JP2004211175A - Production method of copper composite material - Google Patents
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- JP2004211175A JP2004211175A JP2003000919A JP2003000919A JP2004211175A JP 2004211175 A JP2004211175 A JP 2004211175A JP 2003000919 A JP2003000919 A JP 2003000919A JP 2003000919 A JP2003000919 A JP 2003000919A JP 2004211175 A JP2004211175 A JP 2004211175A
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、溶接の電極材料などとして好適する銅複合材の製造方法に関する。
【0002】
【従来の技術】
銅マトリックス中にアルミナなどの酸化物を分散させた銅合金は導電性及び耐熱性に優れるため電気部品材料に広く利用され、この銅合金の特性や製法を改善する提案が多数なされている。
例えば、内部酸化する元素としてアルミニウムのみでなく、第3の元素としてスズを添加し、導電性と軟化特性を改善する提案がなされている。(特許文献1)
また、アトマイズ法にて製造した300μm以下のアルミニウムなどの易酸化性金属を固溶させた銅合金粉末を用いることで、50μm以下の粒子が70重量%以上となるものが提案されている。(特許文献2)
また、Cu−Al合金粉末を内部酸化してAlをAl2O3にした後、この合金粉末の表面を平滑にし、その後圧粉成形して成形体とし、この成形体を600〜1000℃で熱間鍛造する方法が提案されている。(特許文献3)
また、Alを含む板状銅合金を内部酸化せしめてAlをAl2O3にした後、この板状合金をコイル状にし、このコイル状合金を金属管内に密封し、この金属管を所望形状に900℃で熱間加工する方法が提案されている。(特許文献4)
また、Cu−Al合金の切粉を内部酸化せしめて得た合金粉末をカーボン型内に充填し、900℃、400kg/cm2の圧力でホットプレスする方法が提案されている。(特許文献5)
また、Cu−Al合金粉末の内部にAl2O3の環状硬質層が存在するようにして焼結性を高める方法が提案されている。(特許文献6)
【0003】
(特許文献1) 特開昭59−150043号公報 特許請求の範囲
(特許文献2) 特開昭60−141802号公報 特許請求の範囲
(特許文献3) 特開昭63−241126号公報 第2頁右上欄6行〜11行
(特許文献4) 特開平2−38541号公報 第3頁右上欄16行〜左下欄最終行
(特許文献5) 特開平2−93029号公報 第3頁右下欄15行〜第4頁左上欄17行
(特許文献6) 特開平4−80301号公報 特許請求の範囲
【0004】
【発明が解決しようとする課題】
上述した先行技術にあって、はいずれも高温での熱間加工を行うため、粒成長によって組織が粗大化する傾向にある。金属材料の結晶組織が粗大化すると機械的強度が低下することがホール・ペッチの法則として知られており、従来の方法では溶接の電極材料として要求される特性として、硬度が60(HRB)以上、導電率が85(IACS%)以上、熱伝導率が350(W/(m・K))以上を同時に満足するものを得ることができない。
【0005】
そこで、本発明者らは先に溶体化処理したCu−Cr合金に対し、200%の伸びに相当する歪を与えて時効処理することで、機械的強度と熱的・電気的特性の両方を満足する銅複合材を特願2002−210152号及び特願2002−210153号として提案している。
【0006】
しかしながら、Al2O3はCuに固溶せず、Cu−Cr合金に対する処理方法をCu−Al合金に適用することはできない。
【0007】
また、Cuに固溶するAl量は少なく、内部酸化法による複合化では、微細なAl2O3の析出量を多くして導電性を高く維持しつつ機械的強度を上げることが難しい。尚、ボールミル、振動ミル、アトライタを用いることでCuとAlの配合割合を任意に設定した合金を製造できるが、これらの方法による場合には、無酸化雰囲気にするなど設備的な問題と、不純物の混入を避けることができないという欠点がある。
【0008】
【課題を解決するための手段】
上記課題を解決するため、本発明に係る銅複合材の製造方法は、従来行っている内部酸化処理を行わずに、銅粉末とセラミック粉末とを混合し、この混合粉末を1次形状体とし、この1次形状体に歪を付与しながら押出しをすることで母材の粒径は微細化し、セラミック粒子を微細に粉砕し、一様に分散した2次形状体とした。
【0009】
前記歪を付与する手段としては、押出し、引き抜き、せん断、圧延または鍛造などが考えられる。押出しの場合には金型温度400〜1000℃、押出し速度0.5〜2.0mm/secで行う側方押出しが有効であり、また押出しの回数は10〜20回繰り返すことが必要である。
押出しの金型温度を400〜1000℃以上としたのは、400℃未満では変形抵抗が大きく押出しが困難となり、母相と粒子間に十分な結合強度が得られなくなり、また1000℃を超えると、銅の融点を超え溶融してしまい、歪の付与ができないためである。そのため上記範囲が好ましい。
また、押出し速度は速いほど歪が入りやすいが、0.5〜2.0mm/secとしたのは、0.5mm/sec未満では製造時間がかかり好ましくなく、2.0mm/secを超えると金型との摩擦が上昇し、金型寿命が極端に短くなるので、上記範囲が好ましい。
また、押出しを行うには合金粉末を所定の形状(1次形状)にする必要があるが、そのためには、圧粉成形または管に混合粉末を充填する等の手段が考えられる。
【0010】
また、溶接の電極材料として要求される機械的強度及び熱的・電気的特性を満足するには、得られた銅複合材の母材の平均粒径が20μm以下、セラミック粒子の平均粒径が500nm以下であることが好ましい。これよりも大きい粒径では溶接時の加圧による変形(素材の圧縮強度が低いため)が大きくなってしまう。溶接時の変形を防止するために必要な圧縮強度を得るには上記の粒径以下にすることが好ましい。
このためには、材料として用いるセラミック粉末の平均粒径を0.3〜10μmとし、且つ1次形状体に与える歪を200%以上の伸びに相当するものとする。セラミック粉末の径を0.3μm未満とするのは製造が困難でコスト的に見合わず、また10μmを超えると後工程で歪を与えるための繰り返し数が増加するためである。
【0011】
本発明において銅マトリックスに添加するセラミック粉末としては、アルミナまたは硼化チタンが好適である。
【0012】
前記素材に歪を与える手段としては、押出し、引き抜き、せん断、圧延または鍛造などが考えられる。特に側方押出し場合には、金型温度を400〜1000℃、押出し速度を0.5〜2.0mm/secとすることで、粒子結合温度を低下させ十分な強度が得られる。
【0013】
【発明の実施の形態】
以下に本発明の実施の形態を添付図面に基づいて説明する。図1は本発明に係る銅複合材を得る工程を説明した図であり、先ず、母材(Cu粉末)にアルミナ(Al2O3)粉末や硼化チタン(TiB2)粉末を混合する。混合割合は0.1wt%〜5.0wt%とする。0.1wt%未満では耐磨耗性が向上せず、5.0wt%を超えると導電率が低下し、金型の寿命も短くなるため、上記の範囲となる。
【0014】
次いで上記の混合粉末を側方押出しするために1次形状体とする。1次形状体にするには、例えば、圧粉成形或いはCu(銅)管内に混合粉末を充填することで行う。次いで、1次形状体に側方押出しによって200%以上、好ましくは約220%の伸びに相当する歪を与える。
尚、図1では説明を分りやすくするため、Cu管の径を側方押出し金型に形成した挿入孔の径よりも大きくしているが、実際はCu管の径と金型に形成した挿入孔の径は略等しく、またパンチでCu管を押し込む際にCu管が倒れないように治具等を用いて支持しておく。
【0015】
側方押出しの具体的な条件としては、金型温度を400〜1000℃とし、押し出し速度を約1mm/secとして、12回繰り返して押し出すECAE(equal−channel−angular extrusion)処理。この繰り返しで、母相の微細化とセラミックの粉砕・分散が生じる。
【0016】
このECAE処理によって得られた銅合金の結晶組織の顕微鏡写真を図2に示す。尚、図2(a)はアルミナ粉末を添加した複合材、(b)は硼化チタン粉末を添加した複合材を示す。これらの写真から銅マトリックスに粒径が数nmのアルミナまたは硼化チタンが均一に分散していることが確認される。
【0017】
図3は本発明に係る銅複合材と従来の銅複合材の溶接性を連続打点数で比較したグラフであり、本発明にかかる銅複合材のうち、アルミナが分散した銅複合材を溶接チップとした場合には、1000打点以上が可能で、硼化チタンが分散した銅複合材を溶接チップとした場合には、1400打点が可能であった。
【0018】
【発明の効果】
以上に説明したように本発明に係る銅合金の製造方法によれば、溶体化処理を出発点としていないので、固溶限界による制限がなく、銅合金中の第2元素粒子(Al2O3やTiB2)の割合を任意に設定でき、従来の銅複合材では得られなかった特性を得ることができる。
【0019】
即ち、銅合金のマトリックスの純度は高く、電気的特性に優れ、しかもマトリックス粒子の界面に析出するAl2O3やTiB2の粒子の粒径は粒成長が抑制されるためナノオーダ(500nm以下)と小さく且つ添加量も任意に設定できる。
【図面の簡単な説明】
【図1】本発明に係る銅複合材の製造方法を説明した図。
【図2】本発明に係る製造方法で得られた銅合金の結晶組織を示す顕微鏡写真であり、(a)はアルミナを添加した銅複合材、(b)は硼化チタンを添加した銅複合材を示す。
【図3】本発明に係る製造方法で得られた銅複合材と従来の銅複合材の溶接性を連続打点数で比較したグラフ。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a copper composite material suitable as a welding electrode material or the like.
[0002]
[Prior art]
A copper alloy in which an oxide such as alumina is dispersed in a copper matrix is widely used for electric component materials because of its excellent conductivity and heat resistance, and many proposals have been made to improve the properties and manufacturing method of this copper alloy.
For example, it has been proposed to add not only aluminum as an element to be internally oxidized but also tin as a third element to improve conductivity and softening characteristics. (Patent Document 1)
Further, it has been proposed that particles of 50 μm or less become 70% by weight or more by using a copper alloy powder in which an easily oxidizable metal such as aluminum having a size of 300 μm or less manufactured by an atomizing method is used as a solid solution. (Patent Document 2)
Further, after the Cu-Al alloy powder is internally oxidized to convert Al to Al 2 O 3 , the surface of the alloy powder is smoothed, and then compacted into a compact, and the compact is heated at 600 to 1000 ° C. A hot forging method has been proposed. (Patent Document 3)
Further, after the plate-like copper alloy containing Al is internally oxidized to convert Al into Al 2 O 3 , the plate-like alloy is made into a coil shape, the coil-like alloy is sealed in a metal tube, and the metal tube is formed into a desired shape. A method of hot working at 900 ° C. has been proposed. (Patent Document 4)
Further, a method has been proposed in which a carbon mold is filled with an alloy powder obtained by internally oxidizing a chip of a Cu—Al alloy, and hot-pressed at 900 ° C. under a pressure of 400 kg / cm 2 . (Patent Document 5)
Further, a method has been proposed in which an annular hard layer of Al 2 O 3 is present inside a Cu—Al alloy powder to enhance sinterability. (Patent Document 6)
[0003]
(Patent Document 1) JP-A-59-150043 Patent claims (Patent Document 2) JP-A-60-141802 Patent claims (Patent Document 3) JP-A-63-241126 Page 2 Upper right column, lines 6 to 11 (Patent Document 4) JP-A-2-38541,
[Problems to be solved by the invention]
In any of the above-mentioned prior arts, since hot working is performed at a high temperature, the structure tends to become coarse due to grain growth. It is known as Hall-Petch's law that the mechanical strength is reduced when the crystal structure of the metal material is coarsened. According to the conventional method, a property required as an electrode material for welding is a hardness of 60 (HRB) or more. In addition, it is impossible to obtain a material having an electrical conductivity of 85 (IACS%) or more and a thermal conductivity of 350 (W / (m · K)) or more.
[0005]
Then, the present inventors applied a strain corresponding to elongation of 200% to the Cu—Cr alloy that had been subjected to the solution treatment, and aged to give both mechanical strength and thermal / electrical properties. Satisfactory copper composite materials have been proposed as Japanese Patent Application Nos. 2002-210152 and 2002-210153.
[0006]
However, Al 2 O 3 does not form a solid solution in Cu, and a treatment method for a Cu—Cr alloy cannot be applied to a Cu—Al alloy.
[0007]
Further, the amount of Al dissolved in Cu is small, and it is difficult to increase the mechanical strength while maintaining high conductivity by increasing the amount of fine Al 2 O 3 deposited by complexing by the internal oxidation method. Incidentally, an alloy in which the mixing ratio of Cu and Al is arbitrarily set can be manufactured by using a ball mill, a vibration mill, and an attritor. However, according to these methods, equipment problems such as a non-oxidizing atmosphere and impurities are considered. There is a drawback that the incorporation of phenomena cannot be avoided.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, a method for producing a copper composite material according to the present invention comprises mixing a copper powder and a ceramic powder without performing a conventional internal oxidation treatment, and forming the mixed powder into a primary shape. By extruding the primary body while applying strain to the primary body, the particle diameter of the base material was reduced, and the ceramic particles were pulverized finely to obtain a uniformly dispersed secondary body.
[0009]
Extrusion, drawing, shearing, rolling, forging, and the like can be considered as means for imparting the strain. In the case of extrusion, side extrusion performed at a mold temperature of 400 to 1000 ° C. and an extrusion speed of 0.5 to 2.0 mm / sec is effective, and the number of extrusions needs to be repeated 10 to 20 times.
The reason why the extrusion mold temperature is set to 400 to 1000 ° C. or higher is that if the temperature is lower than 400 ° C., deformation resistance is large and extrusion is difficult, and sufficient bonding strength between the parent phase and the particles cannot be obtained. This is because the melting point exceeds the melting point of copper, and distortion cannot be imparted. Therefore, the above range is preferable.
The higher the extrusion speed, the easier the strain is to be introduced. However, the reason why the extrusion speed is set to 0.5 to 2.0 mm / sec is that if the extrusion speed is less than 0.5 mm / sec, the production time is unfavorably long. The above range is preferable because the friction with the mold increases and the life of the mold is extremely shortened.
In order to perform extrusion, it is necessary to form the alloy powder into a predetermined shape (primary shape). For this purpose, means such as compacting or filling a tube with a mixed powder may be considered.
[0010]
In addition, in order to satisfy the mechanical strength and thermal / electrical properties required as electrode materials for welding, the average particle size of the base material of the obtained copper composite material is 20 μm or less, and the average particle size of the ceramic particles is 20 μm or less. Preferably it is 500 nm or less. If the particle size is larger than this, deformation due to pressurization during welding (because the compressive strength of the material is low) will be large. In order to obtain the compressive strength necessary for preventing deformation during welding, it is preferable that the particle size is equal to or less than the above particle size.
For this purpose, the average particle size of the ceramic powder used as the material is set to 0.3 to 10 μm, and the strain applied to the primary shape body is equivalent to elongation of 200% or more. The reason why the diameter of the ceramic powder is set to less than 0.3 μm is that production is difficult and the cost is unreasonable.
[0011]
In the present invention, alumina or titanium boride is preferable as the ceramic powder added to the copper matrix.
[0012]
Extrusion, drawing, shearing, rolling, forging, and the like can be considered as means for imparting strain to the material. Particularly in the case of lateral extrusion, by setting the mold temperature to 400 to 1000 ° C. and the extrusion speed to 0.5 to 2.0 mm / sec, the particle bonding temperature is lowered and sufficient strength is obtained.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a view for explaining a process of obtaining a copper composite material according to the present invention. First, alumina (Al 2 O 3 ) powder or titanium boride (TiB 2 ) powder is mixed with a base material (Cu powder). The mixing ratio is 0.1 wt% to 5.0 wt%. If it is less than 0.1 wt%, the abrasion resistance is not improved, and if it exceeds 5.0 wt%, the electrical conductivity is reduced and the life of the mold is shortened.
[0014]
Next, the above-mentioned mixed powder is made into a primary shape body for lateral extrusion. In order to obtain a primary shape, for example, compacting or filling a mixed powder in a Cu (copper) tube is performed. The primary profile is then strained by side extrusion, corresponding to an elongation of 200% or more, preferably about 220%.
In FIG. 1, the diameter of the Cu tube is made larger than the diameter of the insertion hole formed in the side-extrusion die for the sake of easy understanding of the description. Are approximately equal, and are supported by using a jig or the like so that the Cu tube does not fall when the Cu tube is pushed in by a punch.
[0015]
As a specific condition of the lateral extrusion, an ECAE (equal-channel-angular extrusion) process of repeatedly extruding 12 times at a mold temperature of 400 to 1000 ° C. and an extrusion speed of about 1 mm / sec. By repetition of the above, the microstructure of the mother phase and the pulverization and dispersion of the ceramic occur.
[0016]
FIG. 2 shows a micrograph of the crystal structure of the copper alloy obtained by the ECAE treatment. 2A shows a composite material to which alumina powder is added, and FIG. 2B shows a composite material to which titanium boride powder is added. From these photographs, it is confirmed that alumina or titanium boride having a particle size of several nm is uniformly dispersed in the copper matrix.
[0017]
FIG. 3 is a graph comparing the weldability of the copper composite material according to the present invention and the conventional copper composite material by the number of continuous dots, and among the copper composite materials according to the present invention, a copper composite material in which alumina is dispersed is used as a welding tip. In this case, 1000 or more dots were possible, and when a copper composite material in which titanium boride was dispersed was used as a welding tip, 1400 dots were possible.
[0018]
【The invention's effect】
As described above, according to the method for producing a copper alloy according to the present invention, since the solution treatment is not a starting point, there is no limitation due to the solid solution limit, and the second element particles (Al 2 O 3) in the copper alloy are not limited. And TiB 2 ) can be set arbitrarily, and characteristics that cannot be obtained with a conventional copper composite material can be obtained.
[0019]
That is, the purity of the matrix of the copper alloy is high, the electrical characteristics are excellent, and the particle size of Al 2 O 3 or TiB 2 particles deposited at the interface of the matrix particles is in the nano order (500 nm or less) because the grain growth is suppressed. And the addition amount can be set arbitrarily.
[Brief description of the drawings]
FIG. 1 is a diagram illustrating a method for producing a copper composite material according to the present invention.
FIGS. 2A and 2B are micrographs showing a crystal structure of a copper alloy obtained by a production method according to the present invention, wherein FIG. 2A is a copper composite material to which alumina is added, and FIG. 2B is a copper composite material to which titanium boride is added. Shows the material.
FIG. 3 is a graph comparing the weldability of the copper composite obtained by the production method according to the present invention and the conventional copper composite by the number of continuous hit points.
Claims (5)
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003000919A JP4212363B2 (en) | 2003-01-07 | 2003-01-07 | Method for producing copper composite material |
GB0601624A GB2419604B (en) | 2002-07-18 | 2003-07-17 | Method of manufacturing composite copper material |
US10/521,333 US7544259B2 (en) | 2002-07-18 | 2003-07-17 | Copper alloy, copper alloy producing method, copper complex material, and copper complex material producing method |
PCT/JP2003/009102 WO2004009859A1 (en) | 2002-07-18 | 2003-07-17 | Copper alloy, copper alloy producing method, copper complex material, and copper complex material producing method |
CN200910262569A CN101760663A (en) | 2002-07-18 | 2003-07-17 | Copper alloy, copper alloy producing method, copper complex material, and copper complex material producing method |
GB0601625A GB2419605B (en) | 2002-07-18 | 2003-07-17 | Method of manufacturing composite copper material |
CA002492925A CA2492925A1 (en) | 2002-07-18 | 2003-07-17 | Copper alloy, copper alloy producing method, copper complex material, and copper complex material producing method |
GB0601627A GB2419603B (en) | 2002-07-18 | 2003-07-17 | Composite copper material |
GB0503149A GB2406579B (en) | 2002-07-18 | 2003-07-17 | Copper alloy, method, of manufacturing copper alloy |
CN03822284A CN100591784C (en) | 2002-07-18 | 2003-07-17 | Copper alloy, copper alloy producing method |
AU2003252210A AU2003252210A1 (en) | 2002-07-18 | 2003-07-17 | Copper alloy, copper alloy producing method, copper complex material, and copper complex material producing method |
US12/387,608 US20100021334A1 (en) | 2002-07-18 | 2009-05-05 | Method of manufacturing composite copper material |
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JP2003000919A JP4212363B2 (en) | 2003-01-07 | 2003-01-07 | Method for producing copper composite material |
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JP4212363B2 JP4212363B2 (en) | 2009-01-21 |
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Cited By (3)
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CN111360262A (en) * | 2020-03-30 | 2020-07-03 | 河南科技大学 | Plastic forming method of copper-based composite material and production method of copper-based composite material plate strip |
CN112725663A (en) * | 2020-12-30 | 2021-04-30 | 江苏智仁景行新材料研究院有限公司 | Ceramic-aluminum composite powder and preparation method thereof |
CN115595461A (en) * | 2022-11-09 | 2023-01-13 | 西安理工大学(Cn) | Microlaminate TiB 2 Reinforced copper-based composite material and preparation method thereof |
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CN111360262A (en) * | 2020-03-30 | 2020-07-03 | 河南科技大学 | Plastic forming method of copper-based composite material and production method of copper-based composite material plate strip |
CN111360262B (en) * | 2020-03-30 | 2022-04-15 | 河南科技大学 | Plastic forming method of copper-based composite material and production method of copper-based composite material plate strip |
CN112725663A (en) * | 2020-12-30 | 2021-04-30 | 江苏智仁景行新材料研究院有限公司 | Ceramic-aluminum composite powder and preparation method thereof |
CN112725663B (en) * | 2020-12-30 | 2022-07-05 | 江苏智仁景行新材料研究院有限公司 | Ceramic-aluminum composite powder and preparation method thereof |
CN115595461A (en) * | 2022-11-09 | 2023-01-13 | 西安理工大学(Cn) | Microlaminate TiB 2 Reinforced copper-based composite material and preparation method thereof |
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