JP5147040B2 - Method for producing copper alloy conductor - Google Patents
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本発明は、パンタグラフ等を介して電車に給電を行う電車線用トロリ線、あるいは機器用ケーブル導体等に用いられる、高導電性、高強度の銅合金材を用いた銅合金導体の製造方法に関するものである。 The present invention relates to a method for producing a copper alloy conductor using a high conductivity, high strength copper alloy material, which is used for a trolley wire for a train line that supplies power to a train via a pantograph or the like, or a cable conductor for equipment. Is.
電車線用トロリ線、あるいは機器用ケーブル導体には、導電率が高い硬銅線又は耐摩耗性、耐熱性を有する銅合金材（銅合金線）が使用されている。銅合金材としては、銅母材にＳｎを０．２５〜０．３５質量％含有させたものが知られており（特許文献１参照）、新幹線、在来線のトロリ線や機器用ケーブル導体として使用されている。 For the trolley wire for train lines or the cable conductor for equipment, a hard copper wire having high conductivity or a copper alloy material (copper alloy wire) having wear resistance and heat resistance is used. As a copper alloy material, a copper base material containing 0.25 to 0.35 mass % of Sn is known (see Patent Document 1), and a trolley wire of a Shinkansen or a conventional line or a cable conductor for equipment. It is used as
近年、電車の高速化が進められており、それに対応すべく、トロリ線の架線張力を高めることが求められており、電車線の架線張力は、１．５ｔから２．０ｔ以上に変更される傾向にある。そこで、これらの高張力に耐えうる高強度の銅合金導体が求められてきている。高強度の銅合金導体は、主に、（１）固溶強化型合金、（２）析出強化型合金の２つに分類される。 In recent years, the speed of trains has been increased, and in order to cope with this, it is required to increase the overhead wire tension of the trolley wire, and the overhead wire tension of the train wire is changed from 1.5 t to 2.0 t or more. There is a tendency. Therefore, a high-strength copper alloy conductor that can withstand these high tensions has been demanded. High-strength copper alloy conductors are mainly classified into two types: (1) solid solution strengthened alloys and (2) precipitation strengthened alloys.
（１）の固溶強化型合金としては、Ｃｕ−Ａｇ合金（高濃度銀）、Ｃｕ−Ｓｎ合金、Ｃｕ−Ｓｎ−Ｉｎ合金、Ｃｕ−Ｍｇ合金、Ｃｕ−Ｓｎ−Ｍｇ合金などが挙げられる。
固溶強化型合金は、いずれも酸素含有量が１０質量ｐｐｍ（０．００１質量％）以下であり、強度と共に伸び特性に優れていることから、トロリ線の母材となる銅合金荒引線を、連続鋳造圧延により、銅合金溶湯から直接製造することができる。
Examples of the solid solution strengthening type alloy (1) include a Cu—Ag alloy (high concentration silver), a Cu—Sn alloy, a Cu—Sn—In alloy, a Cu—Mg alloy, and a Cu—Sn—Mg alloy.
All of the solid solution strengthened alloys have an oxygen content of 10 ppm by mass (0.001% by mass ) or less and are excellent in elongation characteristics as well as strength. It can be directly produced from a molten copper alloy by continuous casting and rolling.
固溶強化型合金を使用した従来のトロリ線の製造方法としては、例えば、Ｓｎを０．４〜０．７質量％含有した銅合金の鋳造材を、７００℃以上の温度で熱間圧延して圧延材とする。この圧延材を再度５００℃以下の温度で加熱し、仕上げ圧延して荒引線とし、この荒引線を伸線加工してトロリ線を製造する方法がある（特許文献２参照）。 As a conventional method for producing a trolley wire using a solid solution strengthened alloy, for example, a copper alloy casting material containing 0.4 to 0.7 mass % of Sn is hot-rolled at a temperature of 700 ° C. or higher. And rolled material. There is a method in which this rolled material is heated again at a temperature of 500 ° C. or less, finish-rolled to form a rough drawn wire, and this rough drawn wire is drawn to produce a trolley wire (see Patent Document 2).
また、他の連続鋳造圧延可能な銅合金として、Ｃｕ−Ｏ−Ｓｎ合金がある。この合金は、その内部にＳｎが２〜３μｍ以上の晶出物（ＳｎＯ2）として存在しており、強度と伸び特性は、酸素含有量が１０質量ｐｐｍ以下のＣｕ−Ｓｎ合金と同等であることが知られている。この合金も、析出強化作用や分散強化作用よりも、固溶強化作用の方が強い合金である。 Moreover, there exists a Cu-O-Sn alloy as another copper alloy which can be continuously cast-rolled. This alloy is present inside as a crystallized substance (SnO 2 ) with Sn of 2 to 3 μm or more, and the strength and elongation characteristics are equivalent to those of a Cu—Sn alloy having an oxygen content of 10 mass ppm or less. It is known. This alloy is also an alloy having stronger solid solution strengthening action than precipitation strengthening action and dispersion strengthening action.
ところで、これらの固溶強化型合金は、固溶強化元素の含有量を多くすればするほど強度向上を図ることができるが、それに伴って極端に導電率が低下してしまうので電流容量を大きくすることができず、電車線として適さなくなってしまう。例えば、特許文献２記載の製造方法は、Ｓｎの含有量が０．４〜０．７質量％と多いので、導電率が低くなってしまう。よって、現状のＣｕ−Ｓｎ系合金では、高張力架線として必要な強度を有し、かつ、良好な導電率を有する銅合金導体を製造することは困難である。ここで、高強度かつ高導電率の電車線を得るためには、Ｓｎと共にさらに別の元素を添加することが考えられる。この場合、仕上げ圧延（最終圧延）を５００℃以下の温度で行うと、圧延時に圧延材の割れが多くなるので、荒引線の外観品質が極端に低下してしまい、延いては電車線の強度が極端に低下するという問題があった。 By the way, these solid solution strengthened alloys can be improved in strength as the content of the solid solution strengthening element is increased. However, since the conductivity is extremely lowered with this, the current capacity is increased. I can't do it and it's not suitable as a train line. For example, the manufacturing method described in Patent Document 2 has a high Sn content of 0.4 to 0.7% by mass , resulting in low electrical conductivity. Therefore, it is difficult to produce a copper alloy conductor having the necessary strength as a high-strength overhead wire and good conductivity with the current Cu—Sn alloy. Here, in order to obtain a high-strength and high-conductivity train line, it is conceivable to add another element together with Sn. In this case, if finish rolling (final rolling) is performed at a temperature of 500 ° C. or less, cracks of the rolled material increase at the time of rolling, so that the appearance quality of the rough drawn wire is extremely deteriorated, and thus the strength of the train line. There has been a problem that is extremely lowered.
他方、（２）の析出強化型合金としては、Ｃｕ−Ｚｒ合金、Ｃｕ−Ｃｒ合金、Ｃｕ−Ｃｒ−Ｚｒ合金などが挙げられる。しかし、これらの析出強化型合金は、硬度及び引張強度は非常に高いものの、硬度が高い分連続鋳造圧延における圧延ロールに過大な負荷がかかってしまい、連続鋳造圧延による製造ができない。このため、押出しなどの方法によるバッチ式でしか製造できない。加えて、析出強化型合金は、中間工程において析出強化物を析出させるための熱処理が必要である。よって、析出強化型合金は、連続鋳造圧延で製造可能な固溶強化型合金と比較して、生産性が低く、製造コストが高くなるという問題があった。 On the other hand, examples of the precipitation strengthening type alloy (2) include a Cu—Zr alloy, a Cu—Cr alloy, and a Cu—Cr—Zr alloy. However, although these precipitation strengthened alloys have very high hardness and tensile strength, an excessive load is applied to the rolling roll in continuous casting and rolling due to the high hardness, and it is impossible to manufacture by continuous casting and rolling. For this reason, it can manufacture only by the batch type by methods, such as extrusion. In addition, the precipitation-strengthened alloy requires heat treatment for precipitating the precipitation strengthened material in an intermediate step. Therefore, the precipitation-strengthened alloy has a problem that the productivity is low and the manufacturing cost is high as compared with a solid solution strengthened alloy that can be manufactured by continuous casting and rolling.
さらに、これらの問題を解決するために、Ｓｎ添加合金に別な元素を添加するとともに、製造方法に工夫を施して高強度化と高導電率化を両立するものが知られている（特許文献３参照）。
最近の電車線路はさらなる高速化が進められており、それに対応すべく、トロリ線の架線張力を高めることが求められている。さらに、電車通過密度の高い線路ではトロリ線の大電流容量化の要求も一段と強い。 Recent train tracks have been further increased in speed, and in order to cope with this, it is required to increase the tension of the trolley wire. In addition, the demand for higher current capacity of the trolley line is even stronger on lines with high train passage density.
また、機器用ケーブル導体においても、使用環境の面から耐屈曲性の高い、つまり高強度の導体が求められており、さらに、軽量化、小型化の要求から導体の高導電性化が必要とされている。 Also, cable conductors for equipment are required to have high bending resistance, that is, high-strength conductors from the viewpoint of the use environment, and further, it is necessary to increase the conductivity of the conductors in order to reduce weight and size. Has been.
しかしながら、特許文献３記載の銅合金導体においても、このような最近の電車線用トロリ線、あるいは機器用ケーブル導体として要求される特性を十分にバランス良く満足しているとは言い難く、更なる高強度化と高導電率化を両立した銅合金導体を、生産性に優れた連続鋳造圧延法を用いて製造することが要望されている。 However, even in the copper alloy conductor described in Patent Document 3, it is difficult to say that the characteristics required for such a recent trolley wire for train lines or cable conductors for equipment are sufficiently satisfied, and further. There is a demand for producing a copper alloy conductor that achieves both high strength and high electrical conductivity by using a continuous casting and rolling method with excellent productivity.
従って、本発明の目的は、近年の電車線用トロリ線、あるいは機器用ケーブル導体等に要求される高強度及び高導電性を両立した銅合金材を用いた銅合金導体の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a copper alloy conductor using a copper alloy material having both high strength and high conductivity required for a recent trolley wire for train lines or cable conductors for equipment. There is.
上記目的を達成すべく本発明に係る銅合金導体の製造方法は、酸素を０．００１〜０．１質量％（１０〜１０００質量ｐｐｍ）含む銅母材に第１の添加元素としてＳｎを０．４（０．４を除く）〜０．７質量％、及び第２の添加元素としてＩｎを０．０１〜０．４質量％、かつ前記第１の添加元素と前記第２の添加元素の合計を０．４１（０．４１を除く）〜０．８質量％の割合として添加して溶解を行い、残部が銅と不可避的不純物からなる銅合金溶湯を形成する溶解工程と、前記銅合金溶湯を用いて１１００〜１１５０℃の温度で鋳造を行うと共に、鋳造材の温度を銅合金溶湯の融点より少なくとも１５℃以上低い温度まで急速冷却して鋳造材とする鋳造工程と、前記鋳造材の温度を９００℃以下に調整した状態で、前記鋳造材に、最終圧延温度が５００〜６００℃となるように調整した複数段の熱間圧延加工を行って、圧延材を形成する熱間圧延工程と前記圧延材に、−１９３〜１００℃の温度で、加工度５０％以上の冷間加工を行って、銅合金導体を形成する冷間圧延工程を備えることを特徴とする。 In order to achieve the above object, the method for producing a copper alloy conductor according to the present invention includes a copper base material containing 0.001 to 0.1 mass % (10 to 1000 ppm by mass ) of oxygen with Sn as the first additive element. .4 (excluding 0.4) 0.7 wt%, and 0.01 to 0.4 wt% in as second additive element, and said first additive element of the second additional element A total of 0.41 (excluding 0.41) to 0.8% by mass is added and dissolved, and a melting step for forming a copper alloy melt comprising the copper and inevitable impurities as the balance, and the copper alloy A casting process using the molten metal at a temperature of 1100 to 1150 ° C., and rapidly cooling the cast material to a temperature at least 15 ° C. lower than the melting point of the copper alloy molten metal to obtain a cast material; In a state where the temperature is adjusted to 900 ° C. or lower, What hot rolling line of a plurality of stages of extension temperature was adjusted to 500 to 600 ° C., the rolled material and hot rolling step of forming a rolled material, at a temperature of -193～100 ° C., processed A cold rolling step of forming a copper alloy conductor by performing cold working at a degree of 50% or more is provided.
更に、前記銅合金導体を用いて電車線用トロリ線としたり、前記銅合金導体で構成される単線材又は撚線材の周りに絶縁層を設けてケーブルとしたりすることができる。 Furthermore, the copper alloy conductor can be used as a trolley wire for a train line, or a cable can be provided by providing an insulating layer around a single wire or a stranded wire made of the copper alloy conductor.
本発明によれば、近年の電車線用トロリ線、あるいは機器用ケーブル導体等に要求される高強度及び高導電性を両立した銅合金材を用いた銅合金導体を良好な生産性で製造可能な製造方法を提供することができる。 According to the present invention, a copper alloy conductor using a copper alloy material having both high strength and high conductivity required for a trolley wire for a train line or a cable conductor for equipment in recent years can be manufactured with good productivity. A simple manufacturing method can be provided.
以下、本発明の好適な実施形態について添付図面に基づいて説明する。 DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.
図１に、本発明の好適な一実施形態に係る銅合金導体の製造工程を説明するフローチャートを示す。 In FIG. 1, the flowchart explaining the manufacturing process of the copper alloy conductor which concerns on suitable one Embodiment of this invention is shown.
図１に示すように、本実施の形態に係る銅合金導体１８の製造方法は、銅母材１１にＳｎ１２及び添加元素１３を添加して溶解し、銅合金溶湯１４を形成する溶解工程（Ｆ１）と、その銅合金溶湯１４を鋳造して鋳造材１５を形成する鋳造工程（Ｆ２）と、その鋳造材１５に複数段（多段）の熱間圧延加工を施して圧延材１６を形成する熱間圧延工程（Ｆ３）と、その圧延材１６を洗浄し、巻取って荒引線１７とする洗浄・巻取り工程（Ｆ４）と、その巻取った荒引線１７を送り出し、その荒引線１７に冷間加工を施して銅合金導体１８を形成する冷間圧延工程（Ｆ５）と、を含むものである。以下、各工程について詳細に説明する。 As shown in FIG. 1, the manufacturing method of the copper alloy conductor 18 which concerns on this Embodiment adds and melt | dissolves Sn12 and the additional element 13 in the copper base material 11, and melt | dissolves (F1) which forms the copper alloy molten metal 14 ), A casting step (F2) for casting the molten copper alloy 14 to form a cast material 15, and heat for forming a rolled material 16 by subjecting the cast material 15 to multiple stages (multi-stage) hot rolling. The intermediate rolling step (F3), the rolling material 16 is washed, wound and wound into a rough drawn wire 17 (F4), and the wound rough drawn wire 17 is sent out, and the rough drawn wire 17 is cooled. And a cold rolling step (F5) for forming the copper alloy conductor 18 by performing a hot work. Hereinafter, each step will be described in detail.
（溶解工程：Ｆ１）
先ず、酸素を０．００１〜０．１質量％（１０〜１０００質量ｐｐｍ）含む銅母材１１に、Ｓｎ１２を０．４（０．４は含まない）〜０．７質量％、好ましくは０．５〜０．６質量％、添加元素１３としてＩｎを０．０１〜０．４質量％、好ましくは０．０１〜０．２質量％、かつＳｎ１２及び添加元素１３を合計０．４１（０．４１を除く）〜０．８質量％、好ましくは０．５１〜０．７質量％の割合で添加して溶解を行うことで、銅合金溶湯１４が形成される。添加元素１３は、Ｓｎ１２よりも酸素との親和力が大きな元素であるため、Ｓｎよりも優先的に酸化され、最終的に得られる銅合金導体１８の結晶組織に生成、分散している酸化物は、その大半（８０％以上）が添加元素の酸化物となり、Ｓｎ酸化物は殆ど生成、分散しない。よって、添加したＳｎ１２の大部分は、銅と合金化され、銅合金導体１８のマトリックスを形成する。
(Dissolution process: F1)
First, the copper base material 11 containing 0.001 to 0.1% by mass (10 to 1000 ppm by mass ) of oxygen is added to Sn12 in the range of 0.4 (not including 0.4) to 0.7% by mass , preferably 0. .5～0.6 mass%, 0.01 to 0.4 mass% of in as an additive element 13, preferably 0.01 to 0.2 wt%, and the sum of Sn12 and additive elements 13 0.41 (0 The molten copper alloy 14 is formed by adding and melting at a ratio of 0.8 to 0.8% by mass , preferably 0.51 to 0.7% by mass . Since the additive element 13 is an element having an affinity for oxygen larger than that of Sn12, the oxide that is preferentially oxidized over Sn and formed and dispersed in the crystal structure of the finally obtained copper alloy conductor 18 is Most of them (80% or more) become oxides of additive elements, and Sn oxides are hardly generated or dispersed. Therefore, most of the added Sn 12 is alloyed with copper to form a matrix of the copper alloy conductor 18.
Ｓｎ１２及び添加元素１３の総含有量が０．４１質量％未満では、本実施の形態に係る製造方法を適用しても、銅合金導体１８の強度向上効果は認められない。また、総含有量が０．８質量％を超えると、鋳造材１５の硬度が高くなり、圧延加工時の変形抵抗が高くなるので、圧延ロールに対する負荷が極端に大きくなってしまい、製品化が困難となってしまう。 When the total content of Sn12 and additive element 13 is less than 0.41% by mass, the effect of improving the strength of the copper alloy conductor 18 is not recognized even when the manufacturing method according to the present embodiment is applied. Further, if the total content exceeds 0.8% by mass, the hardness of the cast material 15 is increased, and the deformation resistance during the rolling process is increased, so that the load on the rolling roll is extremely increased, and the product is commercialized. It becomes difficult.
したがって、本実施の形態では、Ｓｎ１２及び添加元素１３の総含有量を
０．４１〜０．８質量％の範囲で適切に調整することにより、［実施例］において後述するように、銅合金導体１８の引張強度を４５０ＭＰａ以上に向上させると共に導電率を６０％ＩＡＣＳ以上に調整することが可能である。
Accordingly, in the present embodiment, by appropriately adjusting the total content of Sn12 and additive element 13 in the range of 0.41 to 0.8 mass %, as described later in [Example], a copper alloy conductor It is possible to improve the tensile strength of 18 to 450 MPa or higher and to adjust the conductivity to 60% IACS or higher.
Ｓｎ１２及び添加元素１３の総含有量が多くなると、熱間圧延工程（Ｆ３）における熱間圧延加工時に、圧延材１６の表面傷が多くなる傾向にある。よって、Ｓｎ１２及び添加元素１３の総含有量が多い場合（例えば０．６質量％以上の場合）には、圧延材１６の表面傷を減少させるべく、銅母材１１に、Ｓｎ１２及び添加元素１３と共に、さらにＰを添加してもよい。Ｐは好ましくは２ｐｐｍ以上０．０１質量％（１００質量ｐｐｍ）以下の割合で含有させる。Ｐの含有量が２ｐｐｍ未満だと、銅線表面傷を低減させる効果はあまり認められず、Ｐの含有量が１００質量ｐｐｍを超えると、銅合金導体１８の導電率が低
下してしまう。
When the total content of Sn12 and additive element 13 increases, the surface scratches of the rolled material 16 tend to increase during hot rolling in the hot rolling step (F3). Therefore, when the total content of Sn12 and additive element 13 is large (for example, 0.6% by mass or more), Sn 12 and additive element 13 are added to copper base material 11 in order to reduce surface scratches on rolled material 16. In addition, P may be further added. P is preferably contained in a proportion of 2 ppm to 0.01 mass % (100 mass ppm). If the P content is less than 2 ppm, the effect of reducing the surface scratches on the copper wire is not recognized so much. If the P content exceeds 100 ppm by mass , the conductivity of the copper alloy conductor 18 is lowered.
また、Ｓｎ１２及び添加元素１３の総含有量が多くなると、鋳造工程（Ｆ２）後における鋳造材１５の結晶粒がやや大きくなる傾向（延いては銅合金導体１８の強度がやや低下する傾向）にある。よって、Ｓｎ１２及び添加元素１３の総含有量が多い場合（例えば０．５質量％以上の場合）には、鋳造材１５の結晶粒を微細にするべく、銅母材１１に、Ｓｎ１２及び添加元素１３と共に、さらにＢを添加してもよい。Ｂは好ましくは２ｐｐｍ以上０．０１質量％（１００質量ｐｐｍ）以下の割合で含有させる。Ｂの含有量が２ｐｐｍ未満だと、結晶粒を微細にする効果（延いては銅合金導体１８の強度向上効果）はあまり認められず、Ｂの含有量が１００質量ｐｐｍを超えると、銅合金導体１８の導電率が低下してしまう。 Moreover, when the total content of Sn12 and the additive element 13 increases, the crystal grains of the cast material 15 after the casting step (F2) tend to become slightly larger (and thus the strength of the copper alloy conductor 18 tends to decrease slightly). is there. Therefore, when the total content of Sn12 and additive element 13 is large (for example, 0.5% by mass or more), Sn12 and additive element are added to the copper base material 11 in order to make the crystal grains of the cast material 15 fine. In addition to 13, B may be added. B is preferably contained in a proportion of 2 ppm to 0.01 mass % (100 mass ppm). If the content of B is less than 2 ppm, the effect of making the crystal grains fine (and hence the effect of improving the strength of the copper alloy conductor 18) is not so much observed. If the content of B exceeds 100 mass ppm, the copper alloy The electrical conductivity of the conductor 18 will fall.
さらに、Ｐ及びＢの両方を、合計０．０２質量％（２００質量ｐｐｍ）以下の割合で含ませてもよい。 Furthermore, you may contain both P and B in the ratio of a total of 0.02 mass % (200 mass ppm) or less.
（鋳造工程：Ｆ２）
次に、前工程で得られた銅合金溶湯１４は、ＳＣＲ方式の連続鋳造圧延に供される。具体的には、ＳＣＲ連続鋳造の通常の鋳造温度 （１１２０〜１２００℃）よりも低い温度（１１００〜１１５０℃）で鋳造を行うと共に、鋳型（銅鋳型）を強制水冷し、銅合金溶湯１４の凝固温度より少なくとも１５℃以上低い温度まで、鋳造材１５が急速冷却される。
(Casting process: F2)
Next, the molten copper alloy 14 obtained in the previous step is subjected to SCR continuous casting and rolling. Specifically, casting is performed at a temperature (1100 to 1150 ° C.) lower than the normal casting temperature (1120 to 1200 ° C.) of SCR continuous casting, and the mold (copper mold) is forcibly water-cooled, The cast material 15 is rapidly cooled to a temperature that is at least 15 ° C. lower than the solidification temperature.
これらの鋳造処理及び急冷処理によって鋳造材１５中に晶出（又は析出）する酸化物のサイズ、及び鋳造材１５の結晶粒サイズが、通常の鋳造温度で鋳造を行う場合又は鋳造材１５を［銅合金溶湯１４の凝固温度−１５℃］を超える温度までしか冷却しない場合と比較して、それぞれ小さくなる。 The size of the oxide crystallized (or precipitated) in the cast material 15 by the casting process and the quenching process, and the crystal grain size of the cast material 15 are determined when the casting material 15 is cast at a normal casting temperature or [ Compared with the case where it cools only to the temperature exceeding the solidification temperature of the copper alloy molten metal -15 ° C.], each becomes smaller.
（熱間圧延工程：Ｆ３）
次に、連続鋳造圧延における通常の熱間圧延温度よりも５０〜１００℃低い温度、すなわち鋳造材１５の温度を９００℃以下、好ましくは７５０℃〜９００℃に調整した状態で、鋳造材１５に、熱間圧延が多段に施される。最終圧延時において、５００〜６００℃の圧延温度で熱間圧延加工を施し、圧延材１６が形成される。最終圧延温度が、５００℃未満だと、圧延加工時に表面傷が多く発生してしまい、表面品質の低下を招き、また、６００℃を超えると、結晶組織が従来と同レベルの粗大組織となってしまう。
(Hot rolling process: F3)
Next, in a state where the temperature of the casting material 15 is 50 to 100 ° C. lower than the normal hot rolling temperature in continuous casting rolling, that is, the temperature of the casting material 15 is adjusted to 900 ° C. or less, preferably 750 ° C. to 900 ° C. The hot rolling is performed in multiple stages. At the time of final rolling, hot rolling is performed at a rolling temperature of 500 to 600 ° C., and the rolled material 16 is formed. If the final rolling temperature is less than 500 ° C., many surface scratches occur during the rolling process, resulting in deterioration of the surface quality, and if it exceeds 600 ° C., the crystal structure becomes a coarse structure of the same level as before. End up.
この熱間圧延により、前工程で晶出（又は析出）した比較的小サイズの酸化物が分断され、酸化物のサイズが更に小さくなる。また、本実施の形態に係る製造方法における熱間圧延は、通常の熱間圧延よりも低温で行うものであるため、圧延時に導入された転位が再配列し、結晶粒内に微小な亜粒界が形成される。なお、亜粒界は、結晶粒内に存在する方位が少し異なる複数の結晶間の境界である。 By this hot rolling, a relatively small size oxide crystallized (or precipitated) in the previous step is divided, and the size of the oxide is further reduced. In addition, since the hot rolling in the manufacturing method according to the present embodiment is performed at a lower temperature than normal hot rolling, the dislocations introduced during rolling are rearranged, and small subgrains are formed in the crystal grains. A field is formed. The subgrain boundary is a boundary between a plurality of crystals having slightly different orientations existing in the crystal grains.
（洗浄・巻取り工程：Ｆ４）
次に、圧延材１６を洗浄し、巻取りを行い、荒引線１７とされる。巻取った荒引線１７の線径は、例えば、８〜４０ｍｍ、好ましくは３０ｍｍ以下とされる。例えば、トロリ線における荒引線１７の線径は、２０〜３０ｍｍとされる。
(Washing and winding process: F4)
Next, the rolled material 16 is washed and wound to be a rough drawn wire 17. The wire diameter of the wound rough drawing wire 17 is, for example, 8 to 40 mm, preferably 30 mm or less. For example, the wire diameter of the rough drawn wire 17 in the trolley wire is 20 to 30 mm.
（冷間圧延工程：Ｆ５）
最後に、巻取った荒引線１７を送り出し、その荒引線１７に、−１９３℃（液体窒素温度）〜１００℃、好ましくは−１９３〜２５℃以下の温度で冷間加工（伸線加工）を行う。これによって、銅合金導体１８が形成される。ここで、連続伸線時の加工熱が、銅合金導体１８に及ぼす影響（強度低下など）を少なくするため、引抜きダイスなどの冷間加工装置の冷却を行い、線材温度が１００℃以下、好ましくは２５℃以下となるように調整を行う。また、銅合金導体１８の強度を向上させるためには、熱間圧延加工における加工度を高めて圧延材１６、つまり荒引線１７の強度を十分に向上させておくことが必要である他に、冷間加工における加工度を５０％以上とすることが必要である。ここで、加工度が５０％未満だと４５０ＭＰａを超える引張強度が得られない。
(Cold rolling process: F5)
Finally, the drawn rough wire 17 is sent out, and cold working (drawing) is performed on the rough wire 17 at a temperature of −193 ° C. (liquid nitrogen temperature) to 100 ° C., preferably −193 to 25 ° C. or less. Do. Thereby, the copper alloy conductor 18 is formed. Here, in order to reduce the influence (strength reduction, etc.) on the copper alloy conductor 18 due to the processing heat at the time of continuous wire drawing, a cold working apparatus such as a drawing die is cooled, and the wire temperature is preferably 100 ° C. or less. Is adjusted to 25 ° C. or lower. Moreover, in order to improve the strength of the copper alloy conductor 18, it is necessary to increase the workability in the hot rolling process and sufficiently improve the strength of the rolled material 16, that is, the rough drawn wire 17, It is necessary to set the degree of processing in cold working to 50% or more. Here, if the degree of work is less than 50%, a tensile strength exceeding 450 MPa cannot be obtained.
銅合金導体１８は、その後、用途に応じた所望形状の線材、条材（板材）などに加工される。例えば、電車線用トロリ線では、断面積を１１０〜１７０ｍｍ2とされる。 Thereafter, the copper alloy conductor 18 is processed into a wire, strip (plate), or the like having a desired shape according to the application. For example, a trolley wire for a train line has a cross-sectional area of 110 to 170 mm 2 .
以上、説明した各工程において、溶解工程（Ｆ１）から洗浄・巻取り工程（Ｆ４）までは、既存又は慣用の連続鋳造圧延設備（ＳＣＲ連続鋳造機）を適用することができる。また、冷間加工工程（Ｆ５）は、既存又は慣用の冷間加工装置を適用することができる。 As described above, in each of the steps described above, existing or conventional continuous casting and rolling equipment (SCR continuous casting machine) can be applied from the melting step (F1) to the cleaning / winding step (F4). In addition, an existing or conventional cold working apparatus can be applied to the cold working step (F5).
（本実施形態の作用）
従来の銅合金導体は、結晶組織が粗大であった。またＳｎなどの酸化物は、平均粒径（又は長さ）が１μｍを超える粗大酸化物であり、これらの結果、従来の銅合金導体は、引張強度があまり十分ではなかった。
(Operation of this embodiment)
Conventional copper alloy conductors have a coarse crystal structure. Further, the oxide such as Sn is a coarse oxide having an average particle size (or length) exceeding 1 μm, and as a result, the conventional copper alloy conductor has not been sufficiently high in tensile strength.
これに対して、本実施の形態に係る銅合金導体１８の製造方法においては、銅母材１１に、Ｓｎ１２を０．４（０．４は含まない）〜０．７質量％、Ｉｎからなる添加元素１３を０．０１〜０．４質量％かつ、Ｓｎ１２及び添加元素１３を合計０．４１（０．４１を除く）〜０．８質量％の割合で添加して銅合金溶湯１４を形成し、その銅合金溶湯１４を用い、低温で連続鋳造（鋳造温度が１１００〜１１５０℃）、低温圧延加工（最終圧延温度が５００〜６００℃）、及び加工熱が作用しないように１００℃以下に温度調節した冷間加工を行い、銅合金導体１８を製造している。 On the other hand, in the manufacturing method of the copper alloy conductor 18 according to the present embodiment, the copper base material 11 is made of Sn12 from 0.4 (not including 0.4) to 0.7 mass % and In. Additive element 13 is added in an amount of 0.01 to 0.4 mass %, and Sn12 and additive element 13 are added in a ratio of 0.41 (excluding 0.41) to 0.8 mass % to form molten copper alloy 14. Then, using the molten copper alloy 14, continuous casting at a low temperature (casting temperature is 1100 to 1150 ° C.), low-temperature rolling (final rolling temperature is 500 to 600 ° C.), and 100 ° C. or less so that processing heat does not act. The cold-working which adjusted the temperature is performed and the copper alloy conductor 18 is manufactured.
これらによって本実施の形態に係る銅合金導体１８は、従来の銅合金導体と比較して結晶組織が微細、つまり銅合金導体１８の結晶粒の平均粒径が小さくなり、１００μｍ以下となる。また、銅合金導体１８のマトリックスには、添加元素１３の酸化物の８０％以上が、平均粒径が１μｍ以下の微小酸化物として、各結晶粒の結晶粒界に分散する。さらに、結晶粒内には、微小な亜粒界（亜境界）が形成される。この亜粒界と、結晶粒界に分散した微小酸化物とによって、鋳造材１５が有する熱（顕熱）により、結晶粒内に存在する方位が少し異なる結晶や結晶粒界が移動するのが抑制される。その結果、熱間圧延時における各結晶及び各結晶粒の成長が抑制されるため、圧延材１６の結晶組織が微細となる。 As a result, the copper alloy conductor 18 according to the present embodiment has a finer crystal structure than the conventional copper alloy conductor, that is, the average grain size of the crystal grains of the copper alloy conductor 18 is reduced to 100 μm or less. In the matrix of the copper alloy conductor 18, 80% or more of the oxide of the additive element 13 is dispersed as fine oxide having an average particle diameter of 1 μm or less at the crystal grain boundaries of each crystal grain. Furthermore, minute subgrain boundaries (subboundaries) are formed in the crystal grains. Due to the sub-grain boundaries and the minute oxides dispersed in the crystal grain boundaries, the crystals and grain boundaries that have slightly different orientations in the crystal grains move due to the heat (sensible heat) of the cast material 15. It is suppressed. As a result, since the growth of each crystal and each crystal grain during hot rolling is suppressed, the crystal structure of the rolled material 16 becomes fine.
（本実施形態の効果）
以上より、本実施の形態に係る銅合金導体１８の強化は、結晶粒の微細化による銅合金導体マトリックスの強度向上と、マトリックスに微小酸化物を分散させたことによる分散強化とによるものであり、特許文献２等に記載されたＳｎの固溶強化だけによる強化と比較して、導電率低下の割合も低く抑えることができる。よって、本実施の形態に係る製造方法によれば、導電率の大幅な低下を招くことなく、高い引張強度を有する銅合金導体１８を得ることができる。つまり後述の［実施例］で述べるように、６０％ＩＡＣＳ以上の高い導電率を有し、かつ、高張力架線で必要とされる４５０ＭＰａ以上の高い強度（引張
強度）を有する銅合金導体１８を得ることができる。
(Effect of this embodiment)
As described above, the strengthening of the copper alloy conductor 18 according to the present embodiment is due to the improvement in strength of the copper alloy conductor matrix by refining crystal grains and the dispersion strengthening by dispersing fine oxides in the matrix. Compared with the strengthening only by solid solution strengthening of Sn described in Patent Document 2 and the like, the rate of decrease in conductivity can be suppressed to a low level. Therefore, according to the manufacturing method according to the present embodiment, the copper alloy conductor 18 having a high tensile strength can be obtained without causing a significant decrease in conductivity. That is, as described in [Example] described later, the copper alloy conductor 18 having a high conductivity of 60% IACS or more and a high strength (tensile strength) of 450 MPa or more required for a high-tensile overhead wire. Can be obtained.
また、本実施の形態に係る製造方法は、既存あるいは慣用の連続鋳造圧延設備や冷間加工装置を使用することができるので、新規の設備投資を必要とせず、高導電率、高強度の銅合金導体１８を低コストで製造することができる。 In addition, since the manufacturing method according to the present embodiment can use existing or conventional continuous casting and rolling equipment and cold working equipment, it does not require new equipment investment, and has high conductivity and high strength copper. The alloy conductor 18 can be manufactured at low cost.
また、本実施の形態に係る製造方法により得られた銅合金導体１８を用いて、単線材又は撚線材を形成し、その単線材又は撚線材の周りに、絶縁層を設けることで、高導電率、高強度のケーブル（配線材、給電材）を得ることもできる。 Further, by using the copper alloy conductor 18 obtained by the manufacturing method according to the present embodiment, a single wire material or a stranded wire material is formed, and an insulating layer is provided around the single wire material or the stranded wire material. High-strength cables (wiring materials, power supply materials) can also be obtained.
以上、本発明は、上述した実施の形態に限定されるものではなく、他にも種々のものが想定されることは言うまでもない。 As described above, the present invention is not limited to the above-described embodiment, and it goes without saying that various other things are assumed.
次に、本発明について、実施例に基づいて説明するが、本発明はこれらの実施例に限定されるものではない。 Next, although this invention is demonstrated based on an Example, this invention is not limited to these Examples.
銅母材に添加する添加元素の種類及び量、熱間圧延加工の最終圧延温度などを変え、直径が２３ｍｍの銅合金導体（電車線用銅合金荒引線）を作製した。銅合金導体は、本発明に係る銅合金導体の製造方法を用いて製造した。 A copper alloy conductor (copper alloy wire for train wire) having a diameter of 23 mm was prepared by changing the kind and amount of the additive element added to the copper base material, the final rolling temperature of the hot rolling process, and the like. The copper alloy conductor was manufactured using the method for manufacturing a copper alloy conductor according to the present invention.
（実施例１〜３）
酸素を１０質量ｐｐｍ含む各銅母材に、Ｓｎを０．５質量％、Ｉｎをそれぞれ０．１、０．２、０．３質量％の割合で含有させた銅合金材を用い、銅合金導体を作製した。最終圧延温度はいずれも５６０℃とした。
(Examples 1-3)
Oxygen to each copper base material containing 10 mass ppm, 0.5 wt% of Sn, a copper alloy material which contains In at a rate of respectively 0.1, 0.2, 0.3 mass%, a copper alloy A conductor was produced. The final rolling temperature was 560 ° C. for all.
（実施例４〜６）
酸素を３５０質量ｐｐｍ含む各銅母材を使用した以外は、実施例１〜３同様に銅合金導体を作製した。
(Examples 4 to 6)
A copper alloy conductor was produced in the same manner as in Examples 1 to 3, except that each copper base material containing 350 mass ppm of oxygen was used.
（実施例７〜９）
酸素を５００質量ｐｐｍ含む各銅母材を使用した以外は、実施例１〜３同様に銅合金導体を作製した。
(Examples 7 to 9)
A copper alloy conductor was produced in the same manner as in Examples 1 to 3, except that each copper base material containing 500 mass ppm of oxygen was used.
（実施例１０、１１）
酸素を３５０質量ｐｐｍ含む各銅母材にＳｎを０．５質量％、Ｉｎをそれぞれ０．３質量％の割合で含有させた銅合金材を用い、銅合金導体を作製した。最終圧延温度はいずれも５６０℃とした。また、実施例１０については、Ｐを０．００５０質量％の割合で更に含め、実施例１１については、Ｂを０．００５０質量％の割合で更に含めた。
(Examples 10 and 11)
Oxygen 350 mass ppm 0.5 wt% of Sn on each of copper base material containing, a copper alloy material which contains In at a rate of respectively 0.3 wt%, to prepare a copper alloy conductor. The final rolling temperature was 560 ° C. for all. Moreover, about Example 10, P was further included in the ratio of 0.0050 mass %, and about Example 11, B was further included in the ratio of 0.0050 mass %.
（比較例１〜３）
酸素を３５０質量ｐｐｍ含む各銅母材に、Ｓｎを０．２質量％ずつの割合で含有させた以外は、実施例４〜６と同様に銅合金導体を作製した。
(Comparative Examples 1-3)
Copper alloy conductors were produced in the same manner as in Examples 4 to 6 except that each copper base material containing 350 mass ppm of oxygen contained Sn in a proportion of 0.2 mass %.
（比較例４〜６）
最終圧延温度を６５０℃とした以外は、実施例４〜６と同様に銅合金導体を作製した。
（比較例７〜９）
最終圧延温度を４５０℃とした以外は、実施例４〜６と同様に銅合金導体を作製した。
(Comparative Examples 4-6)
Copper alloy conductors were produced in the same manner as in Examples 4 to 6 except that the final rolling temperature was 650 ° C.
(Comparative Examples 7-9)
Copper alloy conductors were produced in the same manner as in Examples 4 to 6 except that the final rolling temperature was 450 ° C.
実施例１〜１１及び比較例１〜６の銅合金導体の製造条件（酸素含有量、添加元素の種類及び含有量、最終圧延温度）を表１に示す。 Table 1 shows the production conditions (oxygen content, type and content of additive element, final rolling temperature) of the copper alloy conductors of Examples 1 to 11 and Comparative Examples 1 to 6.
次に、実施例１〜１１及び比較例１〜６の銅合金導体を用い、断面積が１３０ｍｍ2のトロリ線をそれぞれ作製した。各トロリ線の引張強度（ＭＰａ）、導電率（％ＩＡＣＳ）、酸化物の割合、結晶粒サイズ、表面品質、熱間圧延性を表２に示す。 Next, using the copper alloy conductors of Examples 1 to 11 and Comparative Examples 1 to 6, trolley wires having a cross-sectional area of 130 mm 2 were prepared. Table 2 shows the tensile strength (MPa), electrical conductivity (% IACS), oxide ratio, crystal grain size, surface quality, and hot rollability of each trolley wire.
酸化物の割合については、平均粒径が１μｍ以下の酸化物の割合が８０％以上のものを○、８０％未満のものを×とした。 Regarding the ratio of oxides, the ratio of oxides having an average particle diameter of 1 μm or less is 80% or more, and the case of less than 80% is ×.
結晶粒サイズについては、比較例４の銅合金導体を用いたトロリ線における結晶粒の平均粒径を１とした時、結晶粒のサイズが０．５未満のものを○、０．５〜１のものを×とした。 As for the crystal grain size, when the average grain size of the crystal grains in the trolley wire using the copper alloy conductor of Comparative Example 4 is 1, the crystal grain size is less than 0.5, and 0.5-1 Was marked with x.
表面品質については、熱間圧延後の表面傷が、少ないものを○、やや多いものを△、多いものを×とした。 As for the surface quality, the surface scratches after hot rolling were evaluated as ◯ when the surface scratches were small, Δ when the surface scratches were slightly, and × when the surface scratches were large.
熱間圧延性については、熱間圧延性が良好なものを○、悪いものを×とした。 Regarding the hot rollability, the case where the hot rollability was good was evaluated as ◯, and the case where the hot rollability was poor as x.
表２に示すように、実施例１〜１１の各銅合金導体を用いて作製した各トロリ線は、いずれも４５０ＭＰａ以上の引張強度及び６０％ＩＡＣＳ以上の導電率を有していた。また、各トロリ線は、いずれも平均粒径が１μｍ以下の酸化物の割合は８０％以上であり、結晶粒のサイズは０．５未満であった。さらに、各トロリ線は、いずれも表面品質は良好であり、熱間圧延性も良好であった。 As shown in Table 2, each trolley wire produced using each copper alloy conductor of Examples 1 to 11 had a tensile strength of 450 MPa or more and a conductivity of 60% IACS or more. In each trolley wire, the ratio of the oxide having an average particle diameter of 1 μm or less was 80% or more, and the crystal grain size was less than 0.5. Furthermore, each trolley wire had good surface quality and good hot rollability.
これに対して、比較例１〜３の各銅合金導体を用いて作製した各トロリ線は、微小酸化物の割合、結晶粒径は良好なものの、Ｓｎ添加量が少ないため強度が小さくなった。比較例４〜６の各銅合金導体を用いて作製した各トロリ線は、微小酸化物の割合は少なく、かつ、大きな結晶粒しか得られなかった。また、導電性は良好であるものの、引張強度は実施例よりも小さい値であった。
さらに、比較例７〜９の各銅合金導体は、表面傷が多いとともに熱間圧延性が著しく悪く導体の製造が困難であった。
On the other hand, although each trolley wire produced using the copper alloy conductors of Comparative Examples 1 to 3 had a good ratio of fine oxides and a crystal grain size, the strength was small because the Sn addition amount was small. . Each trolley wire produced using the copper alloy conductors of Comparative Examples 4 to 6 had a small proportion of fine oxides and only large crystal grains. Moreover, although electroconductivity was favorable, tensile strength was a value smaller than an Example.
Further, each of the copper alloy conductors of Comparative Examples 7 to 9 had many surface flaws and remarkably poor hot rollability, making it difficult to produce the conductor.
１１ 銅母材
１２ Ｓｎ
１３ 添加元素
１４ 銅合金溶湯
１５ 鋳造材
１６ 圧延材
１７ 荒引き線
１８ 銅合金導体
11 Copper base material 12 Sn
13 Additive element 14 Copper alloy molten metal 15 Cast material 16 Rolled material 17 Rough drawing wire 18 Copper alloy conductor
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