of 'cracks' defects
- Manganese dissolves in the matrix to strengthen it and stabilize the alloy composition against the heat history. If the content of manganese is less than 0.5%, the above effect can not be obtained. If the content is more than 2%, the corresponding improvement effect can not be obtained. Therefore, the content of manganese is preferred. 0.5 to 2%.
- Silicon has the effect of forming a ⁇ phase to improve the toughness of the copper alloy extruded material, as well as improving the machinability. If the amount added is less than 1.8% by weight, the above improvement effect is not sufficient, while if it is added in the range of 3.5% by weight in the present alloy component range, the toughness of the copper alloy extruded material is lowered. Invite.
- the improvement effect of the machinability by the addition of silicon the effect is smaller than the effect by the formation of the old powder grain boundary described later and the addition effect of the machinability improving element particles such as graphite. Silicon carbide also improves strength, wear resistance, stress corrosion cracking resistance, and high temperature oxidation resistance.
- a ⁇ phase is formed to have the effect of improving the machinability of a copper alloy extruded material. If the addition amount is less than 0.3% by weight, the improvement effect described above will not be sufficient. On the other hand, if it is added in the present alloy component range over 3.5% by weight, the toughness of the copper alloy extruded material will be lowered.
- the effect of improving the machinability by the addition of tin is smaller than the effect of forming the old powder grain boundaries described later and the effect of adding machinability improving element particles such as graphite. It does not necessarily add in all of the copper alloy extrusion materials specified by the invention. It is not an essential element.
- Aluminum like tin, also has the function of forming a ⁇ phase, and it is necessary to add at least 1% by weight to improve machinability. However, even if it exceeds 3.5%, no improvement effect is seen and ductility decreases.
- Phosphorus has the effect of refining the crystal grains of the ex phase constituting the base, thereby improving the strength of the extruded copper alloy and improving the hot workability such as forging. Generation of defects and cracks in forged parts is suppressed. If the addition amount is less than 0.02% by weight, the above effect is sufficient, and even if it is added over 0.25% by weight, the effect corresponding to it is not obtained, and the extrusion property declines by force. And problems such as reduced toughness of extruded material
- zinc is contained in an amount of 26 to 32% by weight, silicon in an amount of 0.5 to 1.5% based on 100% by weight of the entire copper alloy constituting the matrix.
- This alloy is an alloy having improved wear resistance, and aluminum and silicon form a ⁇ phase to increase the hardness and at the same time to make an intermetallic compound with nickel and iron to increase the hardness.
- the improvement effect is insufficient below the lower limit value of each of the additive elements, and in the alloy component range, the ductility is lowered above the upper limit value of the additive elements. Therefore, the appropriate range of the amount of addition of each element is as described above.
- Aluminum contributes to the improvement of the wear resistance, and the reinforcing function of the matrix is exhibited by the addition of 0.2% or more. However, in the range of this alloy component, ductility decreases when it is added over 7.5%.
- iron coexists with aluminum to form an Fe—Al based intermetallic compound to improve the strength, hardness and heat resistance of the copper alloy.
- this alloy component range if the addition amount of iron is less than 0.1% by weight, the improvement effect is not sufficiently obtained. It causes the decrease in toughness of the material.
- the copper alloy extruded material is a copper alloy having improved plastic formability such as forging and drawing.
- the extruded material of the copper alloy according to the fifth embodiment contains, if necessary, 0.20% to 0.5% of phosphorus. This has the effect of improving the dezincing resistance. Below the lower limit, segregation at grain boundaries occurs if the improvement effect exceeds the upper limit sufficiently, resulting in reduced ductility.
- the copper alloy constituting the matrix is, if necessary, 0.1 to 1.5% of titanium on a weight basis.
- a group force consisting of 0.1 to 1.5% chromium and 0.1 to 1.5% cones also contains one or more selected elements. Each of these elements has the effect of improving the strength and hardness of the copper alloy, and the improvement effect is insufficient when the content is below the lower limit of each other, while the extrusion property decreases when the content exceeds the upper limit. This leads to a decrease in the toughness of the extruded material.
- a copper alloy powder having the above-described alloy composition is prepared, filled into a mold or a mold, and then pressed and molded to produce a copper alloy powder solidified billet.
- at least one machinability improvement selected from the group consisting of the above-mentioned graphite, boron nitride, molybdenum disulphide, molybdenum disulphide and calcium fluoride in copper alloy powder in advance.
- the relative density of the billet it is necessary that the bonding strength of the copper alloy powder is such that the billet is not damaged in the transportation process.
- the relative density is 80% or more (the porosity is 20% or less). Desirable to be pressurized.
- the billet After heating the billet produced as described above, the billet is immediately subjected to extrusion processing to obtain a dense copper alloy extruded material. At this time, it is necessary to set the extrusion ratio to 20 or more and 500 or less in order to form the old powder grain boundary while securing the strength * toughness of the extruded material. If the extrusion ratio is less than 20, the strength and toughness will be reduced because the diffusion ′ bonding between the copper alloy powders forming the base is not sufficient. On the other hand, if the extrusion ratio is set to 500 or more, the remaining of the old powder grain boundaries will be reduced and the strength and toughness will be further improved, but the chips (cuttings) discharged during cutting are shown in FIG. 1 (d) and FIG. The continuous curling as shown in (d) results in a decrease in machinability.
- the heating temperature of the billet is desirably controlled in the range of 400 ° C. to 800 ° C. If the temperature is less than 400 ° C., the diffusion and bonding of the copper alloy powders are not sufficient! On the other hand, when heating is carried out at more than 800 ° C., coarsening of the crystal grains constituting the copper alloy base occurs, and the tensile strength of the extruded copper alloy is lowered. In addition, cracks occur along the circumferential direction on the surface of the extruded material, which causes some problems.
- an object of the present invention is to provide a copper alloy extruded material having excellent machinability and a method for producing the same without using lead or cadmium which is considered to have an influence on the human body or the environment.
- European * RoHS regulations exclude the lead content in the copper alloy by up to 4% by weight! /
- the copper alloy extruded material according to the present invention is made compatible with this. OK. That is, the extruded copper alloy according to one embodiment of the present invention may contain 0.3 to 4% of lead on a weight basis, assuming that the total extruded copper alloy is 100% by weight. As mentioned above, the inclusion of lead can achieve excellent free-cutting performance.
- the addition amount of lead 0.3% by weight or more.
- the addition of more than 4% by weight is not preferable from the viewpoint of the previous RoHS regulation and the decrease in strength of the extruded material.
- lead is not necessarily an additive element required.
- Example 1 corresponds to the copper alloy extruded material according to the first embodiment described above.
- a truss-made copper alloy ingot having the composition shown in Table 1 is prepared, and powder (length: 0.5 to 4 mm) collected by cutting is used as a starting material, and this is used in a mold attached to a press.
- powder length: 0.5 to 4 mm
- a cylindrical powder-solidified billet with a diameter of 59.8 mm ⁇ and a total length of 98 mm was produced.
- This billet is heated and held at 650 to 720 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into an extrusion container with an inner diameter of 60 ⁇ and extrusion of a diameter of 9.8 ⁇ under conditions of an extrusion ratio of 37.5 The material was made.
- the cutting conditions were as follows.
- Example 2 corresponds to the copper alloy extruded material according to the second embodiment described above.
- a gold-plated copper alloy ingot having a composition shown in Table 2 was prepared, and powder (length: 0.5 to 4.5 mm) collected by cutting was used as a starting material, and this was mounted on a press.
- powder length: 0.5 to 4.5 mm
- Hold the billet in a nitrogen gas atmosphere for 30 minutes at 660 to 725 ° C The mixture was immediately filled into an extrusion container with an inner diameter of 60 ⁇ , and an extruded material of a diameter of 9. 8 ⁇ was produced under the conditions of an extrusion ratio of 37.5.
- a tensile test piece with a diameter of 3.5 mm and a parallel part of 20 mm was collected from the extruded material produced as described above, and a tensile test was conducted at room temperature under the conditions of strain rate of 5 ⁇ 10 — 4 Z seconds. In addition, a cutting test was conducted to compare the shapes of generated chips.
- the cutting conditions were as follows.
- Sample Nos. 10 to 21 a brass alloy extruded material having high strength and high toughness (high elongation value) is obtained by having an appropriate alloy component.
- sample No. 22 has a low Si content of 0.8% by weight and strength decreases compared to other copper alloys
- sample No. 23 has an A1 content of 0.5% by weight The strength was reduced compared to other copper alloys due to the small size.
- Example 3 corresponds to the copper alloy extruded material according to the third embodiment described above.
- a forged copper alloy ingot having the composition shown in Table 3 is prepared, and powder (length 1. to 4. 8 mm) collected by cutting is used as a starting material, and this is mounted on a press.
- powder length 1. to 4. 8 mm collected by cutting
- a cylindrical powder-solidified billet with a diameter of 59.8 mm ⁇ and a total length of 98 mm was produced.
- Hold the billet in a nitrogen gas atmosphere at 640 to 705 ° C for 30 minutes The mixture was immediately filled into an extrusion container with an inner diameter of 60 ⁇ , and an extruded material of a diameter of 9. 8 ⁇ was produced under the conditions of an extrusion ratio of 37.5.
- the cutting conditions were as follows.
- Samples No. 25 to 29 it is possible to obtain a brass alloy extruded material having high strength and high toughness (high elongation value) by having appropriate alloy components.
- the strength is increased by containing 0.8% by weight of Co.
- sample No. 30 contained A3 at 3.3% by weight, and the Si content was high at 1.6% by weight, so that although the strength increased, a marked decrease in elongation occurred, and the sample In the case of No. 31, since the Si content was as low as 0.3% by weight, the strength was reduced compared to other copper alloys.
- Example 4 corresponds to the copper alloy extruded material according to the fourth embodiment described above.
- a structured copper alloy ingot having the composition shown in Table 4 is prepared, and a powder (length 0.5 to 4.2 mm) collected by cutting is used as a starting material, and this is mounted on a press.
- a cylindrical powder-solidified billet with a diameter of 59.8 mm ⁇ and a total length of 98 mm was produced.
- This billet is heated and held at 660 to 725 ° C. for 30 minutes in a nitrogen gas atmosphere and immediately filled into an extrusion container with an inner diameter of 60 ⁇ and extrusion of a diameter of 9.8 ⁇ under conditions of an extrusion ratio of 37.5.
- the material was made.
- the cutting conditions were as follows.
- the V and the displacement are also excellent in dischargeability ( It is a chip having b) and showed good cutting properties.
- Example 5 corresponds to the copper alloy extruded material according to the fifth embodiment described above.
- a structured copper alloy ingot having the composition shown in Table 5 is prepared, and powder (length: 0.7 to 3.9 mm) collected by cutting is used as a starting material, and this is mounted on a press.
- powder length: 0.7 to 3.9 mm
- This billet is heated and held at 640-700 ° C for 30 minutes in a nitrogen gas atmosphere
- the mixture was immediately filled into a container for extrusion having an inner diameter of 60 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , and an extruded material having a diameter of 9. 8 ⁇ ⁇ ⁇ was produced under the conditions of an extrusion ratio of 37.5.
- a tensile test piece with a diameter of 3.5 mm and a parallel portion of 20 mm was collected from the extruded material produced as described above, and a tensile test was performed at room temperature under conditions of strain rate of 5 ⁇ 10 4 Z seconds. . In addition, a cutting test was conducted to compare the shapes of generated chips.
- the cutting conditions were as follows.
- sample Nos. 42 to 50 a brass alloy extruded material having high strength and high toughness (high elongation value) is obtained by having appropriate alloy components.
- sample No. 51 contained a small amount of only 0.2% by weight of Sn as an element other than Cu and Z n, so that the strength decreased compared to other copper alloys.
- FIG. 3 shows metal photographs of Sample No. 42 and Sample No. 52.
- the copper alloy powder solidified billet according to the present invention of (a) (Sample No. 42)
- old powder grain boundaries are observed in the base material of the extruded material as shown by the arrows.
- the twill copper alloy billet of (b) is used (Sample No. 52)
- the old powder grain boundaries as seen in (a) are not observed.
- FIG. 4 is a photograph of the structure of FIG. 3 with a line indicating old powder grain boundaries added.
- a powder (0.5 to 4 mm in length) collected by cutting from a copper alloy ingot made by truss making is used as a starting material, and this is filled in a die mounted on a press and pressurized to solidify the diameter. 5 9.
- a cylindrical powder solidified billet of 8 mm in diameter and 98 mm in total length was produced. This billet is heated and held at 680 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into a container for extrusion with an inner diameter of 60 ⁇ and extruded material of a diameter of 9.8 ⁇ under conditions of an extrusion ratio of 37.5. Was made.
- the extruded material produced as described above was pickled and then drawn at a normal temperature under a reduction ratio of 4.5%. Then, tensile test pieces with a diameter of 3.5 mm and a parallel part of 20 mm were collected from the obtained material, and a tensile test was conducted at room temperature under conditions of strain rate of 5 X 10 4 Z seconds. In addition, the tissue observation of each material with an optical microscope was performed together.
- the cutting conditions were as follows.
- Table 6 shows the results of tensile test and Vickers hardness measurement and the surface properties of the drawn material.
- the mechanical properties of the material after extrusion-drawing processing are not significantly different between the two.
- the copper obtained by the manufacturing process proposed in the present invention It was also confirmed that the copper alloy extruded material using the alloy powder had sufficient mechanical properties.
- the copper alloy powder (length: 0.5 to 4 mm) used in Example 6 is used as a starting material, and natural graphite particles having an average particle size of 65 m are added thereto and mixed, and then similarly added to the mold. Filled in diameter 59. 8mm
- a cylindrical powder solidified billet with a total length of 98 mm was produced.
- This billet is heated and held at 680 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately after that, the billet is filled into an extrusion container with an inner diameter of 60 ⁇ ⁇ ⁇ and the diameter of 9. 8 ⁇ 8 ⁇ under an extrusion ratio of 37.5.
- An extruded material was produced.
- Table 7 shows the addition amount of graphite particles.
- the machinability was evaluated by a drill cutting test method.
- a hole of 5 mm in depth is cut in a copper alloy extruded material with a constant load (in this case, a weight of 58 kg is applied) applied to the drill.
- the time required to do this is compared, and the shorter the time, the better the machinability.
- reference numeral 1 indicates a sample (copper alloy extruded material), 2 indicates a drill, 3 indicates a weight, 4 indicates a string, 10 indicates a drilling machine, and 11 indicates a handle. ing.
- Pb-containing twill copper alloy billet 31.1 d Comparative example [0127] As comparative materials, Cu: 82.5%, Al: 9.3%, Mn: 0.9%, Ni; l. 7%, Fe: 3.2%, Pb; l. 6 based on weight. %, Zn: A copper alloy extruded material obtained by extruding a lead-added copper-made copper alloy billet having the composition of the balance under the same conditions was used.
- a Pb-containing structure is obtained by containing the graphite particles in an appropriate range.
- the machinability is superior to that of an extruded material using a copper alloy ingot, and the machinability also improves with the increase of the content of graphite particles.
- any tuck copper alloy ingot was used, it was continuous curling cutting (d), but the copper alloy powder according to the present invention In the extruded material using the body solidified billet and the copper alloy powder solidified billet containing graphite particles, it was a fine scrap with a good dischargeability, and a granular chip (a or b).
- the extruded material has good tensile strength and machinability (shape a or b).
- the tensile strength of the extruded material is further improved.
- the extrusion ratio is less than 8, since the bondability between the copper alloy powders constituting the base of the extruded material is not sufficient, the tensile strength of the extruded material is lowered.
- the extrusion ratio exceeds 500, the bonding between the copper alloy powder significantly progresses due to the strong plastic working during extrusion, and as a result, the old powder grain boundary which is the feature of the copper alloy extruded material according to the present invention Will not remain in the substrate, and chips (chips) will continuously curl (shape c or d). As a result, problems arise when the machinability of the extruded material is reduced.
- Example 9 Using the copper alloy powder (length: 0.8 to 3 mm) used in Example 9 as a starting material, the powder is filled into a die mounted on a press and solidified by pressing, to obtain a diameter of 59. A cylindrical powder-solidified billet of 8 mm in diameter and 98 mm in total length was produced. This billet is heated and maintained at each temperature shown in Table 10 for 30 minutes in a nitrogen gas atmosphere, immediately filled into an extrusion container with an inner diameter of 60 mm ⁇ 5, and the diameter is 9.8 mm under the conditions of an extrusion ratio of 37.5. An extruded material of ⁇ was produced.
- the extruded material was confirmed to have good mechanical properties by heating and extruding the copper alloy powder solidified billet in an appropriate temperature range defined by the present invention.
- the heating temperature force is lower than 00 ° C.
- the bonding between the powders during extrusion is sufficiently sufficient to generate pores in the inside of the material, resulting in the deterioration of the mechanical properties.
- the temperature exceeds 850 ° C., the copper crystal grains constituting the base of the extruded copper alloy coarsen and grow. This causes a decrease in the strength and hardness of the extruded material.
- Si As a component belonging to the copper alloy extruded material according to the third embodiment, Si; 0.8%, A1 on a weight basis
- each additive particle is boron nitride; 32 ⁇ m, molybdenum disulfide; 42 ⁇ m, calcium fluoride; 26 / z m.
- Each mixed powder was filled in a die fitted to a press and solidified under pressure to produce a cylindrical powder solidified billet with a diameter of 59.8 mm ⁇ and a total length of 98 mm. This billet is heated and held at 650 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into an extrusion container with an inner diameter of 60 mm ⁇ and extruded with a diameter of 8.5 ⁇ ⁇ under an extrusion ratio of 49.8. The material was made.
- a tensile test piece with a diameter of 3.5 mm and a parallel portion of 20 mm was collected from the extruded material produced as described above, and a tensile test was conducted at room temperature under conditions of strain rate of 5 ⁇ 10 4 Z seconds. . Further, in the same manner as in Example 6, a cutting test was conducted to compare the shapes of generated cutting chips.
- the cutting conditions were as follows.
- Table 11 shows the tensile test results and the shape of chips.
- the machinability improvement specified by the present invention By dispersing an appropriate amount of the element particles in the base material of the extruded copper alloy, cutting waste can be reduced without deteriorating the mechanical properties, and machinability can be improved. Can. If it is added in excess of 3% by weight, problems may occur if the tensile strength and elongation of the extruded copper alloy are lowered, as in the case of graphite powder particles.
- the present inventors confirmed that the same effect can be obtained even when two or more types of each of the machinability improving element particles are mixed with the copper alloy powder, including the graphite powder. doing.
- Cu As components belonging to the extruded copper alloy according to the fourth embodiment, Cu: 61. 4%, Al: 3.4%, Mn: 3.2%, Fe: 2.1%, Pb on a weight basis.
- Each copper alloy powder was filled in a die fitted to a press and solidified by pressing, to produce a cylindrical powder-solidified billet with a diameter of 59.8 mm ⁇ and a total length of 100 mm.
- This billet is heated and held at 660 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into an extrusion container with an inner diameter of 60 ⁇ and extruded material of a diameter of 9.8 ⁇ under conditions of an extrusion ratio of 37.5. Was produced.
- forged billet of the same dimension is extracted by machining from a forged copper alloy ingot having the same composition as the above, and this is extruded under the same conditions to produce an extruded material of diameter 9. 8 ⁇ . did.
- Example 6 The same cutting test as in Example 6 and the drill cutting test in Example 8 were carried out for each of the extruded materials produced as described above. In the former test, the shape of the generated cutting chips was evaluated, and in the latter test, the time required to cover a 5 mm deep hole in a copper alloy extruded material was evaluated. The results are shown in Table 12.
- the cutting waste has excellent dischargeability as a discontinuous and fine chip. Indicated. Moreover, as a result of adding an appropriate amount of graphite powder to copper alloy powder, cutting chips are discharged in a discontinuous shape as finer chips, and it has been possible to shorten the processing time in the drill cutting test. .
- This billet The mixture is heated and held at 700 ° C for 30 minutes in a nitrogen gas atmosphere, and immediately filled into an extrusion container with an inner diameter of 60 mm ⁇ , and the extruded material with a diameter of 9. 8 ⁇ ⁇ under conditions of an extrusion ratio of 37.5. Made.
- a steel billet having the same dimensions is extracted by machining from a continuous steel copper alloy ingot having the same composition as described above, and this is extruded under the same conditions.
- the extruded material produced as described above is pickled and then drawn at a room temperature reduction rate of 15.3% at room temperature, and then annealed at 510 ° C for 4.5 hours, It is drawn from the material obtained by drawing at 6% reduction rate, then annealing at 510 ° C. for 4.5 hours, and finally drawing out at 13.5% reduction rate.
- a tensile test piece with a parallel part of 20 mm was collected, and a tensile test was performed at room temperature under the conditions of strain rate of 5 ⁇ 10 4 Z seconds.
- the machinability was evaluated by the drill cutting test method. Here we used a 1.5 kg weight. The test results are shown in Table 13. The material by the melting process is worn away by the tool during 10 times of drill test and the processing time is gradually increased. The powder solidified process material with the addition of graphite by the same component has the machining time constant and the drill wear is observed. Absent. In addition, it was confirmed that the mechanical properties were not inferior to the melting process materials.
- Powder (average particle diameter: 70 ⁇ m) collected by atomizing a molten metal having a composition of 4%, Fe: 0.1%, Sn: 0.2%, and the balance being zinc power
- natural graphite particles having an average particle diameter were added to this and mixed, and the mixture was similarly filled in a mold to prepare a cylindrical powder solidified billet having a diameter of 59.8 mm and a total length of 98 mm.
- This billet is heated and held at 700 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into an extrusion container with an inner diameter of 60 ⁇ and extruded material of a diameter of 9.8 ⁇ 8 ⁇ under conditions of an extrusion ratio of 37.5. Made.
- a steel billet having the same dimensions is extracted by machining from a continuous steel copper alloy ingot having the same composition as described above, and this is extruded under the same conditions to obtain a diameter of 9. 8 mm.
- An extruded material of ⁇ was produced.
- a copper alloy ingot having a composition in which Cu: 61. 1%, Fe: 0.1%, Sn: 0.2%, lead 3.00%, and the balance also has a dumbbell effect on a weight basis
- the same size of billet billet was machined and extruded under the same conditions to produce an extruded material with a diameter of 9.8 mm ⁇ .
- the extruded material prepared as described above is pickled and then drawn at room temperature under a reduction ratio of 26%, then annealed at 460 ° C. for 4.5 hours, and finally 13.
- a tensile test piece with a diameter of 3.5 mm, and a parallel part of 20 mm is collected from the material obtained by drawing at a reduction rate of 5%, and tension is applied at room temperature under conditions of strain rate 5 X 10 _ 4 / s. The test was done.
- Table 14 shows the relationship between the amount of carbon added to the graphite and the mechanical properties.
- the machinability was evaluated by the drill cutting test method. Since this material is relatively soft as the material of Example 8 does, the weight of 1. Okg was used here. The test results are shown in Table 15. From these results, the extruded material strength by billet solidified by adding graphite to brass atomized powder is obtained, and the brass material obtained is considered to have the best machinability among metal materials. It has been confirmed that machinability and mechanical properties can be obtained without any deterioration compared to brass.
- the machinability was evaluated by the drill cutting test method. Here, I used an Okg weight. The results of these tests are shown in Table 16. By adding copper sulfide to the addition of graphite, it was confirmed that the machinability can be further improved without losing the mechanical properties.
- the remaining part is a zinc-alloy-made composition having a composition that also has zinc power, and this is subjected to high-speed cutting with mineral cutting oil and collected from powder (length 0.5 to 8 mm) As a raw material, it was stirred in an alkaline immersion degreaser bath heated to 60 ° C., washed with water and drained and dried to confirm that the oil was completely removed.
- This raw material is applied to a crusher and the powder having an average particle diameter of 100 IX m is mounted on a hydrostatic pressure machine and pressurized to solidify to solidify a cylindrical powder having a diameter of 59.8 mm ⁇ and a total length of 120 mm.
- a billet was made. This billet is heated and held at 640 to 700 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into a container for extrusion with an inner diameter of 60 ⁇ ⁇ ⁇ , and the mixture is extruded under an extrusion ratio of 37.5. An extruded material was produced.
- forged billet of the same size is machined out of a forged copper alloy ingot having the same composition as above, and extruded under the same conditions to obtain a diameter of 9. 8 ⁇ . An extruded material was produced.
- the extruded material produced as described above is subjected to a drawing process under conditions of a surface area reduction rate of 26% at normal temperature, and then annealed at 460 ° C for 4.5 hours, and finally 13. 5% of reduction of area extraction Shin machining diameter of a material obtained by performing 3. 5 mm [Phi, the collected specimens of the parallel portion 20 mm, tensile at room temperature at a strain rate of 5 X 10- 4 sec conditions The test was done.
- the machinability was evaluated by the drill cutting test method. Here, I used an Okg weight. The results of these tests are shown in Table 17. Completely remove the cutting oil adhering to the chip surface After removal, the brass alloy material obtained by using this as the input material via the compacting and extrusion process has excellent mechanical properties and machinability.
- This raw material is crushed by using a powder having an average particle diameter of 100 ⁇ m as a starting material, and 0.3% of natural graphite particles having an average particle diameter of 50 m is added thereto and mixed with hydrostatic pressure.
- a cylindrical powder-solidified billet with a diameter of 59.8 mm ⁇ and a total length of 120 mm was produced by attaching to a press and solidifying under pressure. This billet is heated and held at 640 to 700 ° C. for 30 minutes in a nitrogen gas atmosphere, and immediately filled into an extrusion container with an inner diameter of 60 ⁇ and extruded at a diameter of 9.8 ⁇ under conditions of an extrusion ratio of 37.5. The material was made.
- the extruded material produced as described above is pickled and then drawn at room temperature under a reduction ratio of 26%, then annealed at 460 ° C. for 4.5 hours, and finally 13.
- a tensile test specimen with a diameter of 3.5 mm, and a parallel part of 20 mm is collected from the material obtained by drawing at a reduction rate of 5%, and tension is applied at room temperature under conditions of strain rate 5 X 10 _ 4 Z seconds. The test was done.
- the present invention can be advantageously used for a copper alloy extruded material that requires stable high machinability and excellent mechanical properties.
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Abstract
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EP06781540A EP1918389A4 (en) | 2005-07-28 | 2006-07-25 | EXTRUDED COPPER ALLOY MATERIAL AND METHOD OF MANUFACTURING THEREOF |
JP2007528465A JP4190570B2 (ja) | 2005-07-28 | 2006-07-25 | 無鉛快削性銅合金押出材 |
US11/989,492 US20090092517A1 (en) | 2005-07-28 | 2006-07-25 | Copper Alloy Extruded Material and Its Manufacturing Method |
CN2006800277380A CN101233250B (zh) | 2005-07-28 | 2006-07-25 | 铜合金挤压材及其制造方法 |
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US6974509B2 (en) * | 2000-09-07 | 2005-12-13 | Kitz Corporation | Brass |
US6837915B2 (en) * | 2002-09-20 | 2005-01-04 | Scm Metal Products, Inc. | High density, metal-based materials having low coefficients of friction and wear rates |
DE10308779B8 (de) * | 2003-02-28 | 2012-07-05 | Wieland-Werke Ag | Bleifreie Kupferlegierung und deren Verwendung |
CN100336927C (zh) * | 2003-12-12 | 2007-09-12 | 上海第一铜棒厂 | 低铜高速切削合金材料 |
CN1291051C (zh) * | 2004-01-15 | 2006-12-20 | 宁波博威集团有限公司 | 无铅易切削锑黄铜合金 |
-
2006
- 2006-07-25 EP EP06781540A patent/EP1918389A4/en not_active Withdrawn
- 2006-07-25 JP JP2007528465A patent/JP4190570B2/ja not_active Expired - Fee Related
- 2006-07-25 WO PCT/JP2006/314628 patent/WO2007013428A1/ja active Application Filing
- 2006-07-25 KR KR1020077029613A patent/KR100982611B1/ko not_active IP Right Cessation
- 2006-07-25 US US11/989,492 patent/US20090092517A1/en not_active Abandoned
- 2006-07-25 CN CN2006800277380A patent/CN101233250B/zh not_active Expired - Fee Related
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2275582A1 (en) * | 2008-05-07 | 2011-01-19 | Japan Science and Technology Agency | Brass alloy powder, brass alloy extruded material and method for producing the brass alloy extruded material |
EP2275582A4 (en) * | 2008-05-07 | 2014-08-20 | Japan Science & Tech Agency | MEASURING ALLOY POWDER, EXTRUDED MEASUREMENT ALLOY MATERIAL, AND METHOD FOR PRODUCING THE EXTRUDED MEASUREMENT ALLOY MATERIAL |
JP2011179121A (ja) * | 2010-03-02 | 2011-09-15 | Xiamen Lota Internatl Co Ltd | 環境に優しいマンガン黄銅合金およびそれらの製造方法 |
JP2017511841A (ja) * | 2014-02-04 | 2017-04-27 | オットー フックス カーゲー | 潤滑剤適合性銅合金 |
JP2019516868A (ja) * | 2016-05-18 | 2019-06-20 | アルマグ・ソシエタ・ペル・アチオニAlmag S.P.A. | 無鉛または低鉛含有量の真鍮ビレットの製造方法およびこれにより得られるビレット |
JP2021185265A (ja) * | 2016-05-18 | 2021-12-09 | アルマグ・ソシエタ・ペル・アチオニAlmag S.P.A. | 無鉛または低鉛含有量の真鍮ビレットの製造方法およびこれにより得られるビレット |
US11679436B2 (en) | 2016-05-18 | 2023-06-20 | Almag S.P.A. | Method for manufacturing a lead-free or low lead content brass billet and billet thus obtained |
IT202000004480A1 (it) * | 2020-03-03 | 2021-09-03 | A L M A G S P A Azienda Lavorazioni Metallurgiche E Affini Gnutti | Processo per l’ottenimento di una billetta di ottone a ridotto tenore di piombo e billetta così ottenuta |
JP2022059922A (ja) * | 2020-10-02 | 2022-04-14 | 大豊工業株式会社 | すべり軸受用銅合金およびすべり軸受 |
JP7455039B2 (ja) | 2020-10-02 | 2024-03-25 | 大豊工業株式会社 | すべり軸受用銅合金およびすべり軸受 |
WO2022124280A1 (ja) * | 2020-12-11 | 2022-06-16 | 国立大学法人豊橋技術科学大学 | 棒状または管状の高強度銅合金およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN101233250B (zh) | 2010-11-24 |
KR20080043737A (ko) | 2008-05-19 |
US20090092517A1 (en) | 2009-04-09 |
EP1918389A1 (en) | 2008-05-07 |
JP4190570B2 (ja) | 2008-12-03 |
EP1918389A4 (en) | 2010-06-23 |
KR100982611B1 (ko) | 2010-09-15 |
CN101233250A (zh) | 2008-07-30 |
JPWO2007013428A1 (ja) | 2009-02-05 |
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