JP5367999B2 - Cu-Ni-Si alloy for electronic materials - Google Patents
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- JP5367999B2 JP5367999B2 JP2008093888A JP2008093888A JP5367999B2 JP 5367999 B2 JP5367999 B2 JP 5367999B2 JP 2008093888 A JP2008093888 A JP 2008093888A JP 2008093888 A JP2008093888 A JP 2008093888A JP 5367999 B2 JP5367999 B2 JP 5367999B2
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- 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
Abstract
Description
本発明は析出硬化型銅合金に関し、とりわけ各種電子機器部品に用いるのに好適なＣｕ−Ｎｉ−Ｓｉ系合金に関する。 The present invention relates to a precipitation hardening type copper alloy, and more particularly to a Cu—Ni—Si based alloy suitable for use in various electronic device parts.
リードフレーム、コネクタ、ピン、端子、リレー、スイッチ等の各種電子機器部品に使用される電子材料用銅合金には、基本特性として高強度及び高導電性（又は熱伝導性）を両立させることが要求される。近年、電子部品の高集積化及び小型化・薄肉化が急速に進み、これに対応して電子機器部品に使用される銅合金に対する要求レベルはますます高度化している。 Copper alloys for electronic materials used in various electronic equipment components such as lead frames, connectors, pins, terminals, relays, switches, etc., have both high strength and high conductivity (or thermal conductivity) as basic characteristics. Required. In recent years, high integration and miniaturization / thinning of electronic components have been rapidly progressing, and the level of demand for copper alloys used in electronic device components has been increased accordingly.
高強度及び高導電性の観点から、近年、電子材料用銅合金として従来のりん青銅、黄銅等に代表される固溶強化型銅合金に替わり、析出硬化型の銅合金の使用量が増加している。析出硬化型銅合金では、溶体化処理された過飽和固溶体を時効処理することにより、微細な析出物が均一に分散して、合金の強度が高くなると同時に、銅中の固溶元素量が減少し電気伝導性が向上する。このため、強度、ばね性などの機械的性質に優れ、しかも電気伝導性、熱伝導性が良好な材料が得られる。 From the viewpoint of high strength and high conductivity, in recent years, the amount of precipitation hardening type copper alloys has increased in place of conventional solid solution strengthened copper alloys such as phosphor bronze and brass as copper alloys for electronic materials. ing. In precipitation-hardened copper alloys, by aging the supersaturated solid solution that has undergone solution treatment, fine precipitates are uniformly dispersed, increasing the strength of the alloy and reducing the amount of solid solution elements in the copper. Electrical conductivity is improved. For this reason, a material excellent in mechanical properties such as strength and spring property and having good electrical conductivity and thermal conductivity can be obtained.
析出硬化型銅合金のうち、コルソン系合金と一般に呼ばれるＣｕ−Ｎｉ−Ｓｉ系銅合金は比較的高い導電性、強度、応力緩和特性及び曲げ加工性を兼備する代表的な銅合金であり、業界において現在活発に開発が行われている合金の一つである。この銅合金では、銅マトリックス中に微細なＮｉ−Ｓｉ系金属間化合物粒子を析出させることによって強度と導電率の向上が図れる。 Among precipitation hardening copper alloys, Cu-Ni-Si copper alloys, commonly called Corson alloys, are representative copper alloys that have relatively high electrical conductivity, strength, stress relaxation characteristics and bending workability. Is one of the alloys that is currently under active development. In this copper alloy, strength and conductivity can be improved by precipitating fine Ni—Si intermetallic compound particles in a copper matrix.
Ｎｉ−Ｓｉ化合物粒子の析出状態は合金特性に影響を与えることが知られている。 It is known that the precipitation state of Ni—Si compound particles affects the alloy characteristics.
特許３７９７７３６号公報（特許文献１）では、Ｎｉ−Ｓｉ化合物粒子の粒径が０．００３μｍ以上０．０３μｍ未満のもの（小粒子）及び０．０３μｍ〜１００μｍのもの（大粒子）が存在し、かつ小粒子／大粒子の数の比率が１．５以上とすることが記載されている。そして、粒径が０．０３μｍ未満の小粒子は、主に合金の強度及び耐熱性を向上させるが剪断加工性にはあまり寄与しない。一方、粒径が０．０３μｍ以上の大粒子は合金の強度及び耐熱性の向上にはあまり寄与しないが、剪断加工時に応力を集中的に受け、ミクロクラックの発生源となり剪断加工性を著しく向上させることが記載されている。そして、特許文献１に記載の銅合金は電気電子部品用銅合金として要求される強度や耐熱性などの特性を有するとともに、剪断加工性に優れた銅合金であることが述べられている。
特許文献１に記載の銅合金を製造する方法として、以下が開示されている。
１）Ｎｉの含有量が４ｗｔ％、Ｓｉの含有量が１ｗｔ％以上になると、晶出粒子の粗大化が特に発生しやすくなるので、晶出粒子の寸法を目的の範囲内とするには、Ｎｉ及びＳｉ添加後溶湯を１３００℃以上の温度に５分以上保持し、両者を完全に溶解させ、鋳造温度〜凝固温度まで鋳型内での冷却速度を０．３℃／秒以上とする。
２）熱間圧延後の熱延材を水中急冷し、さらに冷間圧延した材料を５００〜７００℃で１分〜２時間の加熱を行って大粒子を析出させる。その後、さらに冷間圧延を加え、今度は３００〜６００℃で３０分以上の加熱を行い小粒子を析出させる。
３）熱間圧延終了時に冷却する際に急冷せず、５００〜７００℃で１分〜２時間保持して大粒子を析出させた後急冷する。さらに冷間圧延を加えた後、今度は３００〜６００℃で３０分以上の加熱を行って小粒子を析出させる。
In Japanese Patent No. 3797736 (Patent Document 1), there are Ni-Si compound particles having a particle size of 0.003 to 0.03 μm (small particles) and 0.03 to 100 μm (large particles), In addition, it is described that the ratio of the number of small particles / large particles is 1.5 or more. Small particles having a particle size of less than 0.03 μm mainly improve the strength and heat resistance of the alloy, but do not contribute much to the shear processability. On the other hand, large particles with a particle size of 0.03μm or more do not contribute much to the improvement of the strength and heat resistance of the alloy, but receive stress intensively during the shearing process and become a source of microcracking, which significantly improves the shearing processability. Is described. And it is described that the copper alloy of patent document 1 is a copper alloy which has characteristics, such as intensity | strength and heat resistance which are requested | required as a copper alloy for electrical and electronic parts, and was excellent in shear workability.
The following is disclosed as a method for producing the copper alloy described in Patent Document 1.
1) When the Ni content is 4 wt% and the Si content is 1 wt% or more, coarsening of the crystallized particles is particularly likely to occur. Therefore, in order to keep the size of the crystallized particles within the target range, After addition of Ni and Si, the molten metal is held at a temperature of 1300 ° C. or higher for 5 minutes or longer, and both are completely dissolved, and the cooling rate in the mold is set to 0.3 ° C./second or higher from the casting temperature to the solidification temperature.
2) The hot-rolled material after hot rolling is quenched in water, and the cold-rolled material is heated at 500 to 700 ° C. for 1 minute to 2 hours to precipitate large particles. Thereafter, cold rolling is further performed, and this time heating is performed at 300 to 600 ° C. for 30 minutes or more to precipitate small particles.
3) When cooling at the end of hot rolling, do not quench rapidly, hold at 500 to 700 ° C. for 1 minute to 2 hours to precipitate large particles, and then cool rapidly. After further cold rolling, this time heating is performed at 300 to 600 ° C. for 30 minutes or more to precipitate small particles.
特許３９７７３７６号公報（特許文献２）では、銅合金の組織中のＮｉ−Ｓｉ析出物、それ以外の析出物の粒径、さらにその分布密度の割合と、結晶粒の粗大化抑制との関連に着目して、Ｎｉ及びＳｉからなる析出物Ｘと、ＮｉとＳｉの一方若しくは両方を含有しない析出物Ｙを有し、前記析出物Ｘの粒径が０．００１〜０．１μｍで、前記析出物Ｙの粒径を０．０１〜１μｍとすることが記載されている。また、強度と曲げ加工性の両立を図るためには、析出物Ｘの数を析出物Ｙの２０〜２０００倍とすることや、析出物Ｘの数を１ｍｍ2あたり１０8〜１０12個、析出物Ｙの数を１ｍｍ2あたり１０4〜１０8個とすることが記載されている。
特許文献２に記載の銅合金を製造する方法として、以下が開示されている。
鋳塊を熱間圧延する際、鋳塊を昇温速度２０〜２００℃／時間で加熱し、８５０〜１０５０℃×０．５〜５時間の間に熱間圧延し、熱間圧延の終了温度は３００〜７００℃として急冷する。これにより析出物Ｘ及びＹが生成する。熱間圧延後は、例えば、溶体化熱処理、焼鈍、冷間圧延を組み合わせ、所望の板厚にする。
前記溶体化熱処理の目的は鋳造や熱間加工時に析出したＮｉとＳｉを再固溶させると同時に再結晶させる熱処理である。前記溶体化熱処理の温度は添加したＮｉ量によって調整を行い、例えば、Ｎｉ量が２．０〜２．５質量％未満は６５０℃、２．５〜３．０質量％未満は８００℃、３．０〜３．５質量％未満は８５０℃、３．５〜４．０質量％未満は９００℃、４．０〜４．５質量％未満は９５０℃、４．５〜５．０質量％は９８０℃とする。
The following is disclosed as a method for producing the copper alloy described in Patent Document 2.
When the ingot is hot-rolled, the ingot is heated at a heating rate of 20 to 200 ° C./hour, hot-rolled between 850 to 1050 ° C. × 0.5 to 5 hours, and the end temperature of hot rolling Rapidly cools to 300-700 ° C. Thereby, precipitates X and Y are generated. After hot rolling, for example, solution heat treatment, annealing, and cold rolling are combined to obtain a desired plate thickness.
The purpose of the solution heat treatment is a heat treatment in which Ni and Si precipitated during casting and hot working are re-solidified and recrystallized at the same time. The temperature of the solution heat treatment is adjusted by the amount of added Ni. For example, the Ni amount is 650 ° C. when the Ni amount is less than 2.0 to 2.5% by mass, and the 800 ° C. 0.0 to less than 3.5% by mass is 850 ° C., 3.5 to less than 4.0% by mass is 900 ° C., and less than 4.0 to 4.5% by mass is 950 ° C., 4.5 to 5.0% by mass. Is 980 ° C.
特許文献１に記載の銅合金では小粒子と大粒子の個数について比率しか検討されておらず、粒子の個数密度については言及されていない。また、特許文献１では二回時効することで大粒子と小粒子をそれぞれ析出させるとしているが、二回目に析出させる小粒子は、一回目に比較して固溶しているＮｉ、Ｓｉ濃度が低いため析出しにくく、数密度、粒子径ともに小さいため、強度に与える好影響が不十分である（後述する比較例５参照）。二回時効するという手法は、また一回目の時効によっては固溶するＮｉ、Ｓｉ量が変化してしまうため、粒子径、密度の制御が困難であるという問題もある。 In the copper alloy described in Patent Document 1, only the ratio of the number of small particles and large particles has been studied, and the number density of particles is not mentioned. In Patent Document 1, the large particles and the small particles are precipitated by being aged twice, but the small particles precipitated in the second time have a concentration of Ni and Si dissolved in comparison with the first time. Since it is low, it is difficult to precipitate, and since both the number density and the particle diameter are small, the positive effect on the strength is insufficient (see Comparative Example 5 described later). The method of aging twice also has a problem that it is difficult to control the particle diameter and density because the amount of Ni and Si dissolved in the solution changes depending on the first aging.
特許文献２に記載の銅合金ではＮｉ−Ｓｉ化合物粒子を粒径が０．００１〜０．１μｍの範囲においてしか制御しておらず、より粒径の大きなＮｉ−Ｓｉ化合物粒子が合金特性に与える影響について検討がされていない。特許文献２に記載の大粒子はＮｉとＳｉの一方若しくは両方を含有しない析出物である。このような大粒子は添加元素の量や温度条件によっては粗大化して、曲げ加工性に悪影響を与えやすくなる（後述する比較例１５、１６及び１７参照）。 In the copper alloy described in Patent Document 2, the Ni—Si compound particles are controlled only in the range of 0.001 to 0.1 μm in particle size, and Ni—Si compound particles having a larger particle size give the alloy characteristics. The impact has not been studied. The large particles described in Patent Document 2 are precipitates that do not contain one or both of Ni and Si. Such large particles are coarsened depending on the amount of additive element and temperature conditions, and are liable to adversely affect bending workability (see Comparative Examples 15, 16, and 17 described later).
そこで、本発明ではＮｉ−Ｓｉ化合物粒子の分布状態をより厳密に制御することでコルソン系合金の特性向上を図ることを課題とする。 Accordingly, an object of the present invention is to improve the characteristics of the Corson alloy by controlling the distribution state of the Ni—Si compound particles more strictly.
本発明者は上記課題を解決するために鋭意研究を重ねたところ、銅マトリックス中に析出するＮｉ−Ｓｉ化合物粒子を、主として結晶粒内に析出しやすい粒径が０．０１μｍ以上で０．０５μｍ未満であるＮｉ−Ｓｉ化合物粒子（小粒子）と、主として結晶粒界に析出しやすい粒径が０．０５μｍ以上で５．０μｍ未満であるＮｉ−Ｓｉ化合物粒子（大粒子）に分けてそれぞれの大きさと個数密度を制御することで強度及び導電率のバランスに優れ、曲げ加工性も良好なコルソン系合金を得ることができることが分かった。具体的には、小粒子を０．０１μｍ以上で０．０５μｍ未満の範囲の大きさに制御してその個数密度を１ｍｍ2当たり１０6−１０10個に制御するとともに、大粒子を０．０５μｍ以上で５．０μｍ未満の範囲の大きさに制御してその個数密度を前記小粒子の個数密度に対して１／１００００〜１／１０とすることが有効であることを見いだした。 The present inventor has made extensive studies to solve the above problems, and as a result, the Ni—Si compound particles precipitated in the copper matrix have a particle size of 0.01 μm or more and 0.05 μm which are likely to precipitate mainly in the crystal grains. The Ni-Si compound particles (small particles) which are less than the particle size and the Ni-Si compound particles (large particles) whose particle size which tends to precipitate mainly at the grain boundaries is 0.05 μm or more and less than 5.0 μm are divided into the respective particles. It was found that by controlling the size and number density, it is possible to obtain a Corson-based alloy having an excellent balance between strength and electrical conductivity and excellent bending workability. Specifically, the small particles are controlled to have a size in the range of 0.01 μm or more and less than 0.05 μm to control the number density to 10 6 -10 10 per 1 mm 2 , and the large particles are 0.05 μm. It has been found that it is effective to control the number density within the range of less than 5.0 μm so that the number density is 1/10000 to 1/10 of the number density of the small particles.
かかる知見を基礎として完成した本発明は一側面において、Ｎｉ：０．４〜６．０質量％、Ｓｉ：０．１〜２．０質量％を含有し、残部Ｃｕおよび不可避的不純物から構成され、ＮｉとＳｉの質量比がＮｉ／Ｓｉ＝３〜７である電子材料用銅合金であって、粒径が０．０１μｍ以上で０．０５μｍ未満であるＮｉ−Ｓｉ化合物小粒子と、粒径が０．０５μｍ以上で５．０μｍ未満であるＮｉ−Ｓｉ化合物大粒子が存在しており、小粒子の個数密度が１ｍｍ2当たり１０6−１０10個であり、大粒子の個数密度が前記小粒子の個数密度と比べて１／１００００〜１／１０である電子材料用銅合金である。 The present invention completed on the basis of such knowledge includes, in one aspect, Ni: 0.4 to 6.0% by mass, Si: 0.1 to 2.0% by mass, the balance being Cu and inevitable impurities. , a copper alloy for electronic materials mass ratio of Ni and Si are Ni / Si = 3 to 7, a Ni-Si compound small particles less than 0.05μm in particle size 0.01μm or more, the particle size Ni-Si compound large particles having a particle size of 0.05 μm or more and less than 5.0 μm are present, the number density of small particles is 10 6 -10 10 per mm 2 , and the number density of large particles is small It is a copper alloy for electronic materials which is 1/10000 to 1/10 compared with the number density of particles.
本発明に係る電子材料用銅合金は一実施形態において、小粒子の平均粒径に対する大粒子の平均粒径の比が２〜１００である。 In one embodiment of the copper alloy for electronic materials according to the present invention, the ratio of the average particle size of the large particles to the average particle size of the small particles is 2 to 100.
本発明に係る電子材料用銅合金は更に別の一実施形態において、平均結晶粒径が圧延方向に平行な厚み方向の断面から観察した時に円相当径で表して５〜３０μｍである。 In another embodiment, the copper alloy for electronic materials according to the present invention has an average crystal grain size of 5 to 30 μm in terms of a circle-equivalent diameter when observed from a cross section in the thickness direction parallel to the rolling direction.
本発明に係る電子材料用銅合金は別の一実施形態において、更にＣｒ、Ｃｏ、Ｍｇ、Ｍｎ、Ｆｅ、Ｓｎ、Ｚｎ、Ａｌ及びＰから選択される１種又は２種以上を合計で１．０質量％まで含有する。 In another embodiment, the copper alloy for electronic materials according to the present invention further includes one or more selected from Cr, Co, Mg, Mn, Fe, Sn, Zn, Al and P in a total of 1. Contains up to 0% by weight.
本発明は別の一側面において、本発明に係る電子材料用銅合金からなる伸銅品である。 In another aspect, the present invention is a copper-drawn product comprising the copper alloy for electronic materials according to the present invention.
本発明は更に別の一側面において、本発明に係る電子材料用銅合金を備えた電子部品である。 In yet another aspect, the present invention is an electronic component including the copper alloy for electronic materials according to the present invention.
本発明によれば、銅マトリクス中に析出したＮｉ−Ｓｉ化合物粒子による合金特性への恩恵をより効果的に享受できるので、コルソン系合金の特性向上を図ることができる。 According to the present invention, it is possible to more effectively enjoy the benefit of alloy properties due to the Ni—Si compound particles precipitated in the copper matrix, so that the properties of the Corson alloy can be improved.
Ｎｉ及びＳｉの添加量
Ｎｉ及びＳｉは、適当な熱処理を施すことにより金属間化合物としてＮｉ−Ｓｉ化合物粒子（Ｎｉ2Ｓｉ等）を形成し、導電率を劣化させずに高強度化が図れる。
ＳｉやＮｉ添加量は少なすぎると所望の強度が得られず、多すぎると高強度化は図れるが導電率が著しく低下し、熱間加工性が低下する。また、Ｎｉ中には水素が固溶することがあり、溶解鋳造時のブローホールの原因となったりするため、Ｎｉ添加量を多くすると中間の加工において破断の原因となる可能性がある。ＳｉはＣと反応したり、Ｏと反応したりするため、添加量が多いと極めて多くの介在物を形成し、曲げの際に破断の原因になる。
Addition amounts of Ni and Si Ni and Si form Ni—Si compound particles (Ni 2 Si or the like) as an intermetallic compound by performing an appropriate heat treatment, and can increase the strength without deteriorating the conductivity.
If the amount of Si or Ni added is too small, the desired strength cannot be obtained. If it is too large, the strength can be increased, but the electrical conductivity is remarkably lowered, and the hot workability is lowered. In addition, hydrogen may be dissolved in Ni, which may cause blowholes during melt casting, so increasing the amount of Ni added may cause breakage in intermediate processing. Since Si reacts with C and reacts with O, if the addition amount is large, a very large amount of inclusions are formed, which causes breakage during bending.
そこで、適切なＳｉ添加量は０．１〜２．０質量％であり、好ましくは０．２〜１．５％である。適切なＮｉ添加量は０．４〜６．０質量％であり、好ましくは１．０〜５．０％質量％である。 Therefore, an appropriate Si addition amount is 0.1 to 2.0% by mass, preferably 0.2 to 1.5%. A suitable Ni addition amount is 0.4 to 6.0% by mass, preferably 1.0 to 5.0% by mass.
Ｎｉ−Ｓｉ化合物粒子の析出物は化学量論組成で一般に構成されており、ＮｉとＳｉの質量比を金属間化合物であるＮｉ2Ｓｉの質量組成比（Ｎｉの原子量×２：Ｓｉの原子量×１）に近づけることにより、すなわちＮｉとＳｉの質量比をＮｉ／Ｓｉ＝３〜７、好ましくは３．５〜５とすることにより良好な電気伝導性が得られる。Ｎｉの比率が上記質量組成比よりも高いと導電率が低下しやすく、Ｓｉの比率が上記質量組成比よりも高いと粗大なＮｉ−Ｓｉ晶出物により熱間加工性が劣化しやすい。 The precipitate of Ni—Si compound particles is generally composed of a stoichiometric composition, and the mass ratio of Ni and Si is the mass composition ratio of Ni 2 Si which is an intermetallic compound (Ni atomic weight × 2: Si atomic weight × By bringing the ratio closer to 1), that is, by setting the mass ratio of Ni and Si to Ni / Si = 3 to 7, preferably 3.5 to 5, good electrical conductivity can be obtained. If the Ni ratio is higher than the mass composition ratio, the electrical conductivity tends to decrease, and if the Si ratio is higher than the mass composition ratio, hot workability is likely to be deteriorated due to coarse Ni-Si crystallized products.
その他の元素の添加量
（１）Ｃｒ、Ｃｏ
Ｃｒ、ＣｏはＣｕ中に固溶し、溶体化処理時の結晶粒の粗大化を抑制する。また合金強度が底上げされる。時効処理時にはシリサイドを形成して析出し、強度及び導電率の改善に寄与することもできる。これらの添加元素は導電率をほとんど低下しないことから積極的に添加しても良いが、添加量が多い場合は逆に特性を損なう恐れがある。そこで、Ｃｒ及びＣｏは一方又は両方を合計で１．０質量％まで添加するのがよく、０．００５〜１．０質量％添加するのが好ましい。
（２）Ｍｇ、Ｍｎ
ＭｇやＭｎはＯと反応するため溶湯の脱酸効果が得られる。また、一般的に合金強度を向上させる元素として添加される元素である。最も有名な効果としては応力緩和特性の向上であり、いわゆる耐クリープ特性である。近年、電子機器の高集積化にともない、高電流が流れ、またＢＧＡタイプのような熱放散性が低い半導体パッケージにおいては、熱により素材が劣化する恐れがあり、故障の原因となる。特に、車載する場合はエンジンまわりの熱による劣化が懸念され、耐熱性は重要な課題である。これらの理由で積極的に添加しても良い元素である。ただし、添加量が多すぎると曲げ加工性への悪影響が無視できなくなる。そこで、Ｍｇ及びＭｎは一方又は両方を合計で０．５質量％まで添加するのがよく、０．００５〜０．４質量％添加するのが好ましい。
（３）Ｓｎ
ＳｎはＭｇと同様の効果がある。しかしＭｇと異なり、Ｃｕ中に固溶する量が多いため、より耐熱性が必要な場合に添加される。しかしながら、量が増えれば導電率は著しく低下する。よって、Ｓｎは０．５質量％まで添加するのがよく、０．１〜０．４質量％質量％添加するのが好ましい。ただし、ＭｇとＳｎを共に添加するときは導電率への悪影響を抑えるために両者の合計濃度を１．０質量％までとし、好ましくは０．８質量％までとするのが望ましい。
（４）Ｚｎ
Ｚｎははんだ脆化を抑制する効果がある。ただし、添加量が多いと導電率が低下するので、０．５質量％まで添加するのがよく、０．１〜０．４質量％添加するのが好ましい。
（５）Ｆｅ、Ａｌ、Ｐ
これらの元素も合金強度を向上させることのできる元素である。必要に応じて添加すればよい。ただし、添加量が多いと添加元素に応じて特性が悪化するので、０．５質量％まで添加するのがよく、０．００５〜０．４質量％添加するのが好ましい。
Addition amount of other elements (1) Cr, Co
Cr and Co are dissolved in Cu to suppress the coarsening of crystal grains during the solution treatment. Also, the alloy strength is raised. During the aging treatment, silicide is formed and deposited, which can contribute to improvement in strength and conductivity. These additive elements may be positively added because they do not substantially lower the electrical conductivity. However, if the added amount is large, the characteristics may be adversely affected. Therefore, one or both of Cr and Co are preferably added up to a total of 1.0% by mass, preferably 0.005 to 1.0% by mass.
(2) Mg, Mn
Since Mg and Mn react with O, the deoxidation effect of the molten metal can be obtained. In general, it is an element added as an element for improving the alloy strength. The most famous effect is the improvement of stress relaxation characteristics, so-called creep resistance. In recent years, with the high integration of electronic devices, a high current flows, and in a semiconductor package with low heat dissipation such as a BGA type, the material may be deteriorated by heat, which causes a failure. In particular, when mounted on a vehicle, there is a concern about deterioration due to heat around the engine, and heat resistance is an important issue. For these reasons, it is an element that may be positively added. However, if the amount added is too large, the adverse effect on bending workability cannot be ignored. Therefore, it is preferable to add one or both of Mg and Mn to 0.5% by mass in total, and it is preferable to add 0.005 to 0.4% by mass.
(3) Sn
Sn has the same effect as Mg. However, unlike Mg, the amount dissolved in Cu is large, so it is added when more heat resistance is required. However, the conductivity decreases significantly as the amount increases. Therefore, Sn is preferably added up to 0.5% by mass, and preferably 0.1 to 0.4% by mass. However, when adding both Mg and Sn, in order to suppress the adverse effect on the electrical conductivity, the total concentration of both is up to 1.0 mass%, preferably up to 0.8 mass%.
(4) Zn
Zn has an effect of suppressing solder embrittlement. However, if the amount added is large, the electrical conductivity decreases, so it is preferable to add up to 0.5% by mass, and preferably 0.1 to 0.4% by mass.
(5) Fe, Al, P
These elements are also elements that can improve the alloy strength. What is necessary is just to add as needed. However, if the addition amount is large, the characteristics deteriorate depending on the added element. Therefore, it is preferable to add up to 0.5% by mass, and it is preferable to add 0.005 to 0.4% by mass.
上記のＣｒ、Ｃｏ、Ｍｇ、Ｍｎ、Ｓｎ、Ｆｅ、Ａｌ及びＰは合計で１．０質量％を超えると製造性を損ないやすいので、好ましくはこれらの合計は１．０質量％以下とし、より好ましくは０．５質量％以下とする。 Since the above Cr, Co, Mg, Mn, Sn, Fe, Al, and P are more than 1.0% by mass in total, the productivity is likely to be impaired. Therefore, preferably these totals are 1.0% by mass or less. Preferably it is 0.5 mass% or less.
Ｎｉ−Ｓｉ化合物粒子
本発明においては、銅マトリックス中に析出するＮｉ−Ｓｉ化合物粒子を小粒子と大粒子の二種類に分け、それぞれの個数密度及び粒径、さらにはそれらの相互関係も制御する。本発明において、小粒子とは粒径が０．０１μｍ以上で０．０５μｍ未満であるＮｉ−Ｓｉ化合物粒子を指し、大粒子とは粒径が０．０５μｍ以上で５．０μｍ未満であるＮｉ−Ｓｉ化合物粒子を指す。小粒子は主として結晶粒内に析出した粒子であり、大粒子は主として結晶粒界に析出した粒子である。また、Ｎｉ−Ｓｉ化合物粒子とは、元素分析によってＮｉ及びＳｉの両者が検出される粒子のことを指す。小粒子は主に合金の強度及び耐熱性に寄与し、大粒子は主に導電率の維持及び結晶粒の微細化に寄与する。
Ni-Si compound particles In the present invention, Ni-Si compound particles precipitated in a copper matrix are divided into two types, small particles and large particles, and the number density and particle size of each particle, and also their interrelationships are controlled. . In the present invention, small particles refer to Ni—Si compound particles having a particle size of 0.01 μm or more and less than 0.05 μm, and large particles are Ni— having a particle size of 0.05 μm or more and less than 5.0 μm. Refers to Si compound particles. Small particles are mainly particles precipitated in crystal grains, and large particles are mainly particles precipitated in crystal grain boundaries. Ni-Si compound particles refer to particles in which both Ni and Si are detected by elemental analysis. The small particles mainly contribute to the strength and heat resistance of the alloy, and the large particles mainly contribute to maintenance of conductivity and refinement of crystal grains.
結晶粒内に析出するＮｉ−Ｓｉ化合物粒子は一般に数十ｎｍ程度の微細な析出物となることができる。そのうち、０．０５μｍ未満であるＮｉ−Ｓｉ化合物粒子は転位のピン止め効果を有するため、転位密度が高くなり、合金全体の強度が向上しやすい。この程度の粒径のＮｉ−Ｓｉ化合物粒子は粒子間距離が小さく、数も多いために強度に寄与する率が高い。また、加熱時による転移の移動を妨げる作用があることから、耐熱性を向上させる。
しかしながら、この程度の大きさの粒子、とりわけ０．０１μｍ未満のＮｉ−Ｓｉ化合物粒子は大きなひずみが加えられると剪断されて粒子の表面積が減少するために、剪断に必要な力が減少する。従って転位ループが残されずに転位密度が高くならない。従って０．０１μｍ未満のＮｉ−Ｓｉ化合物粒子は強度に寄与しにくい。剪断された粒子は銅母相中に再度固溶し、導電率の低下を招くおそれもある。また、剪断された粒子は再結晶の核生成サイトとして働かないので、再結晶粒も粗大になる可能性が高くなる。粗大な結晶粒は強度や曲げ性に悪影響を与える。
Ni—Si compound particles precipitated in crystal grains can generally be fine precipitates of about several tens of nm. Among these, Ni—Si compound particles having a diameter of less than 0.05 μm have a dislocation pinning effect, so that the dislocation density is increased and the strength of the entire alloy is easily improved. Since the Ni—Si compound particles having such a particle size have a small inter-particle distance and a large number, the rate contributing to the strength is high. Moreover, since it has the effect | action which prevents the movement of the transition by the time of a heating, heat resistance is improved.
However, particles of this size, especially Ni—Si compound particles of less than 0.01 μm, are sheared when the large strain is applied, and the surface area of the particles is reduced, so that the force required for shearing is reduced. Therefore, the dislocation density is not increased without leaving a dislocation loop. Therefore, Ni—Si compound particles of less than 0.01 μm hardly contribute to the strength. The sheared particles may be dissolved again in the copper matrix, leading to a decrease in conductivity. Further, since the sheared particles do not act as nucleation sites for recrystallization, there is a high possibility that the recrystallized grains become coarse. Coarse crystal grains have an adverse effect on strength and bendability.
従って、粒径が０．０１μｍ以上で０．０５μｍ未満の小粒子の個数密度を制御することが有利となる。小粒子は強度向上に大きく寄与する一方で多くなると導電率を低下させやすいことから、強度及び導電率のバランスを図る上では、小粒子の個数密度を１ｍｍ2当たり１０6−１０10個とすることが必要である。小粒子の個数密度は、透過型電子顕微鏡で組織観察して測定することができる。 Therefore, it is advantageous to control the number density of small particles having a particle size of 0.01 μm or more and less than 0.05 μm. Small particles greatly contribute to the improvement of strength, but if they increase, the conductivity tends to decrease. Therefore, in order to balance the strength and the conductivity, the number density of small particles is 10 6 to 10 10 per mm 2. It is necessary. The number density of the small particles can be measured by observing the structure with a transmission electron microscope.
一方、結晶粒界に析出するＮｉ−Ｓｉ化合物粒子は一般に数百ｎｍ〜数μｍ程度の大きさの析出物となることができる。そのうち、０．０５μｍ以上で５．０μｍ未満であるＮｉ−Ｓｉ化合物粒子は剪断されない強い粒子として作用することができる。小粒子と同様に合金の強度と耐熱性を向上させることができるが、粒径が大きいために粒子の数が少なく、粒子間距離が大きいために強度、耐熱性への寄与は小粒子より小さい。しかしながら大きなひずみが加えられても剪断されないために、導電率の低下がほとんど無い。また、剪断されない粒子は再結晶の際の核生成サイトとして働くことができる。従って、大粒子によって微細な結晶粒が形成しやすくなる。微細な結晶粒は特に強度及び曲げ性に寄与する。大きさが５．０μｍを超える粒子が増加していくと、小粒子の形成に利用されるべきＮｉ及びＳｉが不足して強度が低下しやすくなる。材料にＡｇめっきなどを行った場合に局所的にめっき厚が厚くなり、突起状の欠陥を招くおそれもある。 On the other hand, the Ni—Si compound particles precipitated at the crystal grain boundaries can generally become precipitates having a size of about several hundred nm to several μm. Among them, Ni—Si compound particles that are 0.05 μm or more and less than 5.0 μm can act as strong particles that are not sheared. The strength and heat resistance of the alloy can be improved in the same way as small particles, but the number of particles is small due to the large particle size and the distance between particles is large, so the contribution to strength and heat resistance is smaller than that of small particles. . However, even if a large strain is applied, it is not sheared, so there is almost no decrease in conductivity. Also, the unsheared particles can serve as nucleation sites during recrystallization. Therefore, it becomes easy to form fine crystal grains by the large particles. Fine crystal grains particularly contribute to strength and bendability. As the number of particles with a size exceeding 5.0 μm increases, Ni and Si to be used for the formation of small particles are insufficient and the strength tends to decrease. When Ag plating or the like is performed on the material, the plating thickness locally increases, which may lead to protrusion-like defects.
従って、０．０５μｍ以上で５．０μｍ未満の大粒子の個数密度を制御することが有利となる。大粒子は結晶粒の微細化や導電率の向上に寄与する一方で多くなると小粒子の個数密度を低下させやすいことから、大粒子と小粒子の数の比が適切な範囲に無い場合、強度-導電率の両立はバランスが崩れる。具体的には、大粒子が多くなれば強度が低下し、小粒子が多くなれば導電率が低下する。そこで、強度及び導電率のバランスを図る上では、０．０５μｍ以上で５．０μｍ未満の粒径範囲における個数密度を小粒子と比べて１／１００００〜１／１０とすることが必要である。大粒子の個数密度は、走査電子顕微鏡で組織観察して測定することができる。 Therefore, it is advantageous to control the number density of large particles of 0.05 μm or more and less than 5.0 μm. Large particles contribute to the refinement of crystal grains and electrical conductivity, while increasing the number of small particles tends to reduce the number density of small particles, so if the ratio of the number of large particles to small particles is not within the appropriate range, -The balance of conductivity is out of balance. Specifically, the strength decreases as the number of large particles increases, and the conductivity decreases as the number of small particles increases. Therefore, in order to balance the strength and the electrical conductivity, the number density in the particle size range of 0.05 μm or more and less than 5.0 μm is required to be 1/10000 to 1/10 compared to the small particles. The number density of large particles can be measured by observing the structure with a scanning electron microscope.
小粒子及び大粒子の平均粒径の差を適切な範囲に制御することで、小粒子と大粒子の両者の利点が生かしながら、両者の欠点を補完する効果が大きくなる。小粒子の平均粒径に対する大粒子の平均粒径の比を２〜１００とするのが好ましい。 By controlling the difference between the average particle sizes of the small particles and the large particles within an appropriate range, the advantages of both the small particles and the large particles can be utilized, and the effect of complementing the disadvantages of both can be increased. The ratio of the average particle size of the large particles to the average particle size of the small particles is preferably 2 to 100.
結晶粒は微細であることが強度及び曲げ性の観点から有利であるが、小さすぎると粒界に析出する大粒子と粒内に析出する小粒子のバランスが崩れる。そこで、本発明に係る銅合金では、圧延方向に平行な厚み方向の断面から観察した時に円相当径で表して平均結晶粒径を５〜３０μｍとするのが好ましい。 It is advantageous from the viewpoint of strength and bendability that the crystal grains are fine, but if it is too small, the balance between the large particles precipitated at the grain boundaries and the small particles precipitated within the grains is lost. Therefore, in the copper alloy according to the present invention, it is preferable that the average crystal grain size is 5 to 30 [mu] m expressed by the equivalent circle diameter when observed from the cross section in the thickness direction parallel to the rolling direction.
製造方法
次に本発明に係る銅合金の製造方法に関して説明する。本発明に係る銅合金はＣｕ−Ｎｉ−Ｓｉ系合金の慣例の製造工程を基本としながら、一部の特徴的な工程を経て製造することができる。
Manufacturing Method Next, the manufacturing method of the copper alloy according to the present invention will be described. The copper alloy according to the present invention can be manufactured through some characteristic processes, based on the conventional manufacturing process of Cu-Ni-Si alloys.
まず大気溶解炉を用い、電気銅、Ｎｉ、Ｓｉ等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後、熱間圧延を行い、冷間圧延と熱処理を繰り返して、所望の厚み及び特性を有する条や箔に仕上げる。熱処理には溶体化処理と時効処理がある。溶体化処理では、６００〜１０００℃の高温で加熱して、Ｎｉ−Ｓｉ系化合物をＣｕ母地中に固溶させ、同時にＣｕ母地を再結晶させる。溶体化処理を、熱間圧延で兼ねることもある。 First, using an atmospheric melting furnace, raw materials such as electrolytic copper, Ni, and Si are melted to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. Thereafter, hot rolling is performed, and cold rolling and heat treatment are repeated to finish a strip or foil having a desired thickness and characteristics. Heat treatment includes solution treatment and aging treatment. In the solution treatment, heating is performed at a high temperature of 600 to 1000 ° C., so that the Ni—Si-based compound is dissolved in the Cu matrix, and at the same time, the Cu matrix is recrystallized. The solution treatment may be combined with hot rolling.
晶出粒子の粗大化を抑制するためにはＮｉ及びＳｉ添加後溶湯を１３００℃以上の温度に５分以上保持することが重要となる。
また、その後の熱間圧延前においては加熱温度、保持時間を制御し、かつ熱間圧延終了時の材料温度を制御するのが望ましい。しかしながら、一般的にＮｉ及びＳｉ濃度が高くなると、加熱温度が高い場合は熱間圧延で割れが生じることが知られている。従って、熱間圧延前の加熱温度は８００−１０００℃程度の高い温度とし、割れが生じた場合はより低い温度を選定する。８００℃未満の低い温度を選定した場合は晶出粒子の低減を目的として保持時間を長くすることが必要で、温度にもよるが３時間程度の保持でほとんどの粒子を５μｍより小さくすることができる。熱間圧延終了時の板厚は２０ｍｍより薄くすることで冷却が早くなり、特性に寄与しない析出物の析出を抑制することができる。この際の温度は６００℃以上の高い温度で終了してもよいが、後の工程において溶体化が困難となる場合は、より低い温度で終了する方が有効である。
更に、熱間圧延にて溶体化処理を兼ねる場合は、終了後の空冷（放冷）によって析出粒子が析出する場合があるので、必要に応じて水冷等の冷却を実施すると効果的である。
In order to suppress coarsening of crystallized particles, it is important to maintain the molten metal at a temperature of 1300 ° C. or higher for 5 minutes or longer after addition of Ni and Si.
In addition, before the subsequent hot rolling, it is desirable to control the heating temperature and holding time and to control the material temperature at the end of hot rolling. However, it is generally known that when the Ni and Si concentrations increase, cracking occurs during hot rolling when the heating temperature is high. Therefore, the heating temperature before hot rolling is set to a high temperature of about 800 to 1000 ° C., and a lower temperature is selected when cracking occurs. When a low temperature of less than 800 ° C. is selected, it is necessary to lengthen the holding time for the purpose of reducing crystallized particles, and depending on the temperature, most particles can be made smaller than 5 μm by holding for about 3 hours. it can. By reducing the thickness at the end of hot rolling to less than 20 mm, cooling can be accelerated, and precipitation of precipitates that do not contribute to properties can be suppressed. The temperature at this time may be terminated at a high temperature of 600 ° C. or higher. However, when it is difficult to form a solution in a later step, it is more effective to terminate at a lower temperature.
Furthermore, when the solution treatment is also performed by hot rolling, the precipitated particles may be deposited by air cooling (cooling) after completion, and therefore cooling such as water cooling is effective if necessary.
また、本発明では溶体化処理の条件を厳密に制御する。具体的には添加元素、特にＮｉを十分に固溶させるために、Ｎｉ濃度に応じて一定程度以上の溶体化温度を選定する。但し、あまり高すぎると結晶粒径が大きくなり過ぎるので高ければよいというものでもない。具体的には、Ｎｉ濃度が高ければ高い温度とし、おおまかな目安として１．５％では６５０−７００℃、２．５％では８００−８５０℃、３．５％では９００−９５０℃程度とする。より一般化すれば、ｙ＝１２５ｘ＋５００±２５（式中、ｘはＮｉの添加濃度（質量％）、ｙは溶体化温度（℃））程度とする。そして、大粒子及び小粒子の析出状態を本発明で規定する範囲に収める上では溶体化処理後の結晶粒径が圧延方向に直角な断面で観察したときに５−３０μｍの範囲になるように溶体化処理の温度及び時間を調節することが重要である。また、溶体化処理時の材料の板厚が大きいと、溶体化処理後に水冷しても冷却速度が十分に得られず、固溶させた添加元素が冷却中に析出してしまうおそれがある。従って、溶体化処理を実施する際の板厚は０．３ｍｍ以下とするのが望ましい。また、添加元素の析出を抑制する上では溶体化温度から４００℃までの平均冷却速度を１０℃／秒以上とするのが望ましく、１５℃／秒以上とするのがより望ましい。このような冷却速度は板厚が０．３ｍｍ以下程度であれば空冷で達成できるが、水冷するのがなお良い。ただし、あまり冷却速度を高くしても製品の形状が悪くなるので３０℃／秒以下とするのが好ましく、２０℃／秒以下とするのがより好ましい。 In the present invention, the conditions for the solution treatment are strictly controlled. Specifically, in order to sufficiently dissolve the additive element, particularly Ni, a solution temperature of a certain level or more is selected according to the Ni concentration. However, if it is too high, the crystal grain size becomes too large, so that it is not necessarily high. Specifically, the higher the Ni concentration, the higher the temperature. As a rough guide, 1.5% is 650-700 ° C, 2.5% is 800-850 ° C, and 3.5% is about 900-950 ° C. . More generally, it is assumed that y = 125x + 500 ± 25 (where x is the concentration of Ni added (mass%) and y is the solution temperature (° C.)). And, in order to keep the precipitation state of large particles and small particles within the range specified in the present invention, the crystal grain size after solution treatment is in the range of 5-30 μm when observed in a cross section perpendicular to the rolling direction. It is important to adjust the temperature and time of the solution treatment. In addition, if the thickness of the material during the solution treatment is large, a sufficient cooling rate cannot be obtained even when water-cooled after the solution treatment, and the solidified additive element may be precipitated during the cooling. Accordingly, it is desirable that the thickness of the solution treatment is 0.3 mm or less. In order to suppress the precipitation of the additive element, the average cooling rate from the solution temperature to 400 ° C. is preferably 10 ° C./second or more, and more preferably 15 ° C./second or more. Such a cooling rate can be achieved by air cooling if the plate thickness is about 0.3 mm or less, but water cooling is still better. However, even if the cooling rate is increased too much, the shape of the product is deteriorated, so that it is preferably 30 ° C./second or less, and more preferably 20 ° C./second or less.
溶体化処理の後は求める特性に応じて適切な加工度（圧下率）で冷間加工を行うことが重要である。加工度が高すぎると曲げ加工性に異方性が現れ、低すぎると強度が高くならない。曲げ加工性及び大粒子による特性向上効果の両立を狙うなら、溶体化処理後に加工度２０〜５０％冷間圧延を行うのが好ましい。加工度（％）は（加工前の板厚−加工後の板厚）／加工前の板厚×１００によって表すことができる。 After the solution treatment, it is important to perform cold working at an appropriate working degree (rolling rate) according to the required characteristics. If the degree of work is too high, anisotropy appears in the bending workability, and if it is too low, the strength does not increase. In order to achieve both the bending workability and the effect of improving the properties due to large particles, it is preferable to perform cold rolling with a workability of 20 to 50% after the solution treatment. The degree of processing (%) can be expressed by (plate thickness before processing−plate thickness after processing) / plate thickness before processing × 100.
また、本発明では時効処理の条件も重要となる。本発明に係る銅合金を製造するにあたっては、一回の時効処理で大粒子及び小粒子の分布状態を制御することが望ましい。特許文献１では時効処理を二回することで大粒子と小粒子を析出させる方法を採用しているが、一般的に知られたこととして、一端析出物が析出した状態では、銅中に固溶したＮｉ、Ｓｉ濃度が低くなるために、Ｎｉ、Ｓｉが拡散しにくく、従って析出しにくくなる。そのため、本発明が意図するような個数密度の小粒子が得られない。また、２回目の時効処理時に、１回目の時効処理で既に生成している析出粒子の大きさが影響を受けるため、粒子径や密度の制御が困難である。
一回の時効処理で大粒子と小粒子を所望の範囲にするためには前工程で溶体化処理及び冷間圧延を適切に行っていることが前提であるが、温度と時間を適切な範囲にすることが重要である。この時効処理で強度と導電率が上昇する。時効処理は３００〜６００℃の温度で０．５〜５０ｈとするが、加熱温度が高いほど短時間、加熱温度が低いほど長時間とする。高温で長時間加熱するとＮｉ−Ｓｉ化合物粒子が粗大化しやすく、低温で短時間加熱するとＮｉ−Ｓｉ化合物粒子が十分に析出しないからである。具体的には、３００〜５００℃ではｙ＝−０．１１５ｘ＋６１（ｘは加熱温度（℃）、ｙは時効時間（ｈ））程度とすることができ、５００〜６００℃ではｙ＝−０．０２７５ｘ＋１７．２５（ｘは加熱温度（℃）、ｙは時効時間（ｈ））程度とすることができる。例えば６００℃では０．５ｈ−１ｈ程度、５００℃では２ｈ−５ｈ程度、４００℃では１０ｈ−２０ｈとすればよい。より高い強度を得るために、時効後に冷間圧延を行なうこともできる。時効後に冷間圧延を行なう場合には、冷間圧延後に歪取焼鈍（低温焼鈍）を行なってもよい。
In the present invention, the conditions for aging treatment are also important. In producing the copper alloy according to the present invention, it is desirable to control the distribution state of large particles and small particles by a single aging treatment. Patent Document 1 employs a method of precipitating large particles and small particles by performing aging treatment twice. As generally known, in the state where precipitates are precipitated, the solid particles are solidified in copper. Since the dissolved Ni and Si concentrations are low, Ni and Si are less likely to diffuse and therefore less likely to precipitate. For this reason, small particles having a number density as intended by the present invention cannot be obtained. In addition, since the size of the precipitated particles already generated in the first aging treatment is affected during the second aging treatment, it is difficult to control the particle size and density.
In order to bring large particles and small particles into the desired range in one aging treatment, it is premised that solution treatment and cold rolling are appropriately performed in the previous process, but the temperature and time are in the appropriate range. It is important to make it. This aging treatment increases strength and conductivity. The aging treatment is performed at a temperature of 300 to 600 ° C. for 0.5 to 50 hours, and the shorter the heating temperature is, the longer the heating temperature is. This is because Ni—Si compound particles are likely to be coarsened when heated at a high temperature for a long time, and Ni—Si compound particles are not sufficiently precipitated when heated at a low temperature for a short time. Specifically, y = −0.115x + 61 (x is a heating temperature (° C.), y is an aging time (h)) at 300 to 500 ° C., and y = −0. 0275x + 17.25 (x is the heating temperature (° C.), y is the aging time (h)) or so. For example, it may be about 0.5h-1h at 600 ° C, about 2h-5h at 500 ° C, and 10h-20h at 400 ° C. In order to obtain higher strength, cold rolling can also be performed after aging. When performing cold rolling after aging, strain relief annealing (low temperature annealing) may be performed after cold rolling.
本発明に係る銅合金は種々の伸銅品、例えば板、条、管、棒及び線に加工することができ、更に、本発明による銅合金は、高い強度及び高い電気伝導性（又は熱伝導性）を両立させることが要求されるリードフレーム、コネクタ、ピン、端子、リレー、スイッチ、二次電池用箔材等の電子機器部品に使用することができる。 The copper alloy according to the present invention can be processed into various copper products, such as plates, strips, tubes, rods and wires, and the copper alloy according to the present invention has high strength and high electrical conductivity (or heat conduction). Can be used for electronic device parts such as lead frames, connectors, pins, terminals, relays, switches, and foil materials for secondary batteries.
以下に本発明の具体例を示すが、これら実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。 Specific examples of the present invention are shown below, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the present invention.
表１〜表４に記載の各種成分組成の銅合金を、高周波溶解炉で１３００℃で溶製し、厚さ３０ｍｍのインゴットに鋳造した。次いで、このインゴットを１０００℃で１時間加熱後、板厚１０ｍｍまで熱間圧延し（熱間圧延終了時の材料温度は５００℃）、速やかに水中冷却を行った。表面のスケール除去のため厚さ８ｍｍまで面削を施した後、冷間圧延により厚さ０．２ｍｍの板とした。次に溶体化処理を表１〜表４に記載の各条件で実施した後、室温まで水中冷却した。このとき結晶粒径は添加元素濃度や溶体化条件によって変化する。その後０．１ｍｍまで冷間圧延して、最後に表１〜表４に記載の各条件で不活性雰囲気中で時効処理を施して、各試験片を製造した。表１（実施例）及び表３（比較例）はＣｕ−Ｎｉ−Ｓｉ系銅合金の製造例を示し、表２及び表４は更にＭｇ、Ｃｒ、Ｓｎ、Ｚｎ、Ｍｎ、Ｆｅを適宜添加したＣｕ−Ｎｉ−Ｓｉ系銅合金の製造例を示す。 Copper alloys having various component compositions described in Tables 1 to 4 were melted at 1300 ° C. in a high-frequency melting furnace and cast into an ingot having a thickness of 30 mm. Next, the ingot was heated at 1000 ° C. for 1 hour, and then hot-rolled to a plate thickness of 10 mm (the material temperature at the end of hot rolling was 500 ° C.) and rapidly cooled in water. After surface chamfering to a thickness of 8 mm for removing scale on the surface, a plate having a thickness of 0.2 mm was formed by cold rolling. Next, the solution treatment was performed under the conditions described in Tables 1 to 4, and then cooled to room temperature in water. At this time, the crystal grain size varies depending on the concentration of the additive element and the solution conditions. Thereafter, it was cold-rolled to 0.1 mm, and finally subjected to an aging treatment in an inert atmosphere under the conditions described in Tables 1 to 4 to produce each test piece. Table 1 (Examples) and Table 3 (Comparative Examples) show production examples of Cu—Ni—Si based copper alloys, and Tables 2 and 4 further added Mg, Cr, Sn, Zn, Mn, and Fe as appropriate. The example of manufacture of a Cu-Ni-Si type copper alloy is shown.
このようにして得られた各合金につき各特性評価を行い、結果を表１〜表４に記載した。
強度については圧延平行方向での引っ張り試験を行い、引張り強さ及び０．２％耐力（Ｍｐａ）を測定した。
導電率（％ＩＡＣＳ）についてはダブルブリッジによる体積抵抗率測定により求めた。
曲げ性の評価は、ＪＩＳ Ｈ ３１３０に従って、Ｇｏｏｄｗａｙ（曲げ軸が圧延方向と直角方向）及びＢａｄｗａｙ（曲げ軸が圧延方向と同一方向）のＷ曲げ試験を行って割れの発生しない最小半径（ＭＢＲ）の板厚（ｔ）に対する比であるＭＢＲ／ｔ値を測定した。
結晶粒径は、溶体化処理直後に、走査電子顕微鏡（SEM）：HITACHI-S-4700を用いて測定した。圧延方向に平行な厚み方向の断面をＦＩＢにより切断して試料とした。結晶粒径は加工方向の幅について、１０個の結晶粒の平均値を求めた。なお、溶体化処理後に冷間圧延をしているため、最終製品では結晶粒が厚み方向に潰され、圧延方向に延びているが、面積は保存されることから、最終製品を組織観察したのと同様の結果となる。
最終製品からは以下の方法で結晶粒径を測定することが可能である。まず、圧延方向に平行な厚み方向の断面を電解研磨し、ＳＥＭにより断面組織を観察し、単位面積当たりの結晶粒の数をカウントする。そして、全観察視野の面積を合計し、それをカウントした結晶粒の合計で除し、結晶粒一個あたりの面積を計算する。その面積より、その面積と同じ面積を有する真円の直径（円相当径）を計算し、これを平均結晶粒径とすることができる。
大粒子及び小粒子の粒径は任意の断面から観察して良い。実施例は製品の圧延方向の平行断面に対して、大粒子を走査型電子顕微鏡（HITACHI-S-4700）により、小粒子を透過型電子顕微鏡（HITACHI-H-9000）によりそれぞれ１０視野観察してそれぞれの粒子が１００個程度観察できるように実施した。析出物の大きさが５〜１００ｎｍの場合は５０万倍〜７０万倍の倍率、１００〜５０００ｎｍの場合は５〜１０万倍で撮影を行った。なお析出物の大きさが５ｎｍより小さいものは観察が不可能である。５０００ｎｍより大きいものは走査型電子顕微鏡で観察可能である。
このように観察された粒子について、個々の粒子の長径と短径から面積を計算し、その面積より、その面積と同じ面積を有する真円の直径（円相当径）を計算し、これを粒径とすることができる。粒径から小粒子と大粒子に分け、それぞれ粒子径と粒子の数を集計し、粒子径の和を粒子数で除して平均粒子径とし、粒子数の和を観察視野の合計面積で除して個数密度を求めた。ここで、長径とは、粒子の重心を通り、粒子の境界線との交点を両端にもつ線分のうち、もっとも長い線分の長さを指し、短径とは粒子の重心を通り、粒子の境界線との交点を両端にもつ線分のうち、もっとも短い線分の長さを指す。
観察した粒子がＮｉ−Ｓｉ化合物粒子であることは、ＥＤＳを搭載した走査型電子顕微鏡、特に元素分析の精度が高い電界放射型電子顕微鏡による元素マッピング、小さい析出物についてはＥＥＬＳを搭載した透過型電子顕微鏡による元素マッピングの方法により確認した。
なお、最終製品においては、転位が非常に多く析出物が観察しにくい場合があり、その場合、観察を容易にするために析出しない２００℃程度の温度で歪取り焼鈍を実施しても良い。また、一般的な透過型電子顕微鏡の試料作成において、電解研磨法が用いられるが、FIB（Focused Ion Beam：集束イオンビーム）による薄膜作成を行って測定しても良い。
Thus, each characteristic evaluation was performed about each obtained alloy, and the result was described in Tables 1-4.
As for the strength, a tensile test in the rolling parallel direction was performed, and the tensile strength and 0.2% proof stress (Mpa) were measured.
The electrical conductivity (% IACS) was determined by volume resistivity measurement using a double bridge.
Bendability is evaluated according to JIS H 3130 by performing a W-bending test of Goodway (the bending axis is perpendicular to the rolling direction) and Badway (the bending axis is the same direction as the rolling direction) and the minimum radius (MBR) at which cracks do not occur. The MBR / t value, which is the ratio to the plate thickness (t), was measured.
The crystal grain size was measured using a scanning electron microscope (SEM): HITACHI-S-4700 immediately after the solution treatment. A cross section in the thickness direction parallel to the rolling direction was cut by FIB to obtain a sample. As for the crystal grain size, an average value of 10 crystal grains was obtained for the width in the processing direction. In addition, since the cold rolling was performed after the solution treatment, the crystal grains in the final product were crushed in the thickness direction and extended in the rolling direction, but the area was preserved, so the structure of the final product was observed. Results in the same.
From the final product, the crystal grain size can be measured by the following method. First, a cross section in the thickness direction parallel to the rolling direction is electropolished, the cross-sectional structure is observed by SEM, and the number of crystal grains per unit area is counted. Then, the areas of all observation fields are summed, and the total area is divided by the total number of crystal grains counted to calculate the area per crystal grain. From the area, the diameter (equivalent circle diameter) of a perfect circle having the same area as that area can be calculated and used as the average crystal grain size.
You may observe the particle size of a large particle and a small particle from arbitrary cross sections. In the examples, large particles were observed with a scanning electron microscope (HITACHI-S-4700) and small particles were observed with a transmission electron microscope (HITACHI-H-9000) for 10 fields of view, respectively, on a parallel section in the rolling direction of the product. This was carried out so that about 100 particles could be observed. When the size of the precipitate was 5 to 100 nm, the image was taken at a magnification of 500,000 to 700,000 times, and when it was 100 to 5000 nm, the image was taken at 5 to 100,000 times. It is impossible to observe a precipitate having a size smaller than 5 nm. Those larger than 5000 nm can be observed with a scanning electron microscope.
For the particles observed in this way, the area is calculated from the major axis and minor axis of each particle, and from the area, the diameter of a perfect circle having the same area as that area (equivalent circle diameter) is calculated. It can be a diameter. The particle size is divided into small particles and large particles, the particle size and the number of particles are totaled, the sum of the particle sizes is divided by the number of particles to obtain the average particle size, and the sum of the particle numbers is divided by the total area of the observation field. Thus, the number density was obtained. Here, the major axis refers to the length of the longest line segment that passes through the particle's center of gravity and has intersections at both ends with the boundary line of the particle, and the minor axis refers to the particle's center of gravity. The length of the shortest line segment among the line segments that have intersections with the boundary line.
The observed particles are Ni-Si compound particles, which means that a scanning electron microscope equipped with EDS, particularly element mapping with a field emission electron microscope with high elemental analysis accuracy, and a transmission type equipped with EELS for small precipitates. This was confirmed by the element mapping method using an electron microscope.
In the final product, there are cases in which dislocations are very large and it is difficult to observe precipitates. In that case, strain relief annealing may be performed at a temperature of about 200 ° C. at which no precipitation occurs for easy observation. Further, in the preparation of a sample for a general transmission electron microscope, an electropolishing method is used, but measurement may be performed by forming a thin film by FIB (Focused Ion Beam).
表１及び表２に記載の本発明の実施例に相当する銅合金については、強度、導電率及び曲げ加工性がバランス良く保たれていることが分かる。
比較例１はＮｉ／Ｓｉ比が低く適切な比ではないので、粗大な晶出物により熱間圧延中に割れが生じた。
比較例２はＮｉが組成の範囲を外れたため、Ｎｉが過剰状態となった。これにより熱間加工性が劣化し、熱間圧延中に割れた。
比較例３は溶体化温度が低いため、粗大な粒子が残留した。その結果、導電率は高くなったが、小粒子の数密度が減少したため強度が低くなった。また、曲げの際、粗大な粒子を起点として破断した。
比較例４は溶体化温度が高いため、結晶粒径が大きくなり、大粒子が減少する一方で、小粒子の数が増えた。そのため、強度が高くなったが、導電率は低下した。溶体化時の結晶粒が大きいため、曲げの際、粒界破壊により曲げ性が劣化した。
比較例５は特許文献１に記載の銅合金に相当する。２回時効したため、２回目の時効で析出した小粒子の大きさが小さく、かつ数密度が著しく減少した。大粒子と小粒子の比は適切だが、小粒子の数密度が低すぎるため、強度が低くなった。
比較例６は時効温度が高いため、粗大な析出物が増えた。その結果、小粒子の密度が減少し、強度が低下した。また導電率は高くなると思われたが、時効温度が高いため、再固溶現象により導電率も低下した。曲げは粗大な粒子を起点として破断した。
比較例７は時効時間が長すぎたため、小粒子の大きさが大きくなってしまい、小粒子の数密度もそれに伴い小さくなり、強度が低下した。
比較例８は時効時間が短すぎたため、析出粒子が無く、強度が低下した。
比較例９は時効時間が長すぎたため、大粒子と小粒子の区別がつかず、大粒子がほとんどとなったため、導電率は高いが、強度が低かった。
比較例１０は時効時間が短すぎたため、析出粒子が無く、強度が低かった。
比較例１１は特許文献２に記載の銅合金に相当する。中間の冷間圧延が無いために、大粒子の数が減少して導電率が低下した。
比較例１２はＭｇの添加量が多すぎたためＭｇＯ等の粗大な介在物が増加し、曲げ性が劣化した。但し、ＣｒとＳｉの析出物により強度は高くなった。
比較例１３はＳｎとＺｎにより耐熱剥離性が向上したが、添加量が多いため導電率が低下した。
比較例１４はＰの添加量が多いため粗大な介在物が増加し、曲げ性が劣化した。なお、Ｆｅ析出により強度は高くなった。
比較例１５はＴｉ添加量が多いため、導電率が著しく低下した。
比較例１６はＺｒ添加量が多いため、Ｚｒ起因の介在物が増加し、曲げ性が劣化した。
比較例１７はＡｌ−Ｚｒの粗大析出物が多数析出した。それを起因としてめっき時の欠陥（突起物）を発生させた。
比較例１８はＣｕ−Ｚｒ、Ｃｕ−Ｔｉの粗大析出物（介在物）が起因となってめっき時に多数の欠陥（突起物）を発生させた。
It can be seen that the copper alloys corresponding to the examples of the present invention described in Tables 1 and 2 are maintained in a well-balanced strength, conductivity and bending workability.
Comparative Example 1 than Ino such a proper ratio lower N i / Si ratio, cracks during hot rolling caused by coarse crystals.
In Comparative Example 2, since Ni was out of the composition range, Ni was in an excessive state. This deteriorated hot workability and cracked during hot rolling.
Since Comparative Example 3 had a low solution temperature, coarse particles remained. As a result, the conductivity increased, but the strength decreased because the number density of small particles decreased. Further, during the bending, the fracture occurred starting from coarse particles.
In Comparative Example 4, since the solution temperature was high, the crystal grain size was increased, the large particles were decreased, and the number of small particles was increased. As a result, the strength increased, but the conductivity decreased. Since the crystal grains at the time of solution treatment were large, the bendability deteriorated due to grain boundary fracture during bending.
Comparative Example 5 corresponds to the copper alloy described in Patent Document 1. Since the aging was performed twice, the size of the small particles precipitated by the second aging was small, and the number density was remarkably reduced. The ratio of large particles to small particles is appropriate, but the strength is low because the number density of small particles is too low.
Since Comparative Example 6 had a high aging temperature, coarse precipitates increased. As a result, the density of small particles decreased and the strength decreased. Moreover, although it was thought that electrical conductivity became high, since aging temperature was high, electrical conductivity also fell by the re-solution phenomenon. Bending broke starting from coarse particles.
In Comparative Example 7, since the aging time was too long, the size of the small particles was increased, the number density of the small particles was decreased accordingly, and the strength was decreased.
In Comparative Example 8, the aging time was too short, so there were no precipitated particles, and the strength decreased.
In Comparative Example 9, since the aging time was too long, the large particles and the small particles could not be distinguished, and the large particles were almost all, so that the conductivity was high but the strength was low.
In Comparative Example 10, the aging time was too short, so there were no precipitated particles and the strength was low.
Comparative Example 11 corresponds to the copper alloy described in Patent Document 2. Since there was no intermediate cold rolling, the number of large particles decreased and the conductivity decreased.
In Comparative Example 12, since the amount of Mg added was too large, coarse inclusions such as MgO increased, and the bendability deteriorated. However, the strength was increased by the precipitates of Cr and Si.
In Comparative Example 13, the heat-resistant peelability was improved by Sn and Zn, but the conductivity decreased because of the large amount of addition.
In Comparative Example 14, since the amount of P added was large, coarse inclusions increased and the bendability deteriorated. The strength was increased by Fe precipitation.
Since the comparative example 15 had much Ti addition amount, the electrical conductivity fell remarkably.
In Comparative Example 16, since the Zr addition amount was large, inclusions due to Zr increased, and the bendability deteriorated.
In Comparative Example 17, a large number of coarse precipitates of Al—Zr were precipitated. This caused defects (projections) during plating.
In Comparative Example 18, a large number of defects (projections) were generated during plating due to coarse precipitates (inclusions) of Cu—Zr and Cu—Ti.
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| TWI411693B (en) * | 2010-04-02 | 2013-10-11 | Jx Nippon Mining & Metals Corp | Cu-Ni-Si alloy for electronic materials |
| JP4672804B1 (en) | 2010-05-31 | 2011-04-20 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si based copper alloy for electronic materials and method for producing the same |
| JP4834781B1 (en) | 2010-08-24 | 2011-12-14 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si alloy for electronic materials |
| JP5734156B2 (en) * | 2010-10-15 | 2015-06-10 | Ｄｏｗａメタルテック株式会社 | Copper alloy sheet and manufacturing method thereof |
| JP5827530B2 (en) * | 2011-09-16 | 2015-12-02 | 三菱伸銅株式会社 | Cu-Ni-Si based copper alloy sheet with excellent spring limit and stress relaxation resistance and good shear workability |
| JP6246454B2 (en) * | 2011-11-02 | 2017-12-13 | Ｊｘ金属株式会社 | Cu-Ni-Si alloy and method for producing the same |
| KR101803797B1 (en) | 2011-12-22 | 2017-12-04 | 미츠비시 신도 가부시키가이샤 | Cu-Ni-Si BASED COPPER ALLOY SHEET HAVING HIGH DIE ABRASION RESISTANCE AND GOOD SHEAR PROCESSABILITY AND METHOD FOR PRODUCING SAME |
| JP2016084542A (en) * | 2012-03-26 | 2016-05-19 | Ｊｘ金属株式会社 | Corson alloy and manufacturing method therefor |
| JP6111028B2 (en) * | 2012-03-26 | 2017-04-05 | Ｊｘ金属株式会社 | Corson alloy and manufacturing method thereof |
| JP5773929B2 (en) * | 2012-03-28 | 2015-09-02 | 株式会社神戸製鋼所 | Copper alloy sheet for electrical and electronic parts with excellent bending workability and stress relaxation resistance |
| JP6126791B2 (en) * | 2012-04-24 | 2017-05-10 | Ｊｘ金属株式会社 | Cu-Ni-Si copper alloy |
| JP5988745B2 (en) * | 2012-07-18 | 2016-09-07 | 三菱伸銅株式会社 | Cu-Ni-Si based copper alloy plate with Sn plating and method for producing the same |
| JP6039999B2 (en) * | 2012-10-31 | 2016-12-07 | Ｄｏｗａメタルテック株式会社 | Cu-Ni-Co-Si based copper alloy sheet and method for producing the same |
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| JP6581755B2 (en) * | 2013-08-09 | 2019-09-25 | 古河電気工業株式会社 | Copper alloy sheet and manufacturing method thereof |
| JP6050738B2 (en) * | 2013-11-25 | 2016-12-21 | Ｊｘ金属株式会社 | Copper alloy sheet with excellent conductivity, moldability and stress relaxation properties |
| JP6113061B2 (en) * | 2013-11-25 | 2017-04-12 | Ｊｘ金属株式会社 | Copper alloy sheet with excellent electrical conductivity, stress relaxation resistance and formability |
| WO2016006053A1 (en) * | 2014-07-09 | 2016-01-14 | 古河電気工業株式会社 | Copper alloy sheet material, connector, and method for producing copper alloy sheet material |
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| JP6228941B2 (en) * | 2015-01-09 | 2017-11-08 | Ｊｘ金属株式会社 | Titanium copper with plating layer |
| DE102015001293B4 (en) * | 2015-02-02 | 2022-11-17 | Isabellenhütte Heusler Gmbh & Co. Kg | power rail arrangement |
| JP6830135B2 (en) * | 2019-08-06 | 2021-02-17 | Ｊｘ金属株式会社 | Cu-Ni-Co-Si alloy for electronic components |
| CN111172423B (en) * | 2020-03-08 | 2021-10-29 | 沈阳有色金属研究所有限公司 | Cupronickel alloy and preparation method thereof |
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