JP5724257B2 - Copper or copper alloy rolled plate for electronic parts and method for producing the same - Google Patents
Copper or copper alloy rolled plate for electronic parts and method for producing the same Download PDFInfo
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本発明は、端子・コネクタ、リードフレーム等の電子部品や太陽電池パネルの電極間を接続するインターコネクター用配線材料に好適な、優れた疲労特性を有する電子部品用銅又は銅合金圧延板及びその製造方法に関するものである。 The present invention relates to a copper or copper alloy rolled plate for electronic components having excellent fatigue characteristics, suitable for wiring materials for interconnectors that connect between electronic components such as terminals / connectors and lead frames, and electrodes of solar cell panels, and the like It relates to a manufacturing method.
電子部品やインターコネクターに用いられる銅板又は銅合金板は，タフピッチ銅や高純度無酸素銅、クロム銅、ジルコニウム銅、クロムジルコニウム銅などの合金素材のブロックを熱間圧延したものに、さらに冷間圧延と熱処理とを繰り返し、所望の板厚にして製品としている。端子・コネクタやリードフレームには、０．２〜１．０ｍｍ程度の薄板としたものが使用される。 Copper plates or copper alloy plates used for electronic components and interconnectors are made by hot rolling a block of alloy material such as tough pitch copper, high-purity oxygen-free copper, chromium copper, zirconium copper, and chromium zirconium copper. Rolling and heat treatment are repeated to obtain a desired plate thickness. A thin plate of about 0.2 to 1.0 mm is used for the terminal / connector and the lead frame.
電子部品やインターコネクターにおける疲労特性は非常に重要であり、これを高めるための製造方法として、特許文献１に示されるように、最終冷間圧延時における加工度を９０〜９７％と大きくするプロセスや、特許文献２に示されるように、最終の冷間圧延前の結晶粒径と圧延加工度を所定範囲に制御し、再結晶化処理を行う事により、比較的粗大な結晶粒径でかつ、双晶境界が少ない合金組織とすることなどが試みられている。 Fatigue properties in electronic parts and interconnectors are very important, and as a manufacturing method for enhancing this, as shown in Patent Document 1, a process for increasing the workability at the time of final cold rolling to 90 to 97% Or, as shown in Patent Document 2, the crystal grain size before the final cold rolling and the degree of rolling process are controlled within a predetermined range, and by performing recrystallization treatment, the crystal grain size is relatively coarse and Attempts have been made to make alloy structures with few twin boundaries.
しかし、近年、電子部品や装置が小型化し、より厳しい使用環境となるに伴い、要求される疲労特性は以前より高くなっている。また，材料のリサイクル性の観点から、添加元素を加えずに、加工や熱処理のみによって特性を向上させる手法がより求められるようになってきている。 However, in recent years, as electronic parts and devices have become smaller and become a more severe use environment, the required fatigue characteristics have become higher than before. In addition, from the viewpoint of material recyclability, there is a growing demand for a technique for improving characteristics only by processing and heat treatment without adding an additive element.
近年の電子部品や装置の小型化や高水準化に伴い、端子・コネクタ、リードフレーム、インターコネクター等の素材となる銅板又は銅合金板には高い疲労特性が要求される。 With recent miniaturization and high standardization of electronic parts and devices, high fatigue characteristics are required for copper plates or copper alloy plates used as materials for terminals / connectors, lead frames, interconnectors and the like.
本発明の目的は、従来の銅又は銅合金圧延板より高い疲労特性を持つ圧延板を提供することである。 It is an object of the present invention to provide a rolled sheet having higher fatigue properties than conventional copper or copper alloy rolled sheets.
端子・コネクタ、リードフレーム、インターコネクターなどに用いられる銅又は銅合金圧延板材料には、使用環境下に応じて振動や曲げ・引張・圧縮などの各種モードの応力がが負荷され、結果として板材の弾性変形が繰り返されることで板中の結晶粒界に転位が蓄積され、転位同士が互いの動きを阻害し、転位が移動できなくなることでき裂が進展し、破断に至る。特殊粒界は結晶粒同士の整合性が通常の粒界よりも高く、粒界に転位が蓄積しにくいという性質を持つ。そのため、特殊粒界を増加させた材料は疲労特性に優れる。
疲労特性を向上させる方法として、鋳塊を熱間圧延した後、冷間圧延と焼鈍とを繰り返し、直前に焼鈍を行った後５〜２５％の所定の圧延率で仕上げ冷間圧延を行い、さらに所定温度で仕上げ熱処理を行い、特殊粒界の長さ比率が６０％以上の再結晶組織を有する合金組織とする。
Copper or copper alloy rolled plate materials used for terminals, connectors, lead frames, interconnectors, etc. are subjected to various modes of stress such as vibration, bending, tension, compression, etc., depending on the usage environment. By repeating the elastic deformation, dislocations are accumulated at the crystal grain boundaries in the plate, the dislocations inhibit each other's movement, dislocations cannot move, and the crack progresses, leading to fracture. The special grain boundary has a property that the consistency between crystal grains is higher than that of a normal grain boundary, and dislocations hardly accumulate at the grain boundary. Therefore, a material with increased special grain boundaries is excellent in fatigue characteristics.
As a method for improving the fatigue properties, after hot rolling the ingot, cold rolling and annealing are repeated, and after performing annealing immediately before, finish cold rolling is performed at a predetermined rolling rate of 5 to 25%, Further, finish heat treatment is performed at a predetermined temperature to obtain an alloy structure having a recrystallized structure with a special grain boundary length ratio of 60% or more.
すなわち、本発明の銅又は銅合金圧延板は、銅、クロム銅又はクロム（Ｃｒ）を０．１〜０．４ｍａｓｓ％及びジルコニウム（Ｚｒ）を０．０２〜０．２ｍａｓｓ％含有したクロムジルコニウム銅のいずれかからなる銅又は銅合金圧延板であって、厚さ２００μｍ以上１ｍｍ以下であり、ＥＢＳＤ法にて測定した全ての結晶粒界長さＬに対する特殊粒界長さＬσの比率（Ｌσ／Ｌ）が６０％以上であることを特徴とする。
結晶粒界は、二次元断面観察の結果、隣り合う２つの結晶間の配向方位差が１５°以上となっている場合の当該結晶間の境界として定義される。
特殊粒界とは、結晶学的にＣＳＬ理論（Kronberg et.al.:Trans. Met. Soc. AIME, 185, 501 (1949)）に基づき定義されるΣ値で３≦Σ≦２９を有する結晶粒界（対応粒界）であって、当該粒界における固有対応部位格子方位欠陥Ｄｑが Ｄｑ≦１５°/Σ1/2 （D.G.Brandon:Acta.Metallurgica. Vol.14,p1479,1966）を満たす結晶粒界である。
すべての結晶粒界のうち、この特殊粒界の長さ比率が高いと、組織全体の結晶粒界の整合性が向上して、転位が蓄積しにくくなり、疲労特性を向上させることができる。
That is, the rolled copper or copper alloy plate of the present invention is a chromium zirconium copper containing 0.1 to 0.4 mass% of copper, chromium copper or chromium (Cr) and 0.02 to 0.2 mass% of zirconium (Zr). A copper or copper alloy rolled plate made of any one of the following: a thickness of 200 μm or more and 1 mm or less, and a ratio of the special grain boundary length Lσ to all the grain boundary lengths L measured by the EBSD method (Lσ / L) is 60% or more.
A crystal grain boundary is defined as a boundary between crystals when the orientation difference between two adjacent crystals is 15 ° or more as a result of two-dimensional cross-sectional observation.
A special grain boundary is a crystal having a crystal value of 3 ≦ Σ ≦ 29 with a Σ value defined crystallographically based on CSL theory (Kronberg et.al.:Trans. Met. Soc. AIME, 185, 501 (1949)). A crystal that is a grain boundary (corresponding grain boundary) and has an inherent corresponding site lattice orientation defect Dq at the grain boundary satisfying Dq ≦ 15 ° / Σ 1/2 (DGBrandon: Acta. Metallurgica. Vol. 14, p1479, 1966) It is a grain boundary.
When the length ratio of this special grain boundary is high among all the grain boundaries, the consistency of the crystal grain boundaries in the entire structure is improved, dislocations are less likely to accumulate, and fatigue characteristics can be improved.
本発明の銅又は銅合金圧延板の製造方法は、銅、クロム銅又はクロム（Ｃｒ）を０．１〜０．４ｍａｓｓ％及びジルコニウム（Ｚｒ）を０．０２〜０．２ｍａｓｓ％含有したクロムジルコニウム銅のいずれかからなる銅又は銅合金からなる鋳塊の熱間圧延工程と、前記熱間圧延工程の後に、粗冷間圧延及びその歪みを除去する焼鈍処理を行い、その後、仕上げ圧延及び熱処理を行って、前記粗冷間圧延前の板厚と前記仕上げ圧延後の板厚から計算される総圧延率が８９％以上で、厚さを２００μｍ以上１ｍｍ以下の圧延板とする冷間圧延工程とを有するとともに、前記仕上げ圧延及び熱処理は、圧下率が５〜２５％の仕上げ冷間圧延と、被加工材の再結晶温度をＴｓ（℃）としたときに、熱処理温度Ｔａ（℃）を（Ｔｓ−１５０）＜Ｔａ＜（Ｔｓ＋１５０）とし、熱処理時間を５〜３６００秒とした仕上げ再結晶熱処理とを行って、ＥＢＳＤ法にて測定した全ての結晶粒界長さＬに対する特殊粒界長さＬσの比率（Ｌσ／Ｌ）が６０％以上の再結晶組織を有する圧延板を製造することを特徴とする。 The method for producing a rolled copper or copper alloy sheet according to the present invention comprises chromium, chromium copper or chromium (Cr) containing 0.1 to 0.4 mass% and zirconium (Zr) containing 0.02 to 0.2 mass%. After the hot rolling step of the ingot made of copper or copper alloy made of any of copper and the hot rolling step, rough cold rolling and annealing treatment to remove the distortion are performed, and then finish rolling and heat treatment And performing a cold rolling step in which the total rolling ratio calculated from the plate thickness before the rough cold rolling and the plate thickness after the finish rolling is 89% or more and the thickness is 200 μm or more and 1 mm or less. In addition, the finish rolling and the heat treatment include a finish cold rolling with a rolling reduction of 5 to 25% and a heat treatment temperature Ta (° C.) when the recrystallization temperature of the workpiece is Ts (° C.). (Ts−150) <Ta <( s + 150), and the ratio of the special grain boundary length Lσ to the total grain boundary length L measured by the EBSD method (Lσ / L). Is characterized by producing a rolled sheet having a recrystallized structure of 60% or more.
この製造方法においては、熱間圧延後に総圧延率８９％以上の冷間圧延を行うことにより、厚みが２００μｍ以上１ｍｍ以下の圧延板とするとともに、その冷間圧延の終盤で再結晶温度前後での熱処理と低圧下率の仕上げ冷間圧延とを行うことにより、特殊粒界の長さ比率を高めて、疲労特性を向上させる。
この場合、再結晶温度Ｔｓ（℃）を以下のように定義する。所定の材料を加工率８０％で冷間圧延加工を行った板材について、ＪＩＳ Ｚ ２２４４ ビッカース硬さ試験に準拠した試験方法に基づいてビッカース硬さを測定し、その後１００℃以上９００℃以下の温度範囲において、１００℃から５０℃刻みで昇温変量した各温度で６００秒間保持した後、水焼入れを行い、同様にビッカース硬さを測定して得られたビッカース硬さが、熱処理前(冷間加工放し)のビッカース硬さに対して１／２以下となった熱処理温度を再結晶温度Ｔｓと定義する。
熱処理プロセスは、被加工材の再結晶温度Ｔｓに対して、（Ｔｓ−１５０）＜Ｔａ＜（Ｔｓ＋１５０）となる範囲の熱処理温度Ｔａ（℃）で５〜３６００秒間の部分再結晶熱処理を行い、その後に５〜２５％の比較的低い圧下率で仕上げ冷間圧延と仕上げ再結晶焼鈍とを施すことにより、特殊粒界の長さ比率が６０％以上の再結晶組織を有するように制御する。
In this manufacturing method, by performing cold rolling at a total rolling rate of 89% or more after hot rolling, a rolled plate having a thickness of 200 μm or more and 1 mm or less is obtained, and at the end stage of the cold rolling, around the recrystallization temperature. By performing the heat treatment and finish cold rolling at a low pressure reduction rate, the length ratio of the special grain boundary is increased and the fatigue characteristics are improved.
In this case, the recrystallization temperature Ts (° C.) is defined as follows. About the board | plate material which cold-rolled the predetermined material with the processing rate of 80%, Vickers hardness is measured based on the test method based on JISZ2244 Vickers hardness test, and the temperature of 100 to 900 degreeC after that is measured. In the range, after holding for 600 seconds at each temperature varied from 100 ° C. to 50 ° C., water quenching is performed, and the Vickers hardness obtained by measuring the Vickers hardness is the same as before the heat treatment (cold The heat treatment temperature at which the Vickers hardness of processing is reduced to 1/2 or less is defined as the recrystallization temperature Ts.
In the heat treatment process, a partial recrystallization heat treatment is performed for 5 to 3600 seconds at a heat treatment temperature Ta (° C.) in a range of (Ts−150) <Ta <(Ts + 150) with respect to the recrystallization temperature Ts of the workpiece, Thereafter, finish cold rolling and finish recrystallization annealing are performed at a relatively low rolling reduction of 5 to 25%, thereby controlling the length ratio of the special grain boundaries to be 60% or more.
特殊粒界の長さ比率を高めるためには、この再結晶熱処理と低圧下率での仕上げ冷間圧延とを組み合わせて実施することが重要であり、熱処理温度が（Ｔｓ−１５０）以下であったり、熱処理時間が５秒未満では、冷間圧延により生じた歪みの除去が不十分で、再結晶化が十分に生じず、一方、熱処理温度が（Ｔｓ＋１５０）以上であったり、熱処理時間が３６００秒を超えると、結晶粒の粗大化を招き、所望の特殊粒界長さ比率を得ることは難しい。熱処理時間は、５〜１８００秒がより好ましい。
また、仕上げ冷間圧延の圧下率が５％未満では、再結晶化熱処理の過程において特殊粒界の形成が促進されず、一方、２５％を超える圧下率の場合は、導入歪みが大き過ぎて、再結晶化熱処理の過程において特殊粒界以外の粒界形成比率が増加し、所望の特殊粒界長さ比率を得ることができない。
In order to increase the length ratio of the special grain boundary, it is important to combine this recrystallization heat treatment with finish cold rolling at a low pressure reduction rate, and the heat treatment temperature is (Ts-150) or less. If the heat treatment time is less than 5 seconds, the distortion caused by cold rolling is not sufficiently removed, and recrystallization does not occur sufficiently. On the other hand, the heat treatment temperature is (Ts + 150) or more, or the heat treatment time is 3600. If it exceeds 2 seconds, the crystal grains become coarse and it is difficult to obtain a desired special grain boundary length ratio. The heat treatment time is more preferably 5 to 1800 seconds.
In addition, when the reduction ratio of finish cold rolling is less than 5%, the formation of special grain boundaries is not promoted in the process of recrystallization heat treatment, whereas when the reduction ratio exceeds 25%, the introduced strain is too large. In the course of the recrystallization heat treatment, the grain boundary formation ratio other than the special grain boundary increases, and the desired special grain boundary length ratio cannot be obtained.
本発明の銅又は銅合金板の製造方法において、前記仕上げ冷間圧延と前記仕上げ再結晶熱処理とを２回以上繰り返すようにしてもよい。この処理を繰り返すことにより、さらに特殊粒界の長さ比率を高めて疲労特性を向上させることができる。 In the method for producing a copper or copper alloy plate of the present invention, the finish cold rolling and the finish recrystallization heat treatment may be repeated twice or more. By repeating this process, the length ratio of the special grain boundary can be further increased to improve the fatigue characteristics.
本発明によれば、特殊粒界長さ比率が高くなることにより、転位の蓄積を少なくして疲労特性を向上させることができ、端子・コネクタ、リードフレーム、インターコネクター等の素材として用いることにより、電子部品の小型化、高水準化に対応することができる。また、添加元素を加えることなく、加工と熱処理のみによって特性を向上させるので、リサイクル性も良い。 According to the present invention, by increasing the special grain boundary length ratio, it is possible to improve the fatigue characteristics by reducing the accumulation of dislocations, and by using it as a material for terminals / connectors, lead frames, interconnectors, etc. Therefore, it is possible to cope with miniaturization and high standardization of electronic components. Further, since the characteristics are improved only by processing and heat treatment without adding an additive element, recyclability is also good.
以下、本発明の電子部品用銅又は銅合金圧延板及びその製造方法の一実施形態を説明する。
本実施形態の電子部品用銅又は銅合金圧延板は、銅の純度が９９．９６ｍａｓｓ％以上のタフピッチ銅（酸素含有量１００ｐｐｍ）、銅の純度が９９．９９ｍａｓｓ％以上の無酸素銅（酸素含有量１ｐｐｍ）、又は９９．９９９ｍａｓｓ％以上の高純度無酸素銅（酸素含有量０．１ｐｐｍ）、クロム（Ｃｒ）を０．４〜１．２ｍａｓｓ％含有したクロム銅、クロム（Ｃｒ）を０．１〜０．４ｍａｓｓ％及びジルコニウム（Ｚｒ）を０．０２〜０．２ｍａｓｓ％含有したクロムジルコニウム銅などが用いられる。また、添加元素以外の不純物元素については、Ｚｎ、Ｓｎ、Ｆｅ、Ｃｏ、Ａｌ、Ａｇ、Ｍｎ、Ｂ、Ｐ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、希土類元素、 Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｒｅ、Ｒｕ、Ｏｓ、Ｓｅ、Ｔｅ、Ｒｈ、Ｉｒ、Ｐｄ、Ｐｔ、Ａｕ、Ｃｄ、Ｇａ、Ｉｎ、Ｌｉ、Ｓｉ、Ｇｅ、Ａｓ、Ｓｂ、Ｔｉ、Ｔｌ、Ｐｂ、Ｂｉ、Ｓ、Ｏ、Ｃ、Ｎｉ、Ｂｅ、Ｎ、Ｈ、Ｈｇなどが含まれる場合があるが、これらが含まれる場合は、その合計が０．３ｍａｓｓ％以下とする。
なお、本実施形態で例示した素材は、所定の用途に用いられる材料の一例であり、他の素材で、端子・コネクタ、リードフレーム、太陽電池パネル用インターコネクター等に用いられる素材についても、本特許に示されるのと同様の加工・熱処理を実施することにより、特性向上効果が期待される。
また、圧延板の厚さは、端子・コネクタ、リードフレーム、太陽電池用インターコネクター等の素材として好適な２００μｍ以上１ｍｍ以下とされる。
Hereinafter, an embodiment of a copper or copper alloy rolled sheet for electronic parts and a method for producing the same according to the present invention will be described.
The copper or copper alloy rolled sheet for electronic parts of the present embodiment has a copper purity of 99.96 mass% or more of tough pitch copper (oxygen content of 100 ppm), and a copper purity of 99.99 mass% or more of oxygen-free copper (oxygen-containing). 1 ppm), or high-purity oxygen-free copper of 99.999 mass% or more (oxygen content 0.1 ppm), chromium copper containing 0.4 to 1.2 mass% of chromium (Cr), and chromium (Cr) of 0. Chrome zirconium copper containing 1 to 0.4 mass% and 0.02 to 0.2 mass% of zirconium (Zr) is used. As for impurity elements other than additive elements, Zn, Sn, Fe, Co, Al, Ag, Mn, B, P, Ca, Sr, Ba, Sc, Y, rare earth elements, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Re, Ru, Os, Se, Te, Rh, Ir, Pd, Pt, Au, Cd, Ga, In, Li, Si, Ge, As, Sb, Ti, Tl, Pb, Bi, S, O, C, Ni, Be, N, H, Hg, and the like may be included. If these are included, the total is set to 0.3 mass% or less.
The material exemplified in the present embodiment is an example of a material used for a predetermined application, and other materials used for a terminal / connector, a lead frame, a solar cell panel interconnector, etc. By performing the same processing and heat treatment as shown in the patent, an effect of improving the characteristics is expected.
The thickness of the rolled plate is set to 200 μm or more and 1 mm or less, which is suitable as a material for terminals / connectors, lead frames, solar cell interconnectors, and the like.
そして、ＥＢＳＤ法にて測定した全ての結晶粒界長さＬに対する特殊粒界長さＬσの比率（Ｌσ／Ｌ）が６０％以上とされる。
結晶粒界は、二次元断面観察の結果、隣り合う２つの結晶間の配向方位差が１５°以上となっている場合の当該結晶間の境界として定義される。
特殊粒界とは、結晶学的にＣＳＬ理論（Kronberg et.al.:Trans. Met. Soc. AIME, 185, 501 (1949)）に基づき定義されるΣ値で３≦Σ≦２９を有する結晶粒界（対応粒界）であって、当該粒界における固有対応部位格子方位欠陥Ｄｑが Ｄｑ≦１５°/Σ1/2 （D.G.Brandon:Acta.Metallurgica. Vol.14,p1479,1966）を満たす結晶粒界である。
すべての結晶粒界のうち、この特殊粒界の長さ比率が高いと、結晶粒界の整合性が向上して、転位が蓄積しにくくなり、均一な変形特性を示し、過酷な使用環境の下、熱膨張及び熱収縮を繰り返すような場合や、コネクタのように繰り返し弾性変形させられる場合でも、金属疲労がおきにくく、疲労特性を向上させることができる。
The ratio (Lσ / L) of the special grain boundary length Lσ to all the grain boundary lengths L measured by the EBSD method is set to 60% or more.
A crystal grain boundary is defined as a boundary between crystals when the orientation difference between two adjacent crystals is 15 ° or more as a result of two-dimensional cross-sectional observation.
A special grain boundary is a crystal having a crystal value of 3 ≦ Σ ≦ 29 with a Σ value defined crystallographically based on CSL theory (Kronberg et.al.:Trans. Met. Soc. AIME, 185, 501 (1949)). A crystal that is a grain boundary (corresponding grain boundary) and has an inherent corresponding site lattice orientation defect Dq at the grain boundary satisfying Dq ≦ 15 ° / Σ 1/2 (DGBrandon: Acta. Metallurgica. Vol. 14, p1479, 1966) It is a grain boundary.
If the length ratio of this special grain boundary is high among all the grain boundaries, the consistency of the grain boundaries is improved, dislocations are less likely to accumulate, exhibit uniform deformation characteristics, and are used in harsh usage environments. Even when thermal expansion and thermal contraction are repeated or when elastic deformation is repeatedly performed like a connector, metal fatigue hardly occurs and fatigue characteristics can be improved.
次に、このような銅又は銅合金圧延板を製造する方法について説明する。
上述した組成を有する銅合金の原料を溶解して鋳造する溶解・鋳造工程と、この溶解・鋳造工程の後に、鋳塊を熱間圧延して３〜２０ｍｍの厚さの圧延板とする熱間圧延工程と、この熱間圧延工程の後に、総圧延率８９％以上で冷間圧延を行うとともに、冷間圧延材に所定の温度範囲で再結晶熱処理を行う冷間圧延工程とを有しており、その冷間圧延工程においては、粗冷間圧延の後に、歪み除去のための焼鈍処理を行い、その後、低圧下率の仕上げ冷間圧延と仕上げ再結晶熱処理とを行う仕上げ処理を有している。
熱間圧延工程は、特別な条件ではなく、被加工材の銅又は銅合金に応じて通常用いられる適切な条件で行えばよい。
冷間圧延工程は、３〜２０ｍｍの厚さになった熱間圧延板を２００μｍ以上１ｍｍ以下の薄板に加工するものであり、粗冷間圧延の後に、前段で実施した粗冷間加工で導入された歪みを除去する目的で焼鈍を行う。当該焼鈍条件については、被加工材の銅又は銅合金に応じて通常用いられる適切な条件で行えばよい。
Next, a method for producing such a rolled copper or copper alloy sheet will be described.
A melting / casting process for melting and casting the copper alloy raw material having the above-described composition, and a hot-rolled ingot after the melting / casting process to form a rolled plate having a thickness of 3 to 20 mm A rolling process and a cold rolling process for performing cold rolling at a total rolling rate of 89% or more and performing a recrystallization heat treatment on the cold rolled material in a predetermined temperature range after the hot rolling process. In the cold rolling process, after rough cold rolling, annealing treatment for removing strain is performed, and then finishing cold rolling at a low pressure reduction rate and finishing recrystallization heat treatment are performed. ing.
The hot rolling process may be performed under appropriate conditions that are usually used according to the copper or copper alloy of the workpiece, not special conditions.
The cold rolling process is a process in which a hot rolled sheet having a thickness of 3 to 20 mm is processed into a thin sheet having a thickness of 200 μm or more and 1 mm or less, and is introduced by the rough cold working performed in the previous stage after the rough cold rolling. Annealing is performed for the purpose of removing the generated distortion. About the said annealing conditions, what is necessary is just to perform on the suitable conditions normally used according to the copper or copper alloy of a workpiece.
そして、所望の高い特殊粒界を得るために実施する仕上げ処理では、直前の焼鈍処理の後に、圧下率５〜２５％の仕上げ冷間圧延と、温度Ｔａ℃、時間５〜３６００秒の条件での仕上げ再結晶熱処理のサイクルを１回以上繰り返す。
仕上げ冷間圧延時の圧下率が５％未満であれば、この仕上げ冷間圧延時に素材全体に均質な歪みが導入できず、結果としてその後に行う仕上げ再結晶熱処理の過程において特殊粒界の形成が促進されず、また２５％を超えて大きくなると、導入された均質ひずみ量が大き過ぎ、仕上げ冷間圧延後の再結晶熱過程において、特殊粒界の長さ比率を６０％以上に保つ事が難しい。なお、総圧延率は、粗冷間圧延前の板厚に対する仕上げ冷間圧延後の板厚の減少率であり、仕上げ圧延時の圧下率は、１回のパス時の加工前板厚に対する加工後の板厚の減少率である。
And in the finishing process implemented in order to obtain a desired high special grain boundary, after the last annealing process, the finish cold rolling of 5-25% of rolling reduction, temperature Ta degreeC, and time 5-3600 second conditions. The finish recrystallization heat treatment cycle is repeated one or more times.
If the rolling reduction during finish cold rolling is less than 5%, homogeneous strain cannot be introduced into the entire material during this finish cold rolling, resulting in the formation of special grain boundaries in the subsequent process of finish recrystallization heat treatment. Is not promoted, and if it exceeds 25%, the amount of homogeneous strain introduced is too large, and the length ratio of special grain boundaries should be maintained at 60% or more in the recrystallization heat process after finish cold rolling. Is difficult. The total rolling rate is the reduction rate of the plate thickness after finish cold rolling relative to the plate thickness before rough cold rolling, and the rolling reduction rate during finish rolling is the processing for the plate thickness before processing in one pass. This is the rate of reduction of the subsequent plate thickness.
再結晶熱処理については、素材の再結晶温度をＴｓ（℃）としたときに、熱処理温度Ｔａ（℃）が（Ｔｓ−１５０）＜Ｔａ＜（Ｔｓ＋１５０）の範囲で、５〜３６００秒（より好ましくは５〜１８００秒）行う。
熱処理温度Ｔａが（Ｔｓ−１５０）以下で、５秒未満の条件では、再結晶化が十分に起きない。一方、熱処理温度Ｔａを（Ｔｓ＋１５０）より大きくし、３６００秒より長時間の条件とした場合、二次再結晶化による結晶粒の粗大化が起き、その結果、特殊粒界の長さ比率が低下傾向となり６０％以上に保つことが困難となる。
熱処理雰囲気については、不活性雰囲気(窒素、アルゴン)や還元雰囲気(水素)などが酸化抑制の観点から望ましいが、適切な短時間熱処理条件を選べば大気中であっても良い。
Regarding the recrystallization heat treatment, when the recrystallization temperature of the material is Ts (° C.), the heat treatment temperature Ta (° C.) is in the range of (Ts−150) <Ta <(Ts + 150), and 5 to 3600 seconds (more preferably 5 to 1800 seconds).
When the heat treatment temperature Ta is (Ts-150) or less and less than 5 seconds, recrystallization does not occur sufficiently. On the other hand, when the heat treatment temperature Ta is set higher than (Ts + 150) and the condition is longer than 3600 seconds, the coarsening of crystal grains occurs due to secondary recrystallization, resulting in a decrease in the length ratio of special grain boundaries. It becomes a tendency and it becomes difficult to keep 60% or more.
As the heat treatment atmosphere, an inert atmosphere (nitrogen, argon) or a reducing atmosphere (hydrogen) is desirable from the viewpoint of suppressing oxidation, but it may be in the air if an appropriate short-time heat treatment condition is selected.
次に本発明の実施例を比較例とともに説明する。
被加工材の銅又は銅合金として、タフピッチ銅、無酸素銅、高純度無酸素銅、クロム銅、クロムジルコニウム銅の四種類を用いた。それぞれの概略成分組成は表１に示す通りである。表１中「−」は該当成分を添加していないことを示す。また、添加元素以外のＺｎ、Ｓｎ、Ｆｅ、Ｃｏ、Ａｌ、Ａｇ、Ｍｎなどの不純物については、全て０．３ｍａｓｓ％以下であった。
Next, examples of the present invention will be described together with comparative examples.
Four kinds of copper or copper alloy to be processed were used: tough pitch copper, oxygen-free copper, high-purity oxygen-free copper, chromium copper, and chromium zirconium copper. The general composition of each component is as shown in Table 1. In Table 1, “-” indicates that the corresponding component is not added. Further, impurities such as Zn, Sn, Fe, Co, Al, Ag, and Mn other than the additive elements were all 0.3 mass% or less.
この表１に示す成分の各素材に対して適当な条件で熱間圧延して、３〜２０ｍｍの厚さの熱間圧延板を作製した後、表２〜表６に示す各条件で冷間圧延工程を経て、最終厚み５００μｍの圧延板を作製した。表２は素材がタフピッチ銅である例、表３は素材が無酸素銅である例、表４は素材が高純度無酸素銅であり、表５は素材がクロム銅であり、表６は素材がクロムジルコニウム銅である例をそれぞれ示す。
そして、このような冷間圧延工程により得られた薄肉の圧延板のビッカース硬さ、特殊粒界比率、疲労寿命を以下のように測定した。
＜ビッカース硬さ＞
ビッカース硬さは、圧延方向（Ｒ．Ｄ．方向）に沿う縦断面（Ｔ．Ｄ．方向に見た面）に対して、ＪＩＳ（Ｚ２２４４）に規定される方法（測定荷重５００ｇ）により測定した。
Each material of the components shown in Table 1 is hot-rolled under appropriate conditions to produce a hot-rolled sheet having a thickness of 3 to 20 mm, and then cold-treated under the conditions shown in Tables 2 to 6. A rolled plate having a final thickness of 500 μm was produced through a rolling process. Table 2 is an example in which the material is tough pitch copper, Table 3 is an example in which the material is oxygen-free copper, Table 4 is a material in which high purity oxygen-free copper is used, Table 5 is a material in which chromium copper is used, Table 6 is a material in which Examples in which are chromium zirconium copper.
And the Vickers hardness, the special grain boundary ratio, and the fatigue life of the thin rolled plate obtained by such a cold rolling process were measured as follows.
<Vickers hardness>
The Vickers hardness was measured by a method (measurement load 500 g) defined in JIS (Z2244) with respect to a longitudinal section (surface viewed in the TD direction) along the rolling direction (RD direction). .
＜特殊粒界長さ比率＞
各試料について、耐水研磨紙、ダイヤモンド砥粒を用いて機械研磨を行った後、コロイダルシリカ溶液を用いて仕上げ研磨を行った。
そして、ＥＢＳＤ測定装置（ＨＩＴＡＣＨＩ社製 Ｓ４３００−ＳＥＭ，ＥＤＡＸ／ＴＳＬ社製 ＯＩＭ Ｄａｔａ Ｃｏｌｌｅｃｔｉｏｎ）と、解析ソフト（ＥＤＡＸ／ＴＳＬ社製 ＯＩＭ Ｄａｔａ Ａｎａｌｙｓｉｓ ｖｅｒ．５．２）によって、結晶粒界、特殊粒界を特定し、その長さを算出することにより、平均結晶粒径及び特殊粒界長さ比率の解析を行った。
まず、走査型電子顕微鏡を用いて、試料表面の測定範囲内の個々の測定点（ピクセル）に電子線を照射し、電子線を試料表面に２次元で走査させ、後方散乱電子線回折による方位解析により、隣接する測定点間の方位差が１５°以上となる測定点間を結晶粒界とした。
また、測定範囲における結晶粒界の全粒界長さＬを測定し、隣接する結晶粒の界面が特殊粒界を構成する結晶粒界の位置を決定するとともに、特殊粒界の全特殊粒界長さＬσと、上記測定した結晶粒界の全粒界長さＬとの粒界長比率Ｌσ／Ｌを求め、特殊粒界長さ比率とした。
＜疲労寿命＞
板厚０．５ｍｍ、幅１０ｍｍの試料について、日本伸銅協会が定める「銅及び銅合金薄板条の疲労特性試験方法（ＪＣＢＡ Ｔ３０８：２００２）」に基づいて試験した。試験装置には、株式会社鷺宮製作所製せん断疲労試験機ＬＭＶ３０７５を用い、試料に片側２ｍｍの振幅で両振りとし、５００ＭＰａの最大曲げ応力で繰り返し荷重を付加した。試料に亀裂が生じ、最終的に破断に至るまでの繰り返し回数を測定し、疲労寿命とした。
表２〜表５中の疲労特性の増減の欄は、各表（各材料毎）に、試験Ｎｏ．１（比較例）の疲労寿命を基準とし、その疲労寿命に対する増減率を示しており、向上評価の欄は、疲労寿命が２０％以上増加したものを○、それ以外を×として表した。
<Special grain boundary length ratio>
Each sample was mechanically polished using water-resistant abrasive paper and diamond abrasive grains, and then final polished using a colloidal silica solution.
Then, by using an EBSD measuring device (HITACHI S4300-SEM, EDAX / TSL OIM Data Collection) and analysis software (EDAX / TSL OIM Data Analysis ver.5.2), grain boundaries and special grain boundaries. The average grain size and the special grain boundary length ratio were analyzed by specifying the length and calculating the length.
First, using a scanning electron microscope, each measurement point (pixel) within the measurement range of the sample surface is irradiated with an electron beam, the electron beam is scanned two-dimensionally on the sample surface, and the orientation by backscattered electron diffraction From the analysis, a crystal grain boundary was defined between the measurement points where the orientation difference between adjacent measurement points was 15 ° or more.
In addition, the total grain boundary length L of the crystal grain boundary in the measurement range is measured, the position of the crystal grain boundary where the interface between adjacent crystal grains constitutes the special grain boundary is determined, and all the special grain boundaries of the special grain boundary are determined. The grain boundary length ratio Lσ / L between the length Lσ and the total grain boundary length L of the crystal grain boundary measured above was determined and used as the special grain boundary length ratio.
<Fatigue life>
A sample having a plate thickness of 0.5 mm and a width of 10 mm was tested based on the “Test Method for Fatigue Properties of Copper and Copper Alloy Thin Sheet Strips” (JCBA T308: 2002) defined by the Japan Copper and Brass Association. As a test apparatus, a shear fatigue tester LMV3075 manufactured by Kinomiya Seisakusho Co., Ltd. was used, and the sample was swung with an amplitude of 2 mm on one side, and a repeated load was applied with a maximum bending stress of 500 MPa. The number of repetitions until a crack occurred in the sample until it finally broke was measured as the fatigue life.
The column of increase / decrease in fatigue characteristics in Tables 2 to 5 shows the test No. in each table (each material). The rate of increase / decrease with respect to the fatigue life is shown on the basis of the fatigue life of 1 (Comparative Example), and the column for improvement evaluation is represented by ○ when the fatigue life is increased by 20% or more, and × otherwise.
これら表２〜表６に示されるように、冷間圧延の終盤で再結晶熱処理後に、低圧下率での仕上げ圧延及びその後の仕上げ再結晶熱処理を適切に行うことにより、特殊粒界長さ比率が６０％以上と高くなり、疲労寿命が向上することがわかる。 As shown in Tables 2 to 6, after the recrystallization heat treatment at the end of the cold rolling, the finish rolling at a low pressure rate and the subsequent finish recrystallization heat treatment are appropriately performed to obtain a special grain boundary length ratio. It can be seen that becomes as high as 60% or more and the fatigue life is improved.
なお、本発明は上記実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。
例えば、仕上げ冷間圧延と仕上げ再結晶熱処理とを複数回繰り返す場合、毎回同じ条件で繰り返してもよいし、異なる条件で繰り返してもよい。
In addition, this invention is not limited to the said embodiment, A various change can be added in the range which does not deviate from the meaning of this invention.
For example, when finishing cold rolling and finishing recrystallization heat treatment are repeated a plurality of times, they may be repeated under the same conditions each time, or may be repeated under different conditions.
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