WO2014016934A1 - 銅合金及びその製造方法 - Google Patents
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- WO2014016934A1 WO2014016934A1 PCT/JP2012/068937 JP2012068937W WO2014016934A1 WO 2014016934 A1 WO2014016934 A1 WO 2014016934A1 JP 2012068937 W JP2012068937 W JP 2012068937W WO 2014016934 A1 WO2014016934 A1 WO 2014016934A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Definitions
- the present invention relates to a copper alloy widely used in electrical and electronic equipment and a method for producing the same.
- Beryllium copper represented by C1720 is known as a copper alloy material for electronic parts having both high strength and bending workability.
- alloy materials containing Be has been avoided.
- a Cu—Ni—Sn alloy has attracted attention as a copper alloy replacing beryllium copper.
- This Cu—Ni—Sn based alloy has been found to be a high strength alloy as a result of forming a modulation structure by aging treatment. So far, the composition, processing, heat treatment, additive elements, and structure have been studied, and it has been reported that the strength and bending workability can be further improved.
- the main component is 5 to 20% by mass of Ni, 5 to 10% by mass of Sn and the balance of Cu, and the average diameter x in the plate thickness direction of the crystal grains and rolling
- the ratio (y / x) of the average diameter y parallel to the direction is 1.2 to 12 and 0 ⁇ x ⁇ 15, and the number of second phase particles having a major axis of 0.1 ⁇ m or more observed by cross-sectional microscopy is 1. be .0 ⁇ 10 5 / mm 2 or less has been disclosed (e.g., see Patent Document 2).
- Patent Document 1 the composition of the copper alloy is studied, but the crystal orientation of the copper alloy is not studied. Therefore, there is a problem that the copper alloy does not have an appropriate structure and either strength or bending workability is insufficient.
- Patent Document 2 the number of crystal grains and fine second-phase particles is examined, and bending workability by 90 ° W bending before aging treatment is disclosed.
- bending workability at the stage where the strength is increased after aging treatment has not been studied.
- an alloy of Cu, 9.1% by mass of Ni, and 6.1% by mass of Sn, or an alloy in which 0.39% by mass of Mn or 0.35% by mass of Si is added to the composition alone It is disclosed that the crystal grains after the crystallization treatment are 6 to 22 ⁇ m. However, crystal grains of less than 6 ⁇ m are not obtained. Therefore, there has been a problem that bending workability after aging treatment is not sufficient.
- the present invention has been made to solve the above-described problems, and an object thereof is to obtain a copper alloy capable of simultaneously obtaining high strength and excellent bending workability, and a method for producing the same.
- the copper alloy according to the present invention is a copper alloy rolled into a plate shape, containing 8.5 to 9.5 mass% Ni and 5.5 to 6.5 mass% Sn, with the balance being Cu.
- the average crystal grain size in the cross section perpendicular to the rolling direction is less than 6 ⁇ m, and the ratio x of the average length x in the plate width direction to the average length y in the plate thickness direction / Y satisfies 1 ⁇ x / y ⁇ 2.5, and the X-ray diffraction intensity ratio on the plate surface parallel to the rolling direction of the copper alloy is normalized with the (220) plane X-ray diffraction intensity set to 1
- the (200) plane strength ratio is 0.30 or less, the (111) plane strength ratio is 0.45 or less, and the (311) plane strength ratio is 0.60 or less.
- the intensity ratio is larger than the intensity ratio of the (200) plane and smaller than the intensity ratio of the (311) plane.
- the copper alloy according to the embodiment of the present invention contains 8.5 to 9.5% by mass of Ni and 5.5 to 6.5% by mass of Sn, with the balance being Cu and inevitable impurities.
- the Ni content is less than 8.5% by mass or the Sn content is less than 5.5% by mass, high strength cannot be obtained.
- the Ni content exceeds 9.5 mass% or the Sn content exceeds 6.5 mass% high strength and excellent bending workability cannot be obtained at the same time.
- the inevitable impurities mean impurities contained in normal metal or impurities mixed during the production of a copper alloy. For example, As, Sb, Bi, Pb, Fe, S, O 2 , and H 2nd magnitude.
- the copper alloy of the present embodiment has an average crystal grain size of less than 6 ⁇ m in a cross section perpendicular to the rolling direction.
- the copper alloy of the present embodiment satisfies 1 ⁇ x / y ⁇ 2.5.
- the X-ray diffraction intensity ratio on the plate surface parallel to the rolling direction of the copper alloy of the present embodiment is normalized by setting the (220) plane X-ray diffraction intensity to 1, and the (200) plane intensity ratio. Is 0.30 or less, the intensity ratio of the (111) plane is 0.45 or less, and the intensity ratio of the (311) plane is 0.60 or less.
- the intensity ratio of the (111) plane is larger than the intensity ratio of the (200) plane and smaller than the intensity ratio of the (311) plane. This condition is necessary to obtain high strength and excellent bending workability at the same time.
- the intensity ratio of the (111) plane exceeds 0.45, the intensity ratio of the (200) plane exceeds 0.30, or the intensity ratio of the (311) plane exceeds 0.60, high strength is obtained. Excellent bending workability cannot be obtained at the same time.
- the intensity ratio of the (111) plane is 0.37 to 0.42
- the intensity ratio of the (200) plane is 0.22 to 0.28
- the intensity ratio of the (311) plane is 0.45 to 0. .57.
- it is preferable that the intensity ratio of the (222) plane is less than 0.04 (including 0).
- the maximum height Rz of the surface roughness in the direction perpendicular to the rolling direction of the copper alloy of the present embodiment is 0.6 ⁇ m or less. This condition is necessary to obtain stable bending workability. That is, if the maximum height Rz of the surface roughness exceeds 0.6 ⁇ m, stable bending workability cannot be obtained.
- Inclusions are precipitated at the grain boundaries in the copper alloy.
- the inclusions are fine precipitate particles generated during the production of the copper alloy, and specifically, particles due to an oxide by reaction with the atmosphere or a Cu—Ni—Sn alloy phase.
- the size of the inclusion is a dimension of the diameter if it is a sphere, and is a dimension of a long diameter or a long side if it is an ellipse or a rectangle.
- the grain boundaries and inclusions having a grain size of 1 ⁇ m or less are interspersed within the grain boundaries, and particularly in the cross-sectional structure of the plane perpendicular to the rolling direction, the grain size of 0.5 to If the number of inclusions of 1 ⁇ m exceeds 5 ⁇ 10 4 pieces / mm 2 , the crystal grain boundary becomes a fracture starting point and high strength cannot be obtained, and bending workability is deteriorated. Therefore, in the present embodiment, the number of inclusions having a grain size of 0.5 to 1 ⁇ m existing in the crystal grain boundary in the cross-sectional structure of the plane perpendicular to the rolling direction is set to 5 ⁇ 10 4 / mm 2 or less. .
- the copper alloy of the present embodiment may contain two or more elements selected from Mn, Si, and P in a total amount of 0.1 to 1.0% by mass.
- miniaturization of a crystal grain improves
- strength improves by the solid solution to a parent phase
- corrosion resistance also improves.
- the total amount is less than 0.1% by mass, it does not contribute to the improvement of characteristics, and when it exceeds 1.0% by mass, the strength is increased, but the bending workability and the conductivity are decreased.
- FIG. 1 is a flowchart of a method for manufacturing a copper alloy according to an embodiment of the present invention. The manufacturing method of the copper alloy of this Embodiment is demonstrated along this flowchart.
- step S1 After melting a copper alloy raw material containing 8.5 to 9.5% by mass of Ni and 5.5 to 6.5% by mass of Sn with the balance being Cu and inevitable impurities, using a high frequency melting furnace, A plate-shaped ingot having a width of 60 mm and a thickness of 10 mm is cast (step S1).
- dissolving a copper alloy raw material is not restrict
- step S2 chamfering is performed to remove the oxide film and the like on the ingot surface to obtain an ingot having a thickness of 5 mm (step S2).
- step S3 After rolling the chamfered ingot at room temperature and removing the stress inside the alloy by heating at 800 ° C. for 5 minutes and annealing with water cooling, the rolling is performed again at room temperature, A rolled material having a thickness of 0.22 mm is obtained (step S3).
- a rolled material having a thickness of 0.22 mm is heated at 780 to 900 ° C. (preferably 800 to 850 ° C.), and then rapidly cooled in water to perform a solution treatment (step S4).
- a surface treatment is performed by using both acid treatment and buffing to reduce the thickness of the rolled material to 0.2 mm.
- the heating time varies depending on the dimensions of the rolled material and the specifications of the furnace, but is preferably 20 seconds to 300 seconds in order to avoid crystal grain coarsening. Thereby, good solid solution and crystal grains of the alloy element are achieved.
- the average crystal grain size of the rolled material in the cross section perpendicular to the rolling direction after the solution treatment is less than 6 ⁇ m, more preferably 4 ⁇ m or less. Thereby, bending workability can be improved. When the thickness is 6 ⁇ m or more, the ratio R / t between the minimum value R of the bending radius at which bending does not occur in 180 ° bending and the thickness t of the specimen cannot be made 1 or less.
- step S5 cold rolling with a processing rate of 6 to 12% is performed on the rolled material having a thickness of 0.2 mm.
- the maximum height Rz of the material surface is set to 0.6 ⁇ m or less by using a rolling roll having a surface roughness of less than 0.6 ⁇ m.
- the thin plate is heat-treated at 270 to 400 ° C. for 2 hours (step S6).
- the heating time is preferably 30 to 360 minutes.
- the aging treatment may be performed in two stages.
- step S7 a surface treatment is performed to remove the oxide film formed on the surface by heat treatment. At that time, the surface is finished so that the maximum height is 0.6 ⁇ m or less.
- the copper alloy of this embodiment is manufactured through the above steps.
- the methods of casting, chamfering, rolling, annealing, heating, and quenching are not particularly limited, and a known method may be used.
- the surface treatment method is not particularly limited, and a known method may be used. For example, acid treatment, buffing, or a combination thereof is used.
- the characteristics of the copper alloys of the embodiment and the comparative example were evaluated as follows. (1) The tensile strength was sampled so that the length direction of the tensile test piece was parallel to the rolling direction, and evaluated according to JIS Z 2241. (2) The bending workability conformed to JIS Z 2248 180 ° bending test. Moreover, the test piece of a bending was extract
- the ratio (R / t) between the minimum value R of the bending radius and the test piece thickness t at which cracks do not occur was determined by observing the bent tip surface with an optical microscope.
- the average grain size was measured according to the cutting method of JIS H 0551.
- the metal structure for measuring the average grain size was obtained by polishing a cross section perpendicular to the rolling direction and then performing etching. Then, using an optical microscope, three arbitrarily selected locations were photographed and determined from a 1000 ⁇ photograph by a cutting method.
- the (220) plane, (111) plane, (200) plane, (311) plane, (311) plane, (X) using an X-ray diffractometer manufactured by Rigaku Corporation The peak intensity by X-ray diffraction of the 222) plane was measured. Then, the X-ray diffraction intensity of the (220) plane was normalized as 1, and the X-ray diffraction intensity of each plane with respect to the (220) plane was obtained.
- the surface roughness was measured according to JIS B 0601, and the maximum height Rz was determined from a roughness curve in a direction perpendicular to the rolling direction.
- the number of inclusions present at the grain boundaries per unit mm 2 and the dimensions of the inclusions were determined by the following method. First, after a cross section perpendicular to the rolling direction was polished, etching was performed to obtain a structure. Next, 10 arbitrarily selected points were photographed with an electron microscope at a magnification of 5000 times, and a square region of 15 ⁇ m in length and 20 ⁇ m in width (area 300 ⁇ m 2 ) was aligned on an arbitrary portion, and a grain boundary per 300 ⁇ m 2 The number of inclusions and the dimensions of the inclusions were measured. The number of inclusions present at the grain boundaries was determined by converting the number per unit mm 2 . As for the size of the inclusions, the size of the diameter was obtained from the photograph if it was spherical, and the size of the long diameter was obtained if it was oval.
- Table 1 is a table summarizing the data of the copper alloys of the embodiment and the comparative example. Although the amount of Cu is not clearly shown in this table, it can be estimated from the amounts of other components.
- Numbers 1 to 9 in the embodiment are cases where no impurities are contained, and numbers 10 to 16 are cases where Mn, Si and P are contained in a total amount of 0.1 to 1% by mass.
- the bending workability R / t after aging treatment is 1, and the tensile strength is 930 N / mm 2 or more.
- high strength can be obtained by refining crystal grains.
- Comparative Examples Nos. 17 and 18 are cases where the composition does not correspond to this embodiment.
- Comparative Examples Nos. 19 to 23 are cases where the X-ray diffraction intensity ratio is out of the range of the present embodiment, or the number of inclusions in the crystal grain boundary is larger than the claimed range. In these cases, either the bending workability or the tensile strength does not satisfy the target characteristics.
- No. 24 of the comparative example is a case where Mn, Si, and P are contained in a total amount of less than 0.1% by mass, but the tensile strength is equivalent to that of No. 1 of the embodiment, and the effect of increasing the strength by the addition amount is Absent.
- No. 25 in the comparative example is a case where 1% by mass or more of Mn, Si, and P is contained in a total amount, and high strength is obtained but bending workability is not satisfied.
- the bending workability R / t at 180 ° bending with a tensile strength of 930 N / mm 2 or more and Bad way is 1 or less. You can be satisfied at the same time.
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Abstract
Description
(1)引張強度は、引張試験片の長さの方向が圧延方向と平行となるように採取し、JIS Z 2241に準拠して評価した。
(2)曲げ加工性は、JIS Z 2248の180°曲げ試験に準拠した。また、曲げの試験片はJBMA T307に準拠し圧延方向に直角な試験片を採取してBad way曲げの評価を行った。曲げ加工性として、曲げた先端部表面を光学顕微鏡で観察して割れが発生しない曲げ半径の最小値Rと試験片厚さtの比率(R/t)を求めた。
(3)平均結晶粒度は、JIS H 0551の切断法に準拠して測定した。なお、平均結晶粒度を測定するための金属組織は、圧延方向に対して垂直な断面を研磨した後、エッチングを施して組織を出した。そして、光学顕微鏡を用いて、任意に選択した3箇所を写真撮影し、1000倍の写真上から切断法で求めた。
(4)結晶面の結晶配向性として、(株)リガク製X線回折装置を使用したX線回折法により、(220)面、(111)面、(200)面、(311)面、(222)面のX線回折によるピーク強度を測定した。そして、(220)面のX線回折強度を1として規格化し、(220)面に対する各面のX線回折強度を求めた。
(5)表面粗さは、JIS B 0601に準拠して測定し、圧延方向に対して垂直な方向の粗さ曲線から最大高さRzを求めた。
(6)単位mm2当りの結晶粒界に存在する介在物の個数と介在物の寸法を以下の方法で求めた。まず、圧延方向に対して垂直な断面を研磨した後、エッチングを施して組織を出した。次に、任意に選択した10箇所を5000倍で電子顕微鏡により撮影し、写真上に縦15μm、横20μm(面積300μm2)の正方形の領域を任意の部分に合せ、300μm2当りの結晶粒界に点在する介在物の数と介在物の寸法を測定した。その個数を単位mm2当りに換算して結晶粒界に存在する介在物の個数を求めた。介在物の寸法は、写真上から球形であればその直径の寸法、楕円形であれば長い直径の寸法を求め、測定した介在物の寸法の合計÷測定数から平均値を算出した。
Claims (6)
- 板状に圧延された銅合金であって、
8.5~9.5質量%のNiと5.5~6.5質量%のSnを含有し、残部がCuと不可避の不純物であり、
圧延方向に対して垂直な断面における平均結晶粒径が6μm未満であり、
結晶粒の板幅方向の平均長さxと板厚方向の平均長さyとの比x/yが1≦x/y≦2.5を満たし、
前記銅合金の圧延方向に対して平行な板面におけるX線回折強度比は、(220)面のX線回折強度を1として規格化したときに、(200)面の強度比が0.30以下、(111)面の強度比が0.45以下、(311)面の強度比が0.60以下であり、
前記(111)面の強度比は、前記(200)面の強度比より大きく、前記(311)面の強度比より小さいことを特徴とする銅合金。 - 圧延方向に対して垂直方向の表面粗さの最大高さが0.6μm以下であることを特徴とする請求項1記載の銅合金。
- Mn、Si、Pから選ばれる2つ以上の元素が総量で0.1~1.0質量%含有していること特徴とする請求項1又は2に記載の銅合金。
- 圧延方向に対して垂直な面の断面組織において、結晶粒界に存在する粒径0.5~1μmの介在物の個数が5×104/mm2以下であることを特徴とする請求項1~3の何れか1項に記載の銅合金。
- 8.5~9.5質量%のNiと5.5~6.5質量%のSnを含有し、残部がCuと不可避の不純物である銅合金原料を溶解して鋳塊を形成した後、前記鋳塊を圧延して圧延材を形成する工程と、
前記圧延材を780~900℃で加熱して急冷する溶体化処理を行う工程と、
前記溶体化処理を行った前記圧延材を加工率6~12%で圧延加工する工程と
圧延加工した前記圧延材を270~400℃で加熱する時効処理を行う工程とを備え、
溶体化処理後の圧延方向に対して垂直な断面における前記圧延材の平均結晶粒径が6μm未満であることを特徴とする銅合金の製造方法。 - 前記銅合金原料は、Mn、Si、Pから選ばれる2つ以上の元素が総量で0.1~1.0質量%含有していること特徴とする請求項5に記載の銅合金の製造方法。
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PCT/JP2012/068937 WO2014016934A1 (ja) | 2012-07-26 | 2012-07-26 | 銅合金及びその製造方法 |
CN201280074912.2A CN104583430B (zh) | 2012-07-26 | 2012-07-26 | 铜合金及其制造方法 |
KR1020157001926A KR101715532B1 (ko) | 2012-07-26 | 2012-07-26 | 구리 합금 및 그의 제조 방법 |
US14/413,300 US10002684B2 (en) | 2012-07-26 | 2012-07-26 | Copper alloy and method for manufacturing the same |
JP2014526668A JP5839126B2 (ja) | 2012-07-26 | 2012-07-26 | 銅合金 |
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JP2019065362A (ja) * | 2017-10-03 | 2019-04-25 | Jx金属株式会社 | Cu−Ni−Sn系銅合金箔、伸銅品、電子機器部品およびオートフォーカスカメラモジュール |
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US20150170781A1 (en) | 2015-06-18 |
CN104583430B (zh) | 2017-03-08 |
KR20150023874A (ko) | 2015-03-05 |
JPWO2014016934A1 (ja) | 2016-07-07 |
US10002684B2 (en) | 2018-06-19 |
KR101715532B1 (ko) | 2017-03-10 |
CN104583430A (zh) | 2015-04-29 |
JP5839126B2 (ja) | 2016-01-06 |
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