WO2012111674A1 - 高強度銅合金鍛造材 - Google Patents
高強度銅合金鍛造材 Download PDFInfo
- Publication number
- WO2012111674A1 WO2012111674A1 PCT/JP2012/053414 JP2012053414W WO2012111674A1 WO 2012111674 A1 WO2012111674 A1 WO 2012111674A1 JP 2012053414 W JP2012053414 W JP 2012053414W WO 2012111674 A1 WO2012111674 A1 WO 2012111674A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper alloy
- strength
- alloy forging
- thermal conductivity
- strength copper
- Prior art date
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Classifications
-
- 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J1/00—Preparing metal stock or similar ancillary operations prior, during or post forging, e.g. heating or cooling
- B21J1/003—Selecting material
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
-
- 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 forged material suitable for forged molded articles including resin injection mold materials.
- copper alloys such as brass (Cu—Zn), bronze (Cu—Sn), Be copper, and Corson alloy (Cu—Ni—Si) have been used as alloys having excellent conductivity and thermal conductivity.
- Be copper and Corson alloy are used for resin injection mold materials and aircraft members that require heat conduction and strength and hardness.
- Be copper is concerned about the toxicity of dust generated during melting and processing, and an alternative material is required.
- the Corson alloy is required to have higher thermal conductivity, higher strength, and higher hardness.
- Cu alloys are liable to crack during forging or heat treatment, and it is required to improve ductility in addition to hot workability.
- the copper alloy foil strips as shown in Patent Documents 2, 3, and 5 are added with Sn, Mn, Zr, and the like, and before and after the solution treatment and the aging treatment, hot rolling, cold rolling and hot rolling. By repeatedly performing drawing and cold drawing, it has bending workability and strength exceeding conventional copper alloy foil strips.
- Patent Documents 2, 3, and 5 are shown. Even if a forged molded product is manufactured with various components, high strength cannot be obtained. In order to obtain high strength, it is effective to increase the amounts of Ni and Si. However, as the amounts of Ni and Si increase, the thermal conductivity and hot workability decrease. Moreover, the crystallized substance produced
- the present invention has been made against the background of the above circumstances, and can be used for forged molded articles such as resin injection mold materials, and can obtain characteristics of high hardness, high strength, high ductility, and high thermal conductivity. It aims at providing the high strength copper alloy forging material which can be performed.
- the present invention contains a suitable amount of Zr having an effect of increasing the ductility by suppressing the precipitation of Ni 2 Si to the grain boundary in the Cu—Ni—Si based copper alloy,
- the material having the effect of increasing the density of fine precipitates and having the characteristics of high hardness, high strength, and high thermal conductivity is obtained by containing an appropriate amount of P that forms a compound with Ni, Si and Zr. It makes it possible.
- the first invention in the present invention is, in mass%, Ni: 3 to 7.2%, Si: 0.7 to 1.8%, Zr: 0.02 to 0.35%, P: 0.00. It is a high-strength copper alloy forging containing 002 to 0.05%.
- Ni 3 to 7.2%, Si: 0.7 to 1.8%, Zr: 0.02 to 0.35%, P: 0.002 to 0.05 by mass% Is a high-strength copper alloy forging material that further contains 1.5% or less of one or more of Cr, Mn, and Zn in total.
- a third invention is a high-strength copper alloy forging according to the first invention or the second invention, wherein the 0.2% proof stress is 650 MPa or more, the elongation is 5% or more, and the conductivity is 30% IACS or more. is there.
- the present invention it is possible to obtain a high-strength copper alloy forged material that is less prone to cracking during processing or heat treatment and that has characteristics of high hardness, high strength, and high thermal conductivity.
- Ni and Si form precipitation particles of intermetallic compounds mainly composed of Ni 2 Si in which Ni and Si are fine by performing an aging treatment, and remarkably increase the strength of the alloy. Further, with the precipitation of Ni 2 Si in the aging treatment, the conductivity is improved and the thermal conductivity is improved. However, when the Ni concentration is less than 3% and the Si concentration is less than 0.7%, the desired strength cannot be obtained. Further, when the Ni concentration exceeds 7.2% and the Si concentration exceeds 1.8%, a large amount of Ni 2 Si, Ni 5 Si 2 or the like crystallizes or precipitates during casting, and during forging or heat treatment It becomes easy to break.
- the Ni concentration is desirably a lower limit of 3.5% and an upper limit of 6.6%.
- the Si concentration is desirably a lower limit of 0.8% and an upper limit of 1.7%.
- the Ni / Si ratio is preferably 3.8 to 4.6. If it deviates from this ratio, the excess Ni or Si is dissolved in the Cu matrix and the thermal conductivity is lowered.
- Zr 0.02 to 0.35%
- Zr has a strong affinity with sulfur, so it forms a compound with sulfur and reduces the segregation of sulfides to the grain boundaries that are the cause of work cracking (hot work cracking). Improvement).
- Ni 2 Si precipitated due to the inclusion of Zr was suppressed and Ni 2 Si precipitated at grain boundaries was reduced, and the ductility after aging was improved. Yes. To obtain this effect, 0.02% or more of Zr is contained.
- the upper limit is made 0.35%.
- the lower limit is preferably 0.05% and the upper limit is 0.3%.
- P 0.002 to 0.05% P increases the strength by increasing the density of fine precipitates. Moreover, hardness is increased by forming a compound containing a small amount of P in Ni, Si and Zr and Ni 2 Si or Ni 2 SiZr. In order to acquire these effects, it contains 0.002% or more. However, if it exceeds 0.05%, the thermal conductivity is greatly reduced, so the upper limit is made 0.05%. For the same reason, it is desirable to set the lower limit to 0.01% and the upper limit to 0.04%.
- Cr, Mn, Zn 1.5% or less in total Cr, Mn, Zn contains one or more as desired.
- Cr forms an intermetallic compound with Si, and has the effect of improving the strength and miniaturizing the crystal grains.
- Mn has a strong affinity for sulfur, so it forms a compound with sulfur and reduces workability (hot workability) by reducing the segregation of sulfides to the grain boundaries that cause work cracking (hot work cracking). ).
- Zn improves the strength by solid solution strengthening. Moreover, if an inexpensive brass scrap can be used at the time of melt
- the total amount of Cr, Mn, and Zn is preferably 1.5% or less. More preferably, the total amount of Cr, Mn and Zn is 1.0% or less. Moreover, when it contains 1 or more types of Cr, Mn, and Zn, it is desirable to set it as 0.1% or more in total amount.
- the high-strength copper alloy forged material of the present invention has the above metal composition, and the remainder is composed of Cu and inevitable impurities.
- the high-strength copper alloy forged material of the present invention can be produced by a conventional method.
- the copper alloy used in the present invention can be melted by a conventional method.
- an ingot can be obtained by melting the material in a vacuum atmosphere, an inert atmosphere, or an air atmosphere.
- the atmosphere is preferably a vacuum atmosphere or an inert atmosphere, but may be melted in an atmospheric high-frequency furnace, for example. Further, secondary melting using an electroslag remelting furnace or the like may be performed. It is also possible to obtain a plate material by a continuous casting method.
- Copper alloy is processed as needed.
- the content of processing is not particularly limited as the present invention, and the characteristics of the present invention can be obtained using any processing method.
- the processing is preferably hot processing in consideration of manufacturability, and further, hot processing performed at 600 ° C. or higher is preferable, but the same characteristics as hot processing can be obtained even at processing at room temperature. Further, the processing may be a combination of hot processing and cold processing. Further, forging and hot forging are desirable as processing, and it is more desirable to perform hot forging at 600 ° C. or higher.
- As the forging method for example, a known method such as pressing, hammering or rolling can be adopted.
- the processed copper alloy material can be subjected to a solution treatment after processing or during processing.
- the solution treatment conditions are, for example, holding at 800 to 1000 ° C. for 1 to 10 hours, and then cooling at a temperature range of 500 ° C. or higher at a cooling rate of 5 ° C./second or more in order to sufficiently dissolve Ni and Si. Is mentioned.
- the processed copper alloy material can be subjected to a solution treatment or an aging treatment after processing.
- a condition for the aging treatment is, for example, holding at 400 to 500 ° C. for 1 to 30 hours.
- the obtained high-strength copper alloy material has characteristics such that 0.2% proof stress is 650 MPa or more, elongation is 5% or more, and conductivity is 30% IACS or more.
- the high-strength copper alloy forged material of the present invention has excellent characteristics as a forged material, but the composition of the present invention has good ductility even in a cast material that has not been subjected to the above-described processing such as forging. Etc. can be obtained.
- Raw materials were blended so as to have the component composition shown in Table 1 (including other inevitable impurities) and melted in a vacuum induction melting furnace to prepare an alloy having a diameter of 100 mm ⁇ 200 mm.
- This alloy was hot-forged with a hammer at 900 ° C. to obtain a 25 mm thick plate material, which was kept at 970 ° C. for 4 hours and then subjected to a solution treatment in which it was cooled with water. Thereafter, an aging treatment suitable for each component material was performed at 400 to 500 ° C. for 1 to 30 hours to obtain test materials.
- the specimens of the examples of the present invention had a 0.2% proof stress of 650 MPa or more, an elongation of 5% or more, and a conductivity of 30% IACS or more. Further, it had a hardness equal to or higher than that of the test material of the comparative example.
- the present invention by including appropriate amounts of Zr and P in a Ni—Si—Cu alloy, excellent performance is achieved in that strength, ductility, and hardness are increased while maintaining high conductivity, that is, high thermal conductivity. It was revealed that
- an appropriate amount of Zr and P acts to prevent cracking of the material during processing or heat treatment, and after processing and heat treatment, high hardness, high strength and high heat conduction Rate characteristics and can be suitably used for resin injection mold materials, aircraft members, and the like.
Abstract
Description
また、一般にCu合金は鍛造時や熱処理時に割れが発生しやすく、熱間加工性に加え延性の向上も求められる。
高強度を得るためにはNiとSiの添加量の増加が有効であるが、NiやSi量の増加に伴って、熱伝導率や熱間加工性が低下する。また、凝固中に生成する晶出物や熱処理中に生成する析出物が増加し、熱処理後の延性が低下する。
Si:0.7~1.8%
Ni及びSiは、時効処理を行うことによりNiとSiが微細なNi2Siを主とした金属間化合物の析出粒子を形成し、合金の強度を著しく増加させる。また、時効処理でのNi2Siの析出に伴い、導電性が向上し、熱伝導率が向上する。ただし、Ni濃度が3%未満で、かつSi濃度が0.7%未満の場合は、所望とする強度が得られない。また、Ni濃度が7.2%を超え、かつSi濃度が1.8%を超える場合は、鋳造時にNi2Si、Ni5Si2などが大量に晶出又は析出し、鍛造時や熱処理時に割れやすくなる。加えて、Ni濃度が7.2%を超えると導電率も低下し、熱伝導率が低下する。製造性や特性のバランスを考慮すると、Ni濃度は、下限3.5%、上限6.6%が望ましい。Si濃度は、下限0.8%、上限1.7%が望ましい。なお、Ni/Si比は3.8~4.6が望ましい。この比から外れると、過剰となったNi又はSiがCuマトリックス中に固溶して熱伝導率を低下させる。
Zrは、硫黄との親和性が強いため硫黄と化合物を形成し、加工割れ(熱間加工割れ)の原因である結晶粒界への硫化物の偏析を軽減することで加工性(熱間加工性)を改善する。一方で、発明者らが鋭意調査した結果、Zr含有によりNiやSiの拡散が抑制されて粒界に析出するNi2Siが減少し、時効後の延性が改善されることが見出されている。この効果を得るためにZrを0.02%以上含有させる。しかし、0.35%超含有するとZr酸化物やNi2SiZrなどの晶出物の増加、凝集によって製造性や特性が劣化するため、上限を0.35%とする。製造性や特性のバランスを考慮すると、下限0.05%、上限0.3%が望ましい。
Pは微細析出物の密度を増加させることで強度を向上させる。また、Ni、Si及びZrとNi2SiまたはNi2SiZrなどに微量のPを含有した化合物を形成することで硬さが増加する。これらの効果を得るために0.002%以上含有させる。しかし、0.05%超含有すると熱伝導率が大きく低下するので上限を0.05%とする。同様の理由により、下限を0.01%、上限を0.04%とするのが望ましい。
Cr、Mn、Znは、所望により1種以上を含有させる。
CrはSiと金属間化合物を形成し、強度を向上させたり、結晶粒を微細化したりする効果がある。Mnは硫黄との親和性が強いため硫黄と化合物を形成し、加工割れ(熱間加工割れ)の原因である結晶粒界への硫化物の偏析を低減することで加工性(熱間加工性)を改善する。Znは固溶強化により強度を向上させる。また、溶解時に安価な黄銅スクラップを使用可能であれば製造コストを削減できる。しかし、Cr、Mn、Znを合計量で過剰に含有すると熱伝導率が低下するため、Cr、MnおよびZnの合計量を1.5%以下とすることが好ましい。
より好ましくは、Cr、Mn及びZnの合計量を1.0%以下とするのが望ましい。また、Cr、Mn、及びZnの1種以上を含有させる場合、合計量で0.1%以上とするのが望ましい。
本発明に用いる銅合金は、常法により溶製することができ、例えば、真空雰囲気、不活性雰囲気、または大気雰囲気などで材料を溶解し、鋳塊を得ることができる。雰囲気は真空雰囲気、または不活性雰囲気が望ましいが、例えば大気高周波炉で溶製することもできる。また、エレクトロスラグ再溶解炉などを用いた二次溶解を行ってもよい。連続鋳造法によって板材を得ることも可能である。
加工された銅合金材は、固溶化処理後または加工後時効処理を行うことができる。時効処理の条件は、例えば、400~500℃で1~30時間保持することが挙げられる。
得られた高強度銅合金材は、0.2%耐力が650MPa以上、伸びが5%以上、導電率が30%IACS以上の特性を有している。
表1の成分組成(その他不可避不純物を含む)になるように、原料を配合し真空誘導溶解炉で溶解して100mm径×200mm長の合金を作製した。この合金を、900℃でハンマーにより熱間鍛造して25mm厚の板材とし、970℃で4時間保持した後に水冷する固溶化処理を実施した。その後、400~500℃で1~30時間の各成分の素材に適する時効処理をそれぞれ施して供試材を得た。
(引張試験)
各供試体にJISZ2201(2010)、JISZ2241(2010)に基づき常温引張試験を実施し、0.2%耐力(Y.S)、引張強度(T.S)、伸び、絞りを評価した。測定結果を表2に示した。
(ヴィッカース硬さ)
各供試体に対し、JISZ2244(2010)に基づき、荷重5kgでヴィッカース硬さを測定した。測定結果を表2に示した。
(熱伝導率)
各供試体について導電率を測定した。ヴィーデマン=フランツ則に示されるように熱伝導率と導電率はほぼ比例関係にあり、導電率で熱伝導率を評価することができる。測定結果を表2に示した。
以上のように、本発明は、Ni-Si-Cu合金に適量のZrとPを含有することにより、高導電率すなわち高熱伝導率を維持しつつ強度、延性、硬度が高くなるという優れた性能が得られることが明らかにされた。
Claims (3)
- 質量%で、Ni:3~7.2%、Si:0.7~1.8%、Zr:0.02~0.35%、P:0.002~0.05%を含有する高強度銅合金鍛造材。
- 質量%で、Ni:3~7.2%、Si:0.7~1.8%、Zr:0.02~0.35%、P:0.002~0.05%を含有し、さらに、Cr、Mn、及びZnの1種または2種以上を合計で1.5%以下含有する高強度銅合金鍛造材。
- 0.2%耐力が650MPa以上、伸びが5%以上、導電率が30%IACS以上である請求項1または2に記載の高強度銅合金鍛造材。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12747404.7A EP2677051A4 (en) | 2011-02-16 | 2012-02-14 | FORGING A HIGHEST COPPER ALLOY |
KR1020137021662A KR20130109238A (ko) | 2011-02-16 | 2012-02-14 | 고강도 동합금 단조재 |
US13/985,729 US20130323114A1 (en) | 2011-02-16 | 2012-02-14 | High-strength copper alloy forging material |
CN201280009422.4A CN103384727B (zh) | 2011-02-16 | 2012-02-14 | 高强度铜合金锻造材料 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2011-030660 | 2011-02-16 | ||
JP2011030660A JP5522692B2 (ja) | 2011-02-16 | 2011-02-16 | 高強度銅合金鍛造材 |
Publications (1)
Publication Number | Publication Date |
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WO2012111674A1 true WO2012111674A1 (ja) | 2012-08-23 |
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PCT/JP2012/053414 WO2012111674A1 (ja) | 2011-02-16 | 2012-02-14 | 高強度銅合金鍛造材 |
Country Status (7)
Country | Link |
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US (1) | US20130323114A1 (ja) |
EP (1) | EP2677051A4 (ja) |
JP (1) | JP5522692B2 (ja) |
KR (1) | KR20130109238A (ja) |
CN (1) | CN103384727B (ja) |
TW (1) | TWI539016B (ja) |
WO (1) | WO2012111674A1 (ja) |
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JP5688744B2 (ja) * | 2012-10-04 | 2015-03-25 | 株式会社日本製鋼所 | 高強度高靱性銅合金鍛造材 |
KR101472348B1 (ko) * | 2012-11-09 | 2014-12-15 | 주식회사 풍산 | 전기전자 부품용 동합금재 및 그의 제조 방법 |
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2011
- 2011-02-16 JP JP2011030660A patent/JP5522692B2/ja active Active
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2012
- 2012-02-14 EP EP12747404.7A patent/EP2677051A4/en not_active Withdrawn
- 2012-02-14 US US13/985,729 patent/US20130323114A1/en not_active Abandoned
- 2012-02-14 WO PCT/JP2012/053414 patent/WO2012111674A1/ja active Application Filing
- 2012-02-14 CN CN201280009422.4A patent/CN103384727B/zh active Active
- 2012-02-14 KR KR1020137021662A patent/KR20130109238A/ko not_active Application Discontinuation
- 2012-02-16 TW TW101105033A patent/TWI539016B/zh not_active IP Right Cessation
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JP2006283059A (ja) * | 2005-03-31 | 2006-10-19 | Kobe Steel Ltd | 曲げ加工性に優れた高強度銅合金板及びその製造方法 |
JP2008223136A (ja) | 2007-02-13 | 2008-09-25 | Dowa Metaltech Kk | Cu−Ni−Si系銅合金板材およびその製造法 |
JP2008196042A (ja) | 2007-02-16 | 2008-08-28 | Kobe Steel Ltd | 強度と成形性に優れる電気電子部品用銅合金板 |
JP2008266787A (ja) | 2007-03-28 | 2008-11-06 | Furukawa Electric Co Ltd:The | 銅合金材およびその製造方法 |
JP2010106363A (ja) | 2008-10-03 | 2010-05-13 | Furukawa Electric Co Ltd:The | 時効析出型銅合金、銅合金材料、銅合金部品および銅合金材料の製造方法 |
JP4630387B1 (ja) * | 2010-04-07 | 2011-02-09 | 古河電気工業株式会社 | 銅合金展伸材、銅合金部品および銅合金展伸材の製造方法 |
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EP2677051A1 (en) | 2013-12-25 |
EP2677051A4 (en) | 2014-09-03 |
JP5522692B2 (ja) | 2014-06-18 |
US20130323114A1 (en) | 2013-12-05 |
TW201235485A (en) | 2012-09-01 |
CN103384727B (zh) | 2016-08-10 |
KR20130109238A (ko) | 2013-10-07 |
TWI539016B (zh) | 2016-06-21 |
CN103384727A (zh) | 2013-11-06 |
JP2012167347A (ja) | 2012-09-06 |
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