WO2010122960A1 - Alliage de cuivre à résistance élevée - Google Patents

Alliage de cuivre à résistance élevée Download PDF

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Publication number
WO2010122960A1
WO2010122960A1 PCT/JP2010/056854 JP2010056854W WO2010122960A1 WO 2010122960 A1 WO2010122960 A1 WO 2010122960A1 JP 2010056854 W JP2010056854 W JP 2010056854W WO 2010122960 A1 WO2010122960 A1 WO 2010122960A1
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Prior art keywords
copper alloy
iron
strength copper
chromium
alloy according
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PCT/JP2010/056854
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English (en)
Japanese (ja)
Inventor
勝義 近藤
美治 上坂
明倫 小島
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サンエツ金属株式会社
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Application filed by サンエツ金属株式会社 filed Critical サンエツ金属株式会社
Priority to JP2011510307A priority Critical patent/JP5326114B2/ja
Priority to CN201080013404.4A priority patent/CN102361995B/zh
Priority to EP10767017A priority patent/EP2423339A1/fr
Priority to US13/258,467 priority patent/US20120027638A1/en
Publication of WO2010122960A1 publication Critical patent/WO2010122960A1/fr

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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
    • 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

Definitions

  • the present invention relates to a high strength copper alloy with excellent mechanical properties, and in particular to a high strength copper alloy made by a casting method. More preferably, the present invention seeks to provide a high strength copper alloy having enhanced strength characteristics by subjecting a cast copper alloy to hot plastic working.
  • Copper alloys are widely used in automobile parts, home appliance parts, electric / electronic / optical system parts, piping members (water faucet fittings, valves) and the like. Considering measures to prevent global warming in recent years, size and weight reduction and thickness reduction of products and members are strongly required, and copper alloys with a specific gravity larger than that of iron meet the above needs by strengthening them. There is a need.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-119775 (Patent Document 1) has been proposed as a prior art related to increasing the strength of a brass alloy.
  • Patent Document 1 Japanese Patent Laid-Open No. 2000-119775
  • a brass alloy having high properties of about 600 to 800 MPa in tensile strength can be obtained by subjecting a cast copper alloy to hot extrusion processing.
  • Silicon (Si) which is an additive element, exhibits the advantage of improving the machinability of the copper alloy by causing the ⁇ phase that constitutes the base to appear, but on the other hand, because it is hard, JIS H 3250-C3604, Compared with brass alloys such as C3771, it causes problems such as high cutting resistance and short tool life.
  • the present invention aims at producing a copper alloy having high strength properties by a casting process, and proposes a copper-zinc alloy containing appropriate amounts of iron and chromium in order to achieve this purpose.
  • the high strength copper alloy according to the present invention can be widely applied to automobile parts, home appliance parts, electric / electronic / optical parts, piping members and the like.
  • the high strength copper alloy according to the present invention contains 20 to 45% of zinc, 0.3 to 1.5% of iron, 0.3 to 1.5% of chromium, and the balance is copper, on a weight basis. Become.
  • the high strength copper alloy has a content ratio of iron to chromium (Fe / Cr) of 0.5 to 2 on a weight basis.
  • the high strength copper alloy further comprises, on a weight basis, 0.05 to 4% lead, 0.02 to 3.5% bismuth, 0.02 to 0.4% tellurium, 0. It contains one or more elements selected from the group consisting of 02 to 0.4% selenium and 0.02 to 0.15% antimony. Furthermore, 0.2 to 3% of tin may be contained on a weight basis. Furthermore, it may contain 0.2 to 3.5% of aluminum and 0.3 to 3.5% of calcium based on weight.
  • lanthanoid elements consisting of lanthanum, cerium, neodymium, gadolinium, dysprosium, ytterbium, samarium, and the total content thereof is 0.5 to 5% by weight. It is good. Furthermore, by weight, 0.5 to 3% of manganese, 0.2 to 1% of silicon, 1.5 to 4% of nickel, 0.1 to 1.2% of titanium, 0.1 to 1.5 % Cobalt, and may contain one or more elements selected from the group consisting of 0.5 to 2.5% zirconium.
  • the high strength copper alloy comprises iron-chromium compound particles at grain boundaries.
  • the iron-chromium compound particles are precipitated at grain boundaries in the process of solidification by a casting method, and the preferred particle size is 10 to 50 ⁇ m.
  • the copper alloy is produced by a casting method and then subjected to hot plastic working.
  • the hot plastic working is, for example, at least one working method selected from the group consisting of extrusion, forging, rolling, drawing and drawing.
  • iron and chromium are both essential additive elements.
  • the content is, by weight, iron: 0.3 to 1.5%, chromium: 0.3 to 1.5%. Since chromium has a low solid solubility with respect to copper, a copper-chromium master alloy is prepared, and the copper-chromium master alloy is added to the molten pure copper melt in the crucible to adjust the chromium content. Next, iron is added at a predetermined weight. Thereafter, other elements are added as needed, and finally zinc is added and cast into a mold after stirring. Zinc is added last to molten copper alloy because zinc is easily evaporated compared to other elements because of its high vapor pressure.
  • the molten copper alloy melt is cooled and solidified in the mold, but in the process, chromium which is slightly dissolved in copper crystallizes in the grain boundaries of copper, and then in the vicinity of the chromium crystallized product. Iron crystallizes out.
  • grain boundary compound particles having a size (particle diameter) of about 10 to 50 ⁇ m in which chromium and iron are concentrated are present, and the strength of the brass alloy is increased by the dispersion strengthening of the grain boundary compound particles.
  • the present inventors have also described the strength improvement effect by the addition of iron and chromium in a brass alloy in Japanese Patent No. 4190570 (lead-free machinable copper alloy extruded material).
  • the invention described in this publication assumes a powder metallurgical process by a rapid solidification method as a basic manufacturing method, and chromium or iron solid-dissolved in supersaturation in copper alloy powder is precipitated in the process of extrusion processing, and several hundred nano It precipitates in grain boundaries and grains as fine iron-chromium compounds of meters to several microns.
  • Submicron fine iron-chromium compound particles deposited on the premise of such powder metallurgy process, and iron-chromium grain boundary crystallized product (compound particles) in the solidification process according to the casting method proposed in the present invention Is different in particle size, and the mechanism of generation is also completely different.
  • iron When considering the content of iron and chromium suitable for strengthening a brass alloy, it is desirable that iron is 0.3 to 1.5% and chromium is 0.3 to 1.5% by weight. If the content of iron and chromium is less than 0.3%, respectively, the effect of improving the strength of the brass alloy as described above is small, while if the content of each exceeds 1.5%, the ductility of the brass alloy decreases. Do. With regard to iron, when the content exceeds 2%, there arises a problem that the corrosion resistance of the brass alloy is lowered.
  • the weight ratio of iron to chromium is preferably 0.5 to 2.
  • the content ratio of iron and chromium satisfies the above range, the existing ratio of the above-described chromium and iron enriched grain boundary compound increases. In other words, if the content ratio of both is less than 0.5 or more than 2, iron or chromium is crystallized alone at grain boundaries, so that the strength improvement effect is reduced.
  • [Containing element for improving machinability] To improve the machinability of brass alloys, 0.05 to 4% lead, 0.02 to 3.5% bismuth, 0.02 to 0.4% tellurium, 0.02 to 0.5% by weight It is desirable to contain one or more elements selected from the group consisting of 0.4% selenium, 0.02 to 0.15% antimony. If the lower limit value of the above range is exceeded for each element, sufficient machinability can not be obtained, and problems such as surface roughness of the brass alloy material after cutting and deterioration of tool life occur. On the other hand, when the upper limit value of each element content is exceeded, it becomes a starting point of fracture, which causes deterioration of mechanical properties such as strength and ductility. From the viewpoint of environmental problems in recent years, since the use of lead is restricted, bismuth is more preferably selected as the machinability improving element.
  • Tin is effective in forming the ⁇ phase in the matrix and at the same time is effective in forming a compound with copper to strengthen the alloy.
  • the preferred content of tin is 0.2 to 3% by weight. If the content is less than 0.2%, the above effect is small, while if more than 3% is added, the ductility of the brass alloy is reduced. When the addition amount (content) of tin exceeds 2%, there is an effect of improving the dezincing resistance of the ⁇ phase.
  • Aluminum forms an intermetallic compound with copper, and its spherical particles are dispersed in the matrix to improve mechanical properties such as strength and hardness of copper alloy and high temperature oxidation resistance.
  • the preferred content of aluminum is 0.2 to 3.5% by weight. If the content is less than 0.2%, the above effect is small. On the other hand, if the content is more than 3.5%, the compound with copper is coarsened to cause the ductility of the brass alloy to be lowered. Further, the presence of aluminum together with calcium described later forms an intermetallic compound of Al 2 Ca and contributes to the improvement of strength and hardness.
  • Calcium is included in the copper alloy together with aluminum to form an intermetallic compound of Al 2 Ca, which contributes to improvement in strength and hardness.
  • the preferred content of calcium is 0.3 to 3.5% by weight. If the content is less than 0.3%, the above effect is small. On the other hand, if calcium is added to more than 3.5%, the intermetallic compound of Al 2 Ca becomes coarse, resulting in a decrease in ductility of the brass alloy.
  • the lanthanide series element group (lanthanum, cerium, neodymium, gadolinium, dysprosium, ytterbium, samarium) forms a compound with copper and precipitates at grain boundaries, and strengthens the base by crystallizing at grain boundaries alone. Because it is effective.
  • the total content is preferably 0.5 to 5% by weight. If the content is less than 0.5%, the effect is not sufficient. If the lanthanoid element group is added to more than 5%, the ductility is lowered and, at the same time, the copper alloy becomes too hard and the extrusion processability is lowered.
  • the strength and hardness of the copper alloy can be improved by adding at least one element selected from the group consisting of 1 to 1.5% cobalt and 0.5 to 2.5% zirconium. Below the lower limit value of the content of each element, the effect of the above-mentioned characteristic improvement is not sufficient, and on the other hand, when the upper limit value is exceeded, the ductility of the copper alloy is lowered.
  • a molten copper alloy having the above composition is produced, and the ingot material is produced by a method of casting the molten metal in a mold or a continuous casting method. Further, the ingot material is subjected to hot plastic working such as extrusion processing, forging processing, rolling processing, drawing processing, drawing processing and the like as necessary. At this time, the heating temperature for sufficiently ingot plastic deformation is in the range of 600 to 850.degree. In particular, a heating temperature of 750 ° C. or less is desirable in order to suppress the evaporation of zinc during the heating process.
  • Example 1 A copper alloy cast ingot containing each element listed in Table 1 and Table 2 was prepared, and after heating and holding each ingot at 700 ° C., hot extrusion processing was immediately performed. The extrusion ratio of the extrusion process was 37. A tensile test piece was taken from each copper alloy extruded material, and a tensile test was performed at room temperature under the condition of strain rate of 5 ⁇ 10 ⁇ 4 / s. The results are shown in Tables 1 and 2. The inventive examples are sample numbers 1 to 16, and the comparative examples are sample numbers 17 to 19.
  • the tensile strength (TS) of the extruded material is increased by about 130 to 210 MPa as compared with the sample number 19 which is the comparative example. doing.
  • the reason for this is that the strength of the copper alloy is significantly increased by the dispersion of iron-chromium compound particles consisting of iron and chromium in the grain boundaries. It is also recognized that the tensile strength is also increased as the addition of iron and chromium is increased.
  • Sample Nos. 6 to 8 which are inventive examples are copper alloys containing bismuth (Bi), and sample Nos. 9 to 11 which are inventive examples are copper alloys containing lead (Pb).
  • bismuth and lead are additive elements for improving the machinability of the copper alloy
  • the copper alloys of sample Nos. 9 to 11 have tensile strengths as compared with sample No. 2 of the example of the present invention not containing these. Although it slightly decreases, an increase in strength of about 160 to 190 MPa is observed as compared with the sample No. 17 or 18 of the comparative example. Therefore, by adding bismuth or lead to a brass alloy containing iron and chromium, the machinability can be improved while maintaining excellent tensile strength.
  • sample numbers 12 and 13 of the example of the present invention an increase in strength can be confirmed by containing tin (Sn).
  • the intermetallic compound Al 2 Ca is dispersed in the base of the copper alloy by containing aluminum (Al) and calcium (Ca), and as a result, the tensile strength is increased. It is increasing significantly.
  • Example 2 A copper alloy cast ingot containing each element listed in Table 3 and Table 4 was prepared in the same manner as in Example 1, and each ingot was heated and held at 700 ° C., and immediately subjected to hot extrusion processing. The extrusion ratio of the extrusion process was 37. A tensile test piece was taken from each copper alloy extruded material, and a tensile test was performed at room temperature under the condition of a strain rate of 5 ⁇ 10 ⁇ 4 / s. The results are shown in Table 3 and Table 4. The inventive examples are sample numbers 20-24, 28-33, and the comparative examples are sample numbers 25-27, 34, 35.
  • sample numbers 21, 22, 23, 24 of the inventive example contain a lanthanoid element, the tensile strength is further increased as compared with the sample No. 20 of the inventive example not including them, It reaches 680 MPa.
  • sample numbers 29 and 30 of the inventive example are also brass alloys containing lanthanoid elements, and it is possible to confirm a significant increase in tensile strength as compared to the sample number 28 of the inventive example not including them.
  • Sample No. 31 of the present invention example is a brass alloy containing an appropriate amount of silicon (Si)
  • sample No. 32 of the present invention example is a brass alloy containing an appropriate amount of nickel (Ni)
  • sample No. 33 of the present invention example is titanium (Ti) It is possible to confirm an increase in tensile strength as compared with the sample No. 28 of the example of the present invention which does not contain these elements and is a brass alloy containing an appropriate amount of.
  • the comparative example containing iron and chromium but not containing iron and chromium because the iron to chromium content ratio does not satisfy 0.5 to 2 on a weight basis
  • the brass alloy of the invention example satisfying the content ratio of both of 0.5 and 2 (sample Nos. 1 to 5 of the invention example of Table 1) It has a lower value as compared with the sample No. 20 of the example of the present invention of Table 3 and the sample No. 28 of the example of the present invention of Table 4.
  • Example 3 A tensile test piece was taken from each of the brass alloy extruded materials of Sample No. 3 and Sample No. 5 of the invention example and the brass extruded material of Sample No. 19 of the Comparative Example, and a tensile test was performed. The stress-strain diagram in this tensile test is shown in FIG. It can be seen that the sample numbers 3 and 5 of the inventive example have higher tensile strength and yield strength (yield strength) as compared to the sample number 19 of the comparative example.
  • Example 4 The result of the tissue observation of the sample No. 3 of the inventive example with an optical microscope is shown in FIG. It can be seen that Fe—Cr-based compound particles having a diameter of about 20 to 50 ⁇ m are uniformly dispersed in the brass alloy base.
  • Example 5 The result of SEM-EDS (Scanning Electron Microscopy-Energy Dispersive Spectroscopy) analysis of the brass alloy extruded material of sample No. 12 of the inventive example described in Example 1 is shown in FIG. It can be seen that the main components of the compound to be dispersed are iron (Fe) and chromium (Cr).
  • Example 6 A copper alloy cast ingot containing each element listed in Table 5 and Table 6 is prepared, a tensile test piece is taken from each copper alloy ingot, and a tensile test at room temperature under a strain rate of 5 ⁇ 10 -4 / s. Carried out. The results are shown in Tables 5 and 6.
  • the inventive examples are sample numbers 1 to 16, and the comparative examples are sample numbers 17 to 19. In the example of the present invention, it is understood that the cast ingot material before the extrusion processing has high strength relative to the comparative example by including the appropriate amount of the predetermined element.
  • Example 7 The machinability of the brass alloy extruded materials of sample numbers 5 to 11 of the inventive example described in Example 1 and Example 2 and sample numbers 17 to 19 of the comparative example were evaluated by a drilling test.
  • a drilling test as shown in FIG. 4, the time required to process a hole of 5 mm in depth in each copper alloy extruded material in a state where a constant load (load of 1 kg is applied here) is applied to the drill Compared. The shorter the processing time, the better the machinability means.
  • using a high-speed steel drill with a diameter of 4.8 mm ⁇ the number of rotations of the drill is 1,000 rpm, and a drill test is performed on 10 samples in one extruded material under dry conditions (without cutting oil). The average value was determined from the values. The results are shown in Table 7.
  • sample No. 5 of the example of the present invention which does not contain any bismuth, lead or the like which improves the machinability, under the above conditions, even if drilling with a drill for 3 minutes is performed, the depth is 5 mm I could not make a hole.
  • Sample Nos. 6 to 8 of the inventive example are brass alloys to which bismuth is added, and it is possible to make holes in any case, and the processing time is shortened as the amount of added bismuth increases.
  • Sample Nos. 9 to 11 of the inventive example are alloys to which lead is added, and the cutting time is shortened as the content of lead is increased. Therefore, it was confirmed that machinability can be significantly improved by adding bismuth or lead while maintaining high tensile strength.
  • Example 8 A copper alloy cast ingot containing each element listed in Table 8 was prepared, and after heating and holding each at 650 ° C., hot extrusion processing was immediately performed. The extrusion ratio of the extrusion process was 37. A tensile test piece was taken from each copper alloy extruded material, and a tensile test was performed at room temperature under the condition of strain rate of 5 ⁇ 10 ⁇ 4 / s. With regard to the evaluation of the machinability, the average machining time was calculated using the same method as in Example 7 described above. The results are listed in Table 8. Sample Nos. 40 to 56 are all inventive examples.
  • Example 9 A molten copper alloy containing each element listed in Table 9 is prepared in a crucible, and a powder having a particle diameter of 150 ⁇ m or less (average particle diameter 112 to 138 ⁇ m) is produced by a water atomizing method, and each powder is subjected to discharge plasma sintering Heat and pressure (pressure 40 MPa) in a vacuum atmosphere at 750 ° C. to prepare a dense sintered body. Each sintered body was heated and held at 650 ° C. in nitrogen gas atmosphere (holding time: 15 minutes), and immediately subjected to hot extrusion processing. The extrusion ratio of the extrusion process was 37.
  • the present invention can be advantageously utilized as a high strength copper alloy having excellent mechanical properties.

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Abstract

L'invention porte sur un alliage de cuivre à résistance élevée qui contient, en termes de % poids, 20–45% de zinc, 0,3–1,5% de fer et 0,3-1,5% de chrome, le reste étant du cuivre.
PCT/JP2010/056854 2009-04-24 2010-04-16 Alliage de cuivre à résistance élevée WO2010122960A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2011510307A JP5326114B2 (ja) 2009-04-24 2010-04-16 高強度銅合金
CN201080013404.4A CN102361995B (zh) 2009-04-24 2010-04-16 高强度铜合金
EP10767017A EP2423339A1 (fr) 2009-04-24 2010-04-16 Alliage de cuivre à résistance élevée
US13/258,467 US20120027638A1 (en) 2009-04-24 2010-04-16 High-strength copper alloy

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JP2009-106162 2009-04-24
JP2009106162 2009-04-24

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WO2010122960A1 true WO2010122960A1 (fr) 2010-10-28

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US (1) US20120027638A1 (fr)
EP (1) EP2423339A1 (fr)
JP (1) JP5326114B2 (fr)
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WO (1) WO2010122960A1 (fr)

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EP2333126A1 (fr) * 2009-12-09 2011-06-15 Xiamen Lota International Co., Ltd. Alliages de laiton dotés d'une haute résistance à la corrosion sous contrainte et procédé de leur fabrication
US8580191B2 (en) 2009-12-09 2013-11-12 Xiamen Lota International Co., Ltd. Brass alloys having superior stress corrosion resistance and manufacturing method thereof
WO2013047991A1 (fr) * 2011-09-30 2013-04-04 Poongsan Corporation Alliage de décolletage en cuivre sans plomb et son procédé de production
US9840758B2 (en) 2011-09-30 2017-12-12 Poongsan Corporation Leadless free-cutting copper alloy and method for producing the same
CN113166849A (zh) * 2018-10-29 2021-07-23 奥托福克斯两合公司 特种黄铜合金和特种黄铜合金产品
US11572606B2 (en) 2018-10-29 2023-02-07 Otto Fuchs Kommanditgesellschaft High-tensile brass alloy and high-tensile brass alloy product

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US20120027638A1 (en) 2012-02-02
JP5326114B2 (ja) 2013-10-30

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