JP2013082960A - Titanium-copper, method for production thereof, and wrought copper product and electronic device using the titanium-copper - Google Patents
Titanium-copper, method for production thereof, and wrought copper product and electronic device using the titanium-copper Download PDFInfo
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本発明はチタン銅及びその製造方法に関し、コネクタ、端子、リレ−、スイッチ等の導電性ばね材に好適に用いられるチタン銅及びその製造方法、並びにチタン銅を用いた伸銅品及び電子機器部品に関する。 The present invention relates to titanium copper and a method for manufacturing the same, and relates to titanium copper suitably used for conductive spring materials such as connectors, terminals, relays, switches, and the like, a method for manufacturing the same, and a rolled copper product and an electronic device component using the titanium copper. About.
近年の電子機器の軽薄短小化に伴い、端子、コネクタ等の小型化、薄肉化が進んでいる。このため、電子機器に使用される電子材料用銅合金には、さらなる強度と曲げ加工性の向上が要求されている。この要求に対し、従来のりん青銅や黄銅といった固溶強化型銅合金に替わり、ベリリウム銅やチタン銅といった析出強化型銅合金が使用されるようになり、その需要は増加しつつある。
一般に強度と曲げ加工性は相反する性質であり、チタン銅において高い強度を維持しつつ曲げ加工性を改善することが望まれている。
As electronic devices have become lighter and thinner in recent years, terminals and connectors have become smaller and thinner. For this reason, the copper alloy for electronic materials used for an electronic device is requested | required of the improvement of the further intensity | strength and bending workability. In response to this requirement, precipitation strengthened copper alloys such as beryllium copper and titanium copper have been used instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass, and the demand is increasing.
Generally, strength and bending workability are contradictory properties, and it is desired to improve bending workability while maintaining high strength in titanium copper.
チタン銅の曲げ性を改善する技術として、（２００）面のX線回折強度を高め，（２２０）面のX線回折強度を抑制することが提唱され、その製造方法として、（１）鋳造、（２）熱間圧延（９５０℃から４００℃に温度を下げながら行う）、（３）冷間圧延（加工度５０％以上）、（４）中間焼鈍（４５０〜６００℃、導電率を１．５倍以上にし、硬さを０．８倍以下に調整する）、（５）冷間圧延（加工度７０％以上）、（６）溶体化処理（７００〜９８０℃、結晶粒径５〜２５μm）、（６）冷間圧延（加工度０〜５０％）、（７）時効処理（４００〜６００℃）を順次行う工程が開示されている（特許文献１）。 As a technique for improving the bendability of titanium copper, it has been proposed to increase the X-ray diffraction intensity of the (200) plane and suppress the X-ray diffraction intensity of the (220) plane. (2) Hot rolling (performed while lowering the temperature from 950 ° C to 400 ° C), (3) Cold rolling (working degree of 50% or more), (4) Intermediate annealing (450-600 ° C, conductivity 1. (5) Cold rolling (working degree 70% or more), (6) Solution treatment (700-980 ° C., crystal grain size 5-25 μm) ), (6) cold rolling (working degree 0 to 50%), (7) a process of sequentially performing an aging treatment (400 to 600 ° C.) is disclosed (Patent Document 1).
しかしながら、上記従来技術の場合、曲げ加工性が充分に改善されたとはいえず、さらに溶体化処理の前に中間焼鈍を新たに行うため、製造コストの増加を招くという問題がある。
すなわち、本発明は上記の課題を解決するためになされたものであり、強度と曲げ加工性が共に優れたチタン銅及びその製造方法、並びにチタン銅を用いた伸銅品及び電子機器部品の提供を目的とする。
However, in the case of the above prior art, it cannot be said that the bending workability has been sufficiently improved, and further, since intermediate annealing is newly performed before the solution treatment, there is a problem that the manufacturing cost is increased.
That is, the present invention has been made to solve the above problems, and provides titanium copper excellent in both strength and bending workability, a method for producing the same, and a copper-drawn product and an electronic device component using the titanium copper. With the goal.
本発明者らは種々検討した結果、チタン銅の結晶方位と曲げ性との関係を鋭意研究し、圧延面に対するＸ線回折で測定される（３１１）面の回折強度を適正範囲に調整することにより、曲げ加工性が飛躍的に向上することを見出した。
上記の目的を達成するために、本発明のチタン銅は、１．５〜５．０質量％のＴｉを含有し、残部が銅及び不可避的不純物からなり、圧延面においてＸ線回折を用いて測定した（３１１）面の積分強度（Ｉ（３１１））が、銅粉末のＸ線回折で求めた（３１１）面の積分強度（Ｉ０（３１１））に対し、Ｉ（３１１）／Ｉ０（３１１）≧０．３の関係を満たす。
As a result of various studies, the present inventors have intensively studied the relationship between the crystal orientation of titanium copper and bendability, and adjusted the diffraction intensity of the (311) plane measured by X-ray diffraction with respect to the rolled surface to an appropriate range. As a result, it has been found that the bending workability is dramatically improved.
In order to achieve the above object, the titanium-copper of the present invention contains 1.5 to 5.0% by mass of Ti, the balance is made of copper and inevitable impurities, and X-ray diffraction is used on the rolling surface. The measured integrated intensity (I (311) ) of the (311) plane is I (311) / I 0 with respect to the integrated intensity (I 0 (311) ) of the (311) plane obtained by X-ray diffraction of the copper powder. (311) The relation of ≧ 0.3 is satisfied.
更にＡｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｉ、Ｐ、Ｓｉ及びＺｒの群から選ばれる１種以上を合計０．００５〜１．０質量％含有することが好ましい。 Furthermore, it is preferable to contain 0.005-1.0 mass% of 1 or more types chosen from the group of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si, and Zr in total.
また、本発明のチタン銅は、インゴットを８００〜１０００℃の温度から熱間圧延した後に徐冷し、当該熱間圧延上がりの導電率を１０％ＩＡＣＳ以上に調整して製造されたものである。 In addition, the titanium copper of the present invention is manufactured by gradually cooling an ingot after hot rolling from a temperature of 800 to 1000 ° C., and adjusting the conductivity after the hot rolling to 10% IACS or more. .
本発明のチタン銅の製造方法は、１．５〜５．０質量％のＴｉを含有し、残部が銅及び不可避的不純物からなるインゴットを８００〜１０００℃の温度から熱間圧延した後に徐冷することにより、厚みを５〜２０ｍｍ、導電率を１０％ＩＡＣＳ以上に調整した後、加工度３０〜９９．５％の冷間圧延、７００〜１０００℃で５秒間〜３０分間の溶体化処理、加工度０〜５０％の冷間圧延、３５０〜５５０℃で２時間〜２０時間の時効処理、加工度０〜４０％の及び冷間圧延をこの順で行う。
前記インゴットが更にＡｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｉ、Ｐ、Ｓｉ及びＺｒの群から選ばれる１種以上を合計０．００５〜１．０質量％含有することが好ましい。
The titanium copper production method of the present invention comprises 1.5 to 5.0% by mass of Ti, and the ingot composed of copper and inevitable impurities is hot-rolled after hot rolling from a temperature of 800 to 1000 ° C. By adjusting the thickness to 5 to 20 mm and the conductivity to 10% IACS or more, cold rolling with a workability of 30 to 99.5%, solution treatment at 700 to 1000 ° C. for 5 seconds to 30 minutes, Cold rolling with a working degree of 0 to 50%, aging treatment at 350 to 550 ° C. for 2 to 20 hours, cold working with a working degree of 0 to 40% and cold rolling are performed in this order.
The ingot may further contain 0.005 to 1.0% by mass in total of at least one selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si and Zr. preferable.
本発明の伸銅品は前記チタン銅を用い、本発明の電子機器部品は前記チタン銅を用いたものである。 The copper product of the present invention uses the titanium copper, and the electronic device component of the present invention uses the titanium copper.
本発明によれば、強度と曲げ加工性が共に優れたチタン銅が得られる。 According to the present invention, titanium copper excellent in both strength and bending workability can be obtained.
以下、本発明の実施形態に係るチタン銅について説明する。なお、本発明において％とは、特に断らない限り、質量％を示すものとする。 Hereinafter, titanium copper according to an embodiment of the present invention will be described. In the present invention, “%” means “% by mass” unless otherwise specified.
まず、本発明の技術思想について説明する。チタン銅製品の圧延面における（３１１）面の集積度が一定のレベル以上になると、Ｂａｄ Ｗａｙ方向（曲げ軸が圧延方向に平行）の曲げ加工性が著しく向上する。また、熱間圧延上がりのチタン銅の導電率が高くなると製品圧延面への（３１１）面の集積度が増加し、該導電率が１０％ＩＡＣＳ以上になると（３１１）面発達による曲げ性改善効果が発現する。該導電率を高めるためにはＴｉをできるだけ析出させる必要があり、そのためには熱間圧延終了後の材料を徐冷し、冷却中にＴｉをできるだけ析出させることが有効である。なお、該導電率の上昇に伴い（３１１）面が増加する理由として、析出物の増加が次行程の冷間圧延における結晶の回転に影響すること等が考えられる。
一方、従来のチタン銅の熱間圧延は、後の溶体化処理工程での負荷を下げるために、Ｔｉをできるだけ溶体化させる（Ｃｕ中に固溶させる）条件で行われてきた。Ｔｉを溶体化させるためには、熱間圧延終了後の冷却の際のＴｉ析出を抑制する必要があるので、熱間圧延後の材料は水冷により急冷されてきた。この結果、従来のチタン銅の熱間圧延上がりの導電率は３〜８％ＩＡＣＳ程度であった。
First, the technical idea of the present invention will be described. When the degree of integration of the (311) plane on the rolled surface of the titanium-copper product exceeds a certain level, the bending workability in the Bad Way direction (the bending axis is parallel to the rolling direction) is significantly improved. Further, when the electrical conductivity of titanium copper after hot rolling increases, the degree of integration of the (311) plane on the product rolling surface increases, and when the electrical conductivity exceeds 10% IACS (311), the bendability is improved by the development of the plane. The effect is manifested. In order to increase the electrical conductivity, it is necessary to deposit Ti as much as possible. For that purpose, it is effective to gradually cool the material after the hot rolling and deposit Ti as much as possible during cooling. As the reason why the (311) plane increases with the increase in conductivity, it can be considered that the increase in precipitates affects the rotation of crystals in the cold rolling of the next step.
On the other hand, conventional hot rolling of titanium-copper has been performed under the condition that Ti is solutionized as much as possible (solid solution in Cu) in order to reduce the load in the subsequent solution treatment step. In order to form a solution of Ti, it is necessary to suppress Ti precipitation during cooling after completion of hot rolling, and thus the material after hot rolling has been rapidly cooled by water cooling. As a result, the electrical conductivity after hot rolling of the conventional titanium copper was about 3 to 8% IACS.
次に、本発明のチタン銅の組成及びその他の規定について説明する。
（１）組成
本発明のチタン銅は、１．５〜５．０質量％のＴｉを含有する。チタン銅は、溶体化処理によりＣｕマトリックス中へＴｉを固溶させ、時効処理により微細な析出物を合金中に分散させることにより、強度及び導電率を向上させる。
Ｔｉ濃度が１．５質量％未満になると、析出物の析出が不充分となり所望の強度が得られない。一方、Ｔｉ濃度が５．０質量％を超えると、加工性が劣化し、圧延の際に材料が割れる。より好ましいＴｉ濃度は２．９〜３．５質量％である。
更にＡｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｉ、Ｐ、Ｓｉ及びＺｒの群から選ばれる１種以上を合計０．００１〜１．０質量％含有させることにより、強度（引張強さ）を更に向上させることができる。これらの合計含有量が０．００５質量％未満になると強度上昇の効果は得られ難く、合計含有量が１．０質量％を超えると曲げ加工性が劣化する場合がある。より好ましくは、上記各元素を合計で０．００５〜０．５質量％含有させるとよい。
Next, the composition of the titanium copper of the present invention and other rules will be described.
(1) Composition The titanium-copper of this invention contains 1.5-5.0 mass% Ti. Titanium copper improves strength and electrical conductivity by dissolving Ti in a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment.
If the Ti concentration is less than 1.5% by mass, precipitation of precipitates is insufficient and desired strength cannot be obtained. On the other hand, if the Ti concentration exceeds 5.0% by mass, the workability deteriorates and the material breaks during rolling. A more preferable Ti concentration is 2.9 to 3.5% by mass.
Furthermore, by containing 0.001 to 1.0% by mass in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Si and Zr, the strength ( Tensile strength) can be further improved. When the total content is less than 0.005% by mass, the effect of increasing the strength is difficult to obtain, and when the total content exceeds 1.0% by mass, bending workability may be deteriorated. More preferably, it is good to contain said each element 0.005-0.5 mass% in total.
（２）結晶方位
チタン銅の圧延面に対しＸ線回折を行ったときに得られる（３１１）面のＸ線回折積分強度をＩ（３１１）とし、銅粉末に対し同条件でＸ線回折を行ったときに得られる（３１１）面のＸ線回折積分強度をＩ０（３１１）としたときに、両積分強度の比であるＩ（３１１）／Ｉ０（３１１） が０．３以上、より好ましくは０．４以上になると、曲げ性が向上する。
Ｉ（３１１）／Ｉ０（３１１）の上限値は、曲げ性の点からは特に規制されない。ただし、後述する条件で製造したチタン銅では、Ｉ（３１１）／Ｉ０（３１１）が５．０を超えることは通常はない。
(2) Crystal orientation X-ray diffraction integrated intensity of (311) plane obtained when X-ray diffraction is performed on the rolled surface of titanium copper is I (311), and X-ray diffraction is performed on copper powder under the same conditions. When the X-ray diffraction integrated intensity of the (311) plane obtained when the measurement is performed is I 0 (311) , I (311) / I 0 (311) which is the ratio of both integrated intensities is 0.3 or more, More preferably, when it is 0.4 or more, the bendability is improved.
The upper limit value of I (311) / I 0 (311) is not particularly restricted from the viewpoint of bendability. However, in the titanium copper manufactured on the conditions mentioned later, I (311) / I0 (311) does not usually exceed 5.0.
本発明のチタン銅は、伸銅品又は電子機器部品に好適に適用（加工）することができる。伸銅品としては、例えば板、条及び箔が挙げられる。電子機器部品としては、例えばリードフレーム、コネクタ、ピン、端子、リレー、スイッチ、ソケット等が挙げられる。 The titanium-copper of the present invention can be suitably applied (processed) to a wrought copper product or an electronic device component. Examples of the rolled copper product include plates, strips, and foils. Examples of the electronic device parts include a lead frame, a connector, a pin, a terminal, a relay, a switch, and a socket.
次に、本発明のチタン銅の製造方法について説明する。
本発明のチタン銅は、上記組成を有し残部がＣｕ及び不可避不純物からなるインゴットを８００〜１０００℃の温度から熱間圧延した後に徐冷し、導電率を１０％ＩＡＣＳ以上に調整した後、冷間圧延、溶体化処理、時効処理をこの順で行うことで製造することができる。
Next, the manufacturing method of the titanium copper of this invention is demonstrated.
After the titanium copper of the present invention has the above composition and the remainder comprising Cu and inevitable impurities is hot-rolled from a temperature of 800 to 1000 ° C., the titanium copper is gradually cooled, and the conductivity is adjusted to 10% IACS or more. It can manufacture by performing cold rolling, solution treatment, and aging treatment in this order.
（１）溶解及び鋳造
チタンの酸化損耗を防止するため、溶解及び鋳造は真空中又は不活性ガス雰囲気中で行うことが好ましい。インゴットの厚みは、例えば２０〜３００ｍｍである。
(1) Melting and casting In order to prevent oxidation wear of titanium, melting and casting are preferably performed in a vacuum or in an inert gas atmosphere. The thickness of the ingot is, for example, 20 to 300 mm.
（２）熱間圧延
上記したように、（３１１）面発達による曲げ性改善効果を得るために、熱間圧延上がりの導電率を１０％ＩＡＣＳ以上、好ましくは１２％ＩＡＣＳ以上に調整する。そのために８００〜１０００℃に加熱したインゴットを所定の厚みまで熱間圧延した後に徐冷する。
熱間圧延した後に徐冷する方法としては、大気中に放置すること（空冷）が挙げられる。又、熱間圧延直後の材料を断熱容器に挿入する、バーナーで加熱する、加熱炉（２００〜４００℃程度）に挿入してから炉の加熱を停止して炉冷するなどにより、冷却を積極的に遅らせて析出をより促進することも可能である。すなわち、熱間圧延上がりの導電率が１０％ＩＡＣＳ以上になるような冷却速度で冷却するものは、徐冷に含まれる。ただし、導電率を３０％ＩＡＣＳより上げようとすると、冷却に長時間を要し生産効率が極度に低下するため、導電率の上限値を３０％ＩＡＣＳにすることが好ましい。
一方、熱間圧延直後の材料を水槽中に投入する方法、材料に水を噴射する方法、材料にミストを噴霧する方法等を行うと、熱間圧延上がりの導電率が１０％ＩＡＣＳ以上にならず、最終製品のＩ（３１１）／Ｉ０（３１１）が０．３未満となる。
なお、熱間圧延の厚みを５〜２０ｍｍ程度とすることができる。
(2) Hot rolling As described above, in order to obtain the effect of improving the bendability by (311) plane development, the conductivity after hot rolling is adjusted to 10% IACS or more, preferably 12% IACS or more. For this purpose, an ingot heated to 800 to 1000 ° C. is hot-rolled to a predetermined thickness and then slowly cooled.
Examples of the method of slow cooling after hot rolling include leaving it in the atmosphere (air cooling). In addition, the material immediately after hot rolling is inserted into a heat insulating container, heated by a burner, inserted into a heating furnace (about 200-400 ° C), and then the heating of the furnace is stopped and the furnace is cooled. It is also possible to further accelerate the precipitation by delaying it. That is, what is cooled at a cooling rate such that the electrical conductivity after hot rolling is 10% IACS or higher is included in slow cooling. However, if it is attempted to increase the conductivity from 30% IACS, it takes a long time for cooling and the production efficiency is extremely reduced. Therefore, the upper limit value of the conductivity is preferably set to 30% IACS.
On the other hand, when the method of putting the material immediately after hot rolling into the water tank, the method of spraying water on the material, the method of spraying mist on the material, etc., the conductivity after hot rolling becomes 10% IACS or more. The final product I (311) / I 0 (311) is less than 0.3.
In addition, the thickness of hot rolling can be made into about 5-20 mm.
（３）熱間圧延後の冷間圧延
熱間圧延後の冷間圧延の加工度を３０〜９９．５％とすることが好ましい。溶体化処理で均一な再結晶粒を生成させるためには、その前工程である冷間圧延で歪を導入しておく必要があり、３０％以上の加工度で有効な歪が得られる。一方、加工度が９９．５％を超えると、圧延材のエッジ等に割れが発生し、圧延中の材料が破断することがある。
(3) Cold rolling after hot rolling It is preferable that the degree of cold rolling after hot rolling is 30 to 99.5%. In order to generate uniform recrystallized grains by solution treatment, it is necessary to introduce strain by cold rolling, which is the previous step, and effective strain can be obtained at a workability of 30% or more. On the other hand, if the degree of work exceeds 99.5%, cracks may occur at the edges of the rolled material and the material being rolled may break.
（４）溶体化処理
Ｔｉを充分に固溶させるため、７００〜１０００℃とするのが好ましい。溶体化温度が７００℃未満であると、Ｔｉの固溶が不十分になり時効処理において強度が上昇しない。溶体化温度が１０００℃を超えると、銅合金の融点に近づくため工業的な製造が難しくなる。
溶体化処理時間は、５秒間〜３０分間とするのが好ましい。
(4) Solution treatment In order to sufficiently dissolve Ti, the temperature is preferably set to 700 to 1000 ° C. When the solution temperature is lower than 700 ° C., Ti solid solution becomes insufficient and the strength does not increase in the aging treatment. When the solution temperature exceeds 1000 ° C., industrial production becomes difficult because it approaches the melting point of the copper alloy.
The solution treatment time is preferably 5 seconds to 30 minutes.
（５）時効処理
チタン銅の強度、導電率及び曲げ加工性を向上させるため、時効処理を行う。時効処理の条件は、例えば３５０〜５５０℃で２時間〜２０時間とするとよい。
時効温度が３５０℃未満または時効処理時間が２時間未満になると、Ｔｉの析出が不十分になり強度が上昇しない。時効温度が５５０℃超または時効処理時間が２０時間超になると、Ｔｉの析出が進み過ぎ強度が低下する（過時効）。
時効処理後に、時効時に生成した表面酸化膜を除去するために、表面の酸洗や研磨等を行ってもよい。
(5) Aging treatment An aging treatment is performed in order to improve the strength, conductivity and bending workability of titanium copper. The conditions for the aging treatment may be, for example, 350 to 550 ° C. and 2 to 20 hours.
When the aging temperature is less than 350 ° C. or the aging treatment time is less than 2 hours, the precipitation of Ti is insufficient and the strength does not increase. When the aging temperature exceeds 550 ° C. or the aging treatment time exceeds 20 hours, precipitation of Ti proceeds excessively and the strength decreases (overaging).
After the aging treatment, surface pickling, polishing, or the like may be performed in order to remove the surface oxide film generated during aging.
（６）その他の冷間圧延
製品の強度を高めるために、溶体化処理後で時効処理前に冷間圧延（時効前圧延）を行うことができる。ただし、圧延加工度の増加とともに、Ｉ（３１１）／Ｉ０（３１１）が低下するので、加工度の上限を５０％とする。時効前圧延を行う場合には、高強度化の効果を得るために、圧延加工度を１％以上にすることが好ましい。
同様に、製品の強度を高めるために、時効処理後に冷間圧延（時効後圧延）を行うことができる。ただし、圧延加工度の増加とともに、Ｉ（３１１）／Ｉ０（３１１）が低下するので、加工度の上限を４０％とする。時効後圧延を行う場合には、高強度化の効果を得るために、圧延加工度を１％以上にすることが好ましい。
(6) Other cold rolling Cold rolling (rolling before aging) can be performed after solution treatment and before aging treatment in order to increase the strength of the product. However, since I (311) / I 0 (311) decreases with an increase in the rolling work degree, the upper limit of the work degree is set to 50%. When performing pre-aging rolling, in order to obtain the effect of increasing strength, it is preferable to set the rolling degree to 1% or more.
Similarly, in order to increase the strength of the product, cold rolling (rolling after aging) can be performed after the aging treatment. However, since I (311) / I 0 (311) decreases with an increase in the rolling work degree, the upper limit of the work degree is set to 40%. When rolling after aging, in order to obtain the effect of increasing the strength, it is preferable to set the rolling degree to 1% or more.
（７）歪取り焼鈍
時効後の冷間圧延で低下したばね限界値を改善するため、時効後冷間圧延後に歪取り焼鈍を行ってもよい。歪取り焼鈍の温度は３００〜７００℃、焼鈍時間は５秒〜１０時間とするのが好ましい。
歪取り焼鈍の温度が３００℃未満であるか、又は焼鈍時間が５秒未満になると、ばね限界値が改善されない場合がある。一方、焼鈍時間が１０時間を超えるか、又は歪取り焼鈍の温度が７００℃を超えると、強度が低下する場合がある。
(7) Strain relief annealing In order to improve the spring limit value reduced by cold rolling after aging, strain relief annealing may be performed after cold rolling after aging. The temperature for strain relief annealing is preferably 300 to 700 ° C., and the annealing time is preferably 5 seconds to 10 hours.
If the temperature of the strain relief annealing is less than 300 ° C. or the annealing time is less than 5 seconds, the spring limit value may not be improved. On the other hand, if the annealing time exceeds 10 hours or the temperature of strain relief annealing exceeds 700 ° C., the strength may decrease.
以下に本発明の実施例を比較例と共に示すが、これらの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。
真空溶解炉にて電気銅を溶解し、表１に示す組成が得られるよう合金元素を添加した。この溶湯を鋳鉄製の鋳型に鋳込み、厚さ３０ｍｍ、幅６０ｍｍ、長さ１２０ｍｍのインゴットを製造した。
このインゴットを９５０℃で３時間加熱し、厚さ１０ｍｍまで熱間圧延を行なった。圧延直後の材料は、表１に示す方法で室温まで冷却した。ここで、表１の「空冷」は熱間圧延後の試料を大気中に放置した。「炉冷」は、表１に示す温度に昇温した電気炉に熱間圧延後の試料を挿入した後、炉の通電を切って炉内で冷却した（「３００℃から炉冷」は、３００℃の電気炉に熱間圧延後の試料を挿入した後、炉の通電を切って炉内で冷却したことを示す）。「水冷」は熱間圧延後の試料を水槽中に投入し、「ミスト冷却」は熱間圧延後の試料に水のミストを噴霧して冷却した。
Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
Electrolytic copper was melted in a vacuum melting furnace, and alloying elements were added so that the compositions shown in Table 1 were obtained. This molten metal was cast into a cast iron mold to produce an ingot having a thickness of 30 mm, a width of 60 mm, and a length of 120 mm.
The ingot was heated at 950 ° C. for 3 hours and hot-rolled to a thickness of 10 mm. The material immediately after rolling was cooled to room temperature by the method shown in Table 1. Here, in “air cooling” in Table 1, the sample after hot rolling was left in the atmosphere. In “furnace cooling”, after inserting the hot-rolled sample into an electric furnace heated to the temperature shown in Table 1, the furnace was turned off and cooled in the furnace (“furnace cooling from 300 ° C.” This shows that after inserting the hot-rolled sample into an electric furnace at 300 ° C., the furnace was turned off and cooled in the furnace). In “water cooling”, the sample after hot rolling was put into a water tank, and in “mist cooling”, the sample after hot rolling was cooled by spraying water mist.
次に、表面の酸化スケールを面削した後（研削後の厚み９ｍｍ）、表１に示す加工度で冷間圧延を行った。その後、表１に示す温度で５分間溶体化処理を行った後、試料を水槽に入れ冷却した。
さらに、表１に示す加工度で時効前圧延を行った後、Ａｒ雰囲気中で表１に示す温度で５時間時効処理した。時効処理温度は時効後の引張強さが最大になるように選択した。次いで、表１に示す加工度で時効後圧延した後、表１に示す温度で１０秒間歪取り焼鈍し、試料を大気中に放置し冷却した。最終板厚(製品板厚)は表１に示す通りである。
Next, after chamfering the oxide scale on the surface (thickness after grinding 9 mm), cold rolling was performed at a working degree shown in Table 1. Then, after performing the solution treatment for 5 minutes at the temperature shown in Table 1, the sample was put into a water bath and cooled.
Further, after pre-aging rolling at the workability shown in Table 1, aging treatment was performed for 5 hours at a temperature shown in Table 1 in an Ar atmosphere. The aging treatment temperature was selected so that the tensile strength after aging was maximized. Next, after rolling after aging at the workability shown in Table 1, strain relief annealing was performed at the temperature shown in Table 1 for 10 seconds, and the sample was left in the air to cool. The final thickness (product thickness) is as shown in Table 1.
このようにして得られた各チタン銅試料について、諸特性の評価を行った。
＜熱間圧延後の導電率＞
熱間圧延し冷却した後の試料表面を機械研磨し、スケールを除去するとともに平坦化した。この表面において、フェルスター社製シグマテストＤ２．０６８を用い、周波数６０ｋＨｚの条件で導電率を測定した。
＜溶体化処理後の結晶粒径＞
溶体化処理後の試料の圧延方向と直交する断面を機械研磨により鏡面に仕上げた後、エッチングにより結晶粒界を現出させ、ＪＩＳ Ｈ０５０１の切断法に従い結晶粒径を求めた。
＜Ｘ線回折＞
最終製品の圧延面、及び銅粉末（関東化学株式会社製、銅（粉末），２Ｎ５、＞９９．５％、３２５ｍｅｓｈ）に対し、Ｘ線回折積分強度を測定し、それぞれの積分強度をＩ（３１１）及びＩ０（３１１）とした。Ｘ線回折積装置としては、株式会社リガク製ＲＩＮＴ２５００を使用し、Ｃｕ管球にて、管電圧２５ｋＶ、管電流２０ｍＡで測定を行なった。
Various characteristics of each titanium copper sample thus obtained were evaluated.
<Conductivity after hot rolling>
The sample surface after hot rolling and cooling was mechanically polished to remove scale and flatten. On this surface, conductivity was measured under the condition of a frequency of 60 kHz using Sigma Test D2.068 manufactured by Forster.
<Crystal grain size after solution treatment>
A cross section perpendicular to the rolling direction of the sample after solution treatment was finished to a mirror surface by mechanical polishing, and then a crystal grain boundary was revealed by etching, and the crystal grain size was determined according to the cutting method of JIS H0501.
<X-ray diffraction>
Rolled surface of the final product, and copper powder (manufactured by Kanto Chemical Co., Inc., of copper (powder), 2N5,> 99.5%, 325mesh) to measure the X-ray diffraction integrated intensity, each integrated intensity I ( 311) and I 0 (311) . As an X-ray diffraction product apparatus, RINT2500 manufactured by Rigaku Corporation was used, and measurement was performed with a Cu tube bulb at a tube voltage of 25 kV and a tube current of 20 mA.
＜引張り強さ＞
引張試験機を用いてＪＩＳ Ｚ２２４１に従い、最終製品の圧延方向と平行の引張強さを測定した。
<Tensile strength>
The tensile strength parallel to the rolling direction of the final product was measured according to JIS Z2241 using a tensile tester.
＜曲げ性＞
最終製品の試料の幅を１０ｍｍとし、ＪＩＳ Ｈ ３１３０に従い、種々の曲げ半径（Ｒ）で、Ｂａｄｗａｙ（ＢＷ：曲げ軸が圧延方向と同一方向）のＷ曲げ試験を行った。次に、曲げ断面を機械研磨及びバフ研磨で鏡面に仕上げ、光学顕微鏡にて割れの有無を観察した。そして、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値を求めた。
<Bendability>
The width of the sample of the final product was set to 10 mm, and a W-bend test of Badway (BW: the bending axis was the same as the rolling direction) was performed at various bending radii (R) in accordance with JIS H 3130. Next, the bending section was finished to a mirror surface by mechanical polishing and buffing, and the presence or absence of cracks was observed with an optical microscope. Then, the MBR / t value, which is the ratio of the minimum radius (MBR) at which no cracks occur to the plate thickness (t), was determined.
得られた結果を表１に示す。時効前圧延または時効後圧延を行わなかった場合については加工度の欄に０と記し、歪取り焼鈍を行わなかった場合については温度の欄になしと記している。
表１において、熱間圧延後の冷却方法以外の条件を同一とした発明例及び比較例のグループを２桁目（又は３桁目）の番号を同一としてまとめてある。例えば、発明例１１，１２、及び比較例１１は熱間圧延後の冷却方法以外の条件を同一としたグループである。Ｗ曲げのＭＢＲ／ｔ値には、結晶方位だけでなく、板厚（薄いほど小さくなる）、粗大析出物（少ないほど小さくなる）、結晶粒径（適度な粒径がある）、強度（低いほど小さくなる）等、様々な因子が影響する。各グループ内の実施例は、結晶方位以外の因子が同様になるように調整されたものである。
The obtained results are shown in Table 1. When the pre-aging rolling or post-aging rolling is not performed, 0 is described in the workability column, and when the strain relief annealing is not performed, it is described as none in the temperature column.
In Table 1, groups of invention examples and comparative examples in which conditions other than the cooling method after hot rolling are the same are summarized with the same second digit (or third digit) number. For example, Invention Examples 11 and 12 and Comparative Example 11 are groups in which conditions other than the cooling method after hot rolling are the same. In the MBR / t value of W bending, not only the crystal orientation, but also the plate thickness (smaller the smaller), coarse precipitate (smaller the smaller), crystal grain size (appropriate grain size), strength (low) Various factors, such as small). Examples in each group are adjusted so that factors other than the crystal orientation are the same.
表１から明らかなように、各グループにおいて、熱間圧延後に徐冷して導電率を１０％ＩＡＣＳ以上に調整した各発明例の場合、Ｉ（３１１）／Ｉ０（３１１）が０．３以上となった。
一方、熱間圧延後に水冷又はミスト冷却して導電率が１０％ＩＡＣＳ未満となった各比較例の場合、Ｉ（３１１）／Ｉ０（３１１）が０．３未満となった。同じグループ内で比較すると、各発明例のＭＢＲ／ｔは各比較例のＭＢＲ／ｔより明らかに小さく、曲げ性が著しく向上していることがわかる。
ただし、時効前圧延の加工度が５０％を超えた比較例１０１の場合、熱間圧延後に空冷して導電率を１０％ＩＡＣＳ以上に調整したにも関わらず、Ｉ（３１１）／Ｉ０（３１１）が０．３未満となった。その結果、比較例と同等のＭＢＲ／ｔしか得られず、曲げ性の向上は認められなかった。
As is clear from Table 1, in each case of each invention example where the electrical conductivity was adjusted to 10% IACS or higher by slow cooling after hot rolling in each group, I (311) / I 0 (311) was 0.3. That's it.
On the other hand, I (311) / I 0 (311) was less than 0.3 in the case of each comparative example in which the electrical conductivity was less than 10% IACS after water rolling or mist cooling. When compared within the same group, it can be seen that the MBR / t of each inventive example is clearly smaller than the MBR / t of each comparative example, and the bendability is significantly improved.
However, in the case of Comparative Example 101 in which the workability of pre-aging rolling exceeded 50%, I (311) / I 0 ( ) despite the fact that the electrical conductivity was adjusted to 10% IACS or more by air cooling after hot rolling. 311) was less than 0.3. As a result, only MBR / t equivalent to the comparative example was obtained, and no improvement in bendability was observed.
Claims (7)
Ｉ（３１１）／Ｉ０（３１１）≧０．３の関係を満たすチタン銅。 The integrated intensity (I (311) ) of the (311) plane is 1.5% to 5.0% by mass of Ti, the balance is made of copper and inevitable impurities, and measured using X-ray diffraction on the rolled surface. , With respect to the integrated intensity (I 0 (311) ) of the (311) plane obtained by X-ray diffraction of the copper powder,
Titanium copper satisfying the relationship of I (311) / I 0 (311) ≧ 0.3.
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