JP4497164B2 - Copper alloy conductor and cable using the same - Google Patents
Copper alloy conductor and cable using the same Download PDFInfo
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- JP4497164B2 JP4497164B2 JP2007023674A JP2007023674A JP4497164B2 JP 4497164 B2 JP4497164 B2 JP 4497164B2 JP 2007023674 A JP2007023674 A JP 2007023674A JP 2007023674 A JP2007023674 A JP 2007023674A JP 4497164 B2 JP4497164 B2 JP 4497164B2
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 111
- 239000004020 conductor Substances 0.000 title claims description 92
- 239000013078 crystal Substances 0.000 claims description 68
- 239000000463 material Substances 0.000 claims description 55
- 239000000654 additive Substances 0.000 claims description 33
- 230000000996 additive effect Effects 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 description 35
- 238000005096 rolling process Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 28
- 229910045601 alloy Inorganic materials 0.000 description 26
- 238000005098 hot rolling Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000005266 casting Methods 0.000 description 13
- 238000009749 continuous casting Methods 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 9
- 238000005728 strengthening Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000005482 strain hardening Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 206010052428 Wound Diseases 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 229910017755 Cu-Sn Inorganic materials 0.000 description 3
- 229910017927 Cu—Sn Inorganic materials 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017818 Cu—Mg Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910020944 Sn-Mg Inorganic materials 0.000 description 1
- 229910018956 Sn—In Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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- Non-Insulated Conductors (AREA)
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Description
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銅合金導体（トロリー線）を構成する高導電性、高強度の銅合金材及びそれ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 high-conductivity, high-strength copper alloy material constituting a copper alloy conductor (trolley wire) for a train line that supplies power to a train via a pantograph or the like, and a method for producing a copper alloy conductor using the same It is.
電車線用銅合金導体（トロリー線）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重量％含有させたものが知られており（特許文献１参照）、新幹線、在来線のトロリー線として架線されている。 For the copper alloy conductor for train wires (trolley wire), a hard copper wire with 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% by weight of Sn is known (see Patent Document 1), and is wired as a trolley wire of a Shinkansen or a conventional line. .
近年、電車の高速化が進められており、それに対応すべく、トロリー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トロリー線が求められてきている。 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 trolley wire that can withstand these high tensions has been demanded.
高強度の銅合金導体としては、主に、固溶強化型合金及び析出強化型合金の２つが挙げられる。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。また、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。 As the high-strength copper alloy conductor, there are mainly two types: a solid solution strengthened alloy and a precipitation strengthened alloy. Examples of the solid solution strengthened alloy 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. Further, examples of the precipitation strengthening type alloy include a Cu—Zr alloy, a Cu—Cr alloy, and a Cu—Cr—Zr alloy.
固溶強化型合金は、いずれも酸素含有量が１０重量ｐｐｍ（0.001重量％）以下であり、強度と共に伸び特性に優れていることから、トロリー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。固溶強化型合金を使用した従来のトロリー線の製造方法としては、例えば、Ｓｎを０．４〜０．７重量％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ー線を製造する方法がある（特開平６−２４０４２６号公報参照）。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重量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。 All of the solid solution strengthened alloys have an oxygen content of 10 ppm by weight (0.001% by weight) or less, and are excellent in strength and elongation properties. It can be produced directly from the molten copper alloy by casting and rolling. As a conventional method of manufacturing a trolley wire using a solid solution strengthened alloy, for example, a copper alloy casting material containing 0.4 to 0.7 wt% 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 Japanese Patent Laid-Open No. 6-240426). Another copper alloy that can be continuously cast and rolled is a Cu-O-Sn alloy. This alloy is present inside as a crystallized substance (SnO 2 ) having 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 ppm by weight 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、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、特開平６−２４０４２６号公報記載の製造方法は、Ｓｎの含有量が０．４〜０．７重量％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, the solid solution strengthened type alloy can improve the strength as the content of the solid solution strengthening element is increased. However, the electrical conductivity is drastically decreased with the increase of the content, so that the current capacity is increased. Cannot be used as a train line. For example, in the manufacturing method described in JP-A-6-240426, the Sn content is as high as 0.4 to 0.7% by weight, so that the electrical conductivity is lowered. 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.
また、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。 In addition, although precipitation-strengthened alloys have very high hardness and tensile strength, an excessive load is applied to the rolling roll in continuous casting and rolling because of the high hardness, and production by continuous casting and rolling cannot be performed. 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.
つまり、高強度かつ高導電率の銅合金導体を、生産性に優れた連続鋳造圧延法を用いて製造するには、制約と限界があった。 That is, there are limitations and limitations in producing a copper alloy conductor having high strength and high conductivity using a continuous casting and rolling method with excellent productivity.
以上の事情を考慮して創案された本発明の目的は、高強度、かつ、高導電率の銅合金材、及びそれを用いた銅合金導体の製造方法、並びにその方法により得られた銅合金導体、及びそれを用いたケーブルを提供することにある。 The object of the present invention created in view of the above circumstances is to provide a copper alloy material having high strength and high conductivity, a copper alloy conductor using the same, and a copper alloy obtained by the method. It is to provide a conductor and a cable using the conductor.
上記目的を達成すべく本発明に係る銅合金導体は、酸素を０．００１〜０．１重量％（10〜1000重量ppm）含む銅母材に、Ｓｎを０．１〜０．４重量％、Ｓｎよりも酸素との親和力が大きなＣａ、Ｍｇ、Ｌｉ、Ａｌ、Ｔｉ、Ｓｉ、Ｖ、Ｍｎ、Ｚｎ、Ｉｎ、又はＡｇの中から選択される少なくとも１種の添加元素を０．０１〜０．７重量％、かつ、Ｓｎ及び添加元素を合計０．３〜０．８重量％の割合で含み、残部が銅と不可避的不純物からなる銅合金導体で構成され、結晶組織を構成する結晶粒の平均粒径が１００μｍ以下、かつ、結晶組織のマトリックスに、上記添加元素の内、最も酸素との親和力が大きな元素の酸化物の８０％以上が、平均粒径が１μｍ以下の微小酸化物として分散しており、前記結晶粒内に亜粒界が形成されているものである。 Copper alloy conductor according to the present invention for achieving the above-oxygen 0.001 to 0.1% by weight (10 to 1000 wt ppm) comprises copper base material, the Sn 0.1 to 0.4 wt% , At least one additive element selected from Ca, Mg, Li, Al, Ti, Si, V, Mn, Zn, In, or Ag having a higher affinity for oxygen than Sn is 0.01 to 0 .7 wt%, and, seen contains Sn and the additive element in an amount of total 0.3 to 0.8% by weight, consists of a copper alloy conductor remainder being copper and inevitable impurities, crystal constituting the crystal structure A fine oxide having an average particle size of 100 μm or less and 80% or more of the oxide of the element having the greatest affinity for oxygen among the above additive elements in the matrix of the crystal structure, the average particle size of 1 μm or less And subgrain boundaries are formed in the crystal grains. The
また、Ｓｎ及び添加元素の他に、Ｐ又はＢを０．０１重量％（100重量ppm）以下の割合で含ませてもよい。 Further, in addition to Sn and additive elements, P or B may be contained in a proportion of 0.01% by weight (100 ppm by weight) or less.
Ｓｎ及び添加元素の他に、Ｐ及びＢを合計０．０２重量％（200重量ppm）以下の割合で含ませてもよい。 In addition to Sn and additive elements, P and B may be contained in a total proportion of 0.02% by weight (200 ppm by weight) or less.
また、引張強度が４２０ＭＰａ以上、かつ、導電率が６０％ＩＡＣＳ以上であることが望ましい。Further, it is desirable that the tensile strength is 420 MPa or more and the electrical conductivity is 60% IACS or more.
また、本発明の銅合金導体で構成される単線材又は撚線材の周りに、絶縁層を設けたケーブルとしても使用できる。Moreover, it can be used as a cable in which an insulating layer is provided around a single wire or a stranded wire made of the copper alloy conductor of the present invention.
本発明によれば、高強度、かつ、高導電率の銅合金導体を、良好な生産性で得ることができるという優れた効果を発揮する。 According to the present invention, the copper alloy conductor having high strength and high conductivity can be obtained with good productivity.
以下、本発明の好適一実施の形態を添付図面に基づいて説明する。 DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, a preferred embodiment of the invention will be described with reference to the accompanying drawings.
本発明の好適一実施の形態に係る銅合金導体の製造工程を示すフローチャートを図１に示す。 FIG. 1 shows a flow chart showing a manufacturing process of a copper alloy conductor according to a preferred embodiment of the present invention.
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（伸線）加工工程（Ｆ５）とを、含むものである。
As shown in FIG. 1, the manufacturing method of the copper alloy conductor 18 according to the present embodiment
A melting step (F1) of adding and melting Sn12 and the additive element 13 to the copper base material 11 to form a molten copper alloy 14;
A casting step (F2) of casting the molten copper alloy 14 to form a cast material 15;
A hot rolling step (F3) for forming a rolled material 16 by subjecting the cast material 15 to a multi-stage (multi-stage) hot rolling process;
Cleaning and winding process (F4) for cleaning the rolled material 16 and winding it into a rough wire 17;
This includes a cold (drawing) processing step (F5) in which the rough drawn wire 17 is sent out and the rough drawn wire 17 is cold worked to form a copper alloy conductor 18.
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。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。 The copper alloy conductor 18 is then processed into a wire or strip (plate material) having a desired shape according to the application. 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).
銅合金導体１８の製造方法をより詳細に説明すると、先ず、溶解工程（Ｆ１）において、酸素を０．００１〜０．１重量％（10〜1000重量ppm）含む銅母材１１に、Ｓｎ１２を０．１〜０．４重量％、好ましくは０．２５〜０．３５重量％、Ｓｎよりも酸素との親和力が大きな少なくとも１種の添加元素１３を０．０１〜０．７重量％、好ましくは０．０１〜０．６重量％、かつ、Ｓｎ１２及び添加元素１３を合計０．３〜０．８重量％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。 The manufacturing method of the copper alloy conductor 18 will be described in more detail. First, in the melting step (F1), Sn12 is added to the copper base material 11 containing 0.001 to 0.1 wt% (10 to 1000 ppm by weight) of oxygen. 0.1 to 0.4% by weight, preferably 0.25 to 0.35% by weight, 0.01 to 0.7% by weight, preferably 0.01 to 0.7% by weight of at least one additive element 13 having an affinity for oxygen greater than Sn The copper alloy melt 14 is formed by adding 0.01 to 0.6% by weight of Sn12 and the additive element 13 in a total proportion of 0.3 to 0.8% by weight for melting. 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.
ここで、Ｓｎよりも酸素との親和力が大きな少なくとも１種の添加元素１３は、生成自由エネルギーの観点から、Ｃａ、Ｍｇ、Ｌｉ、Ａｌ、Ｔｉ、Ｓｉ、Ｖ、Ｍｎ、Ｚｎ、Ｉｎ、又はＡｇの中から選択される少なくとも１種の元素又はその化合物が挙げられ、好ましくはＣａ、Ｍｇ、Ａｌ、Ｉｎ、又はＡｇの中から選択される少なくとも１種の元素又はその化合物が挙げられる。 Here, at least one additive element 13 having an affinity for oxygen larger than Sn is Ca, Mg, Li, Al, Ti, Si, V, Mn, Zn, In, or Ag from the viewpoint of free energy of formation. And at least one element selected from the group consisting of Ca, Mg, Al, In, or Ag, or a compound thereof.
Ｓｎ１２及び添加元素１３の総含有量が０．３重量％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重量％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。 If the total content of Sn12 and additive element 13 is less than 0.3% by weight, the strength improvement effect 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 weight, the hardness of the cast material 15 becomes high, and the deformation resistance during the rolling process becomes high, so the load on the rolling roll becomes extremely large, 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０．３〜０．８重量％の範囲で適切に調整することにより、［実施例１］において後述するように、銅合金導体１８の引張強度を４２０ＭＰａ以上に向上させると共に導電率を６０〜９０％ＩＡＣＳの範囲で自在に調整することが可能である。 Therefore, in the present embodiment, by appropriately adjusting the total content of Sn12 and additive element 13 in the range of 0.3 to 0.8% by weight, as described later in [Example 1], a copper alloy It is possible to improve the tensile strength of the conductor 18 to 420 MPa or more and to freely adjust the conductivity in the range of 60 to 90% IACS.
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０．５重量％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０．０１重量％（100重量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重量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, 0.5% by weight or more), Sn12 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 contained at a ratio of 0.01 wt% (100 wt ppm) or less. 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 weight, 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重量％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０．０１重量％（100重量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重量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 weight 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 contained at a ratio of 0.01% by weight (100 ppm by weight) or less. If the B content is less than 2 ppm, the effect of making the crystal grains fine (and hence the strength improvement effect of the copper alloy conductor 18) is not so much observed. If the B content exceeds 100 ppm by weight, 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重量％（200重量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 weight% (200 weight ppm) or less.
次に、鋳造工程（Ｆ２）において、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。 Next, in the casting step (F2), 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 and the crystal grain size of the cast material 15 by these casting treatment and quenching treatment are used when casting is performed at a normal casting temperature. Compared to the case of cooling only to a temperature exceeding [the solidification temperature of the copper alloy melt 14 -15 ° C.], each becomes smaller.
次に、熱間圧延工程（Ｆ３）において、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。 Next, in the hot rolling step (F3), the temperature is 50 to 100 ° C. lower than the normal hot rolling temperature in continuous casting rolling, that is, the temperature of the cast material 15 is 900 ° C. or less, preferably 750 ° C. to 900 ° C. In the adjusted state, the cast material 15 is subjected to hot rolling 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（亜境界；図３（ｂ）参照）が形成される。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 boundary (subboundary; see FIG. 3B) is formed. A sub-grain boundary is a boundary between a plurality of crystals having slightly different orientations in the crystal grains.
次に、洗浄・巻取り工程（Ｆ４）において、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、トロリー線における荒引線１７の線径は、２２〜３０ｍｍとされる。 Next, in the cleaning / winding step (F4), the rolled material 16 is cleaned and wound to form the 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 22 to 30 mm.
最後に、冷間加工工程（Ｆ５）において、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４２０ＭＰａを超える引張強度が得られない。 Finally, in the cold working step (F5), the wound rough drawing wire 17 is sent out, and the rough drawing wire 17 is fed to the rough drawing wire 17 at a temperature of −193 ° C. (liquid nitrogen temperature) to 100 ° C., preferably −193 to 25 ° C. or less. Perform cold working (drawing). 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 420 MPa cannot be obtained.
得られた銅合金導体１８は、その後用途に応じた所望形状、例えば、図２に示すような電車線（トロリー線）２０に形成される。電車線２０は、電車線本体２１の両側部にハンガイヤー取付用のイヤ溝２２ａ，２２ｂが形成される。電車線本体２１の下側の外周面は、電車のパンタグラフが摺動する部位である大弧面２３に、電車線本体２１の上側の外周面は、小弧面２４に形成される。電車線２０の断面積は、例えば、１１０〜１７０ｍｍ2とされる。 The obtained copper alloy conductor 18 is then formed into a desired shape according to the application, for example, a train line (trolley line) 20 as shown in FIG. In the train line 20, ear grooves 22 a and 22 b for attaching hanger ears are formed on both sides of the train line body 21. The lower outer peripheral surface of the train line main body 21 is formed on the large arc surface 23 where the pantograph of the train slides, and the upper outer peripheral surface of the train line main body 21 is formed on the small arc surface 24. The cross-sectional area of the train line 20 is, for example, 110 to 170 mm 2 .
次に、本実施の形態の作用を説明する。 Next, the operation of the present embodiment will be described.
図４に示すように、従来の銅合金導体４０は、結晶組織が粗大、つまり結晶粒４１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４２であり、各結晶粒４１の結晶粒界４３ではなく、結晶組織内にランダムに分散していた。これらの結果、従来の銅合金導体４０は、引張強度があまり十分ではなかった。 As shown in FIG. 4, the conventional copper alloy conductor 40 has a coarse crystal structure, that is, crystal grains 41 are coarse. Further, the oxide such as Sn is a coarse oxide 42 having an average particle size (or length) exceeding 1 μm, and is randomly dispersed not in the crystal grain boundaries 43 of each crystal grain 41 but in the crystal structure. . As a result, the conventional copper alloy conductor 40 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０．１〜０．４重量％、Ｓｎよりも酸素との親和力が大きな少なくとも１種の添加元素１３を０．０１〜０．７重量％、かつ、Ｓｎ１２及び添加元素１３を合計０．３〜０．８重量％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 method for manufacturing the copper alloy conductor 18 according to the present embodiment, the copper base material 11 has 0.1 to 0.4 wt% of Sn12 and at least 1 having a larger affinity with oxygen than Sn. The seed additive element 13 is added in an amount of 0.01 to 0.7% by weight, and Sn 12 and the additive element 13 are added in a total ratio of 0.3 to 0.8% by weight to form a molten copper alloy 14, and the copper Using the molten alloy 14, continuous casting at a low temperature (casting temperature 1100 to 1150 ° C.), low-temperature rolling (final rolling temperature 500 to 600 ° C.), and cooling adjusted to a temperature of 100 ° C. or less so that processing heat does not act The copper alloy conductor 18 is manufactured by performing inter-processing.
これらによって、図３（ａ）に示すように、本実施の形態に係る銅合金導体１８は、従来の銅合金導体４０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３２の平均粒径が、銅合金導体４０の結晶粒４１の平均粒径と比較して小さくなり、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の内、最も酸素との親和力が大きな元素の酸化物の８０％以上が、平均粒径が１μｍ以下の微小酸化物３１として、各結晶粒３２の結晶粒界３３に分散している。さらに、図３（ａ）における領域３Ｂの要部拡大図を図３（ｂ）に示すように、結晶粒３２内には、微小な亜粒界（亜境界）３４が形成されている。 Accordingly, as shown in FIG. 3A, the copper alloy conductor 18 according to the present embodiment has a finer crystal structure than the conventional copper alloy conductor 40, that is, the crystal grains 32 of the copper alloy conductor 18 The average particle size is smaller than the average particle size of the crystal grains 41 of the copper alloy conductor 40, and becomes 100 μm or less. Further, in the matrix of the copper alloy conductor 18, 80% or more of the oxide of the element having the greatest affinity for oxygen among the additive elements 13 is formed as a fine oxide 31 having an average particle diameter of 1 μm or less as each crystal grain. Dispersed in 32 crystal grain boundaries 33. Further, as shown in FIG. 3B, an enlarged view of the main part of the region 3 </ b> B in FIG. 3A, a minute subgrain boundary (subboundary) 34 is formed in the crystal grain 32.
この亜粒界３４と、結晶粒界３３に分散した微小酸化物３１とによって、鋳造材１５が有する熱（顕熱）により、結晶粒３２内に存在する方位が少し異なる結晶３５ａ〜３５ｃや結晶粒界３３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３５ａ〜３５ｃ及び各結晶粒３２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。 Crystals 35a to 35c and crystals having slightly different orientations in the crystal grains 32 due to the heat (sensible heat) of the cast material 15 due to the subgrain boundaries 34 and the minute oxides 31 dispersed in the crystal grain boundaries 33. The movement of the grain boundary 33 is suppressed. As a result, since the growth of the crystals 35a to 35c and the crystal grains 32 during hot rolling is suppressed, the crystal structure of the rolled material 16 becomes fine.
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３２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３１を分散させたことによる分散強化とによるものであり、特開平6-240426号公報などに記載された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４２０ＭＰａ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。 As described above, the strengthening of the copper alloy conductor 18 according to the present embodiment is due to the strength improvement of the copper alloy conductor matrix by making the crystal grains 32 finer and the dispersion strengthening by dispersing the fine oxide 31 in the matrix. Compared with the strengthening by only the solid solution strengthening of Sn described in JP-A-6-240426 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 will be described later in the examples, the copper alloy conductor 18 having a high conductivity of 60% IACS or higher and a high strength (tensile strength) of 420 MPa or higher required for a high tension overhead wire is obtained. be able to.
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）を得ることができる。 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. A high-strength cable (wiring material, power supply material) can 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φが２３ｍｍの銅合金導体（電車線用銅合金荒引線）を３９種類作製した。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。 39 types of copper alloy conductors (copper alloy wire for train wires) having a diameter φ of 23 mm were prepared by changing the kind and amount of additive elements added to the copper base material, the final rolling temperature of hot rolling, 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10，350，1000重量ppm含む各銅母材に、Ｓｎを0.3重量％ずつ、かつ、Ｉｎを0.05，0.1，0.1重量％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)
Each copper base material containing oxygen at 10,350,1000 ppm by weight is made of copper alloy material containing 0.3% by weight of Sn and 0.05,0.1,0.1% by weight of In. Produced. The final rolling temperature was 560 ° C. for all.
（実施例４〜２４）
酸素を350重量ppm含む各銅母材に、Ｓｎを0.3重量％ずつ、かつ、Ｃａ、Ｍｇ、Ｌｉ、Ａｌ、Ｔｉ、Ｓｉ、Ｖ、Ｍｎ、Ｚｎ、Ｉｎ、又はＡｇから選択される少なくとも１種の添加元素を0.05〜0.45重量％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５，６については、Ｐを0.0002，0.0090重量％の割合で更に含み、実施例７，８については、Ｂを0.0015，0.0090重量％の割合で更に含んでいる。
(Examples 4 to 24)
Each copper base material containing 350 ppm by weight of oxygen, at least 0.3% by weight of Sn, and at least one selected from Ca, Mg, Li, Al, Ti, Si, V, Mn, Zn, In, or Ag A copper alloy conductor was prepared using a copper alloy material containing 0.05 to 0.45 wt% of the additive element. The final rolling temperature was 560 ° C. for all. In Examples 5 and 6, P is further included in a proportion of 0.0002, 0.0090% by weight, and in Examples 7 and 8, B is further included in a proportion of 0.0015, 0.0090% by weight.
（実施例２５，２６）
酸素を400，410重量ppm含む各銅母材に、Ｓｎを0.3重量％ずつ、かつ、Ｉｎを0.5重量％ずつ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570，560℃とした。また、実施例２５については、Ｐを0.0038重量％の割合で更に含んでいる。
(Examples 25 and 26)
Copper alloy conductors were produced using copper alloy materials containing 0.3 wt% Sn and 0.5 wt% In in each copper base material containing 400,410 wt ppm of oxygen. The final rolling temperature was 570,560 ° C. Moreover, about Example 25, P is further included in the ratio of 0.0038 weight%.
（比較例１〜５）
酸素を350重量ppm含む各銅母材に、Ｓｎを0.3重量％ずつ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、それぞれ620℃，600℃，580℃，500℃，480℃とした。
(Comparative Examples 1-5)
A copper alloy conductor was prepared using a copper alloy material containing Sn in an amount of 0.3% by weight in each copper base material containing 350 ppm by weight of oxygen. The final rolling temperatures were 620 ° C, 600 ° C, 580 ° C, 500 ° C, and 480 ° C, respectively.
（比較例６〜１２）
酸素を5，10，30，400，800，1000，1200重量ppm含む各銅母材に、Ｓｎを0.3重量％ずつ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。尚、無酸素銅は酸素を含有していないため、無酸素銅を銅母材として用いた銅合金導体は作製しなかった。
(Comparative Examples 6-12)
Copper alloy conductors were prepared using copper alloy materials containing 0.3 wt% of Sn in each copper base material containing 5, 10, 30, 400, 800, 1000, and 1200 ppm by weight of oxygen. The final rolling temperature was 560 ° C. for all. Since oxygen-free copper does not contain oxygen, a copper alloy conductor using oxygen-free copper as a copper base material was not produced.
（比較例１３）
測定できない程の極微量の酸素を含む銅母材（無酸素銅で構成される銅母材）に、Ｓｎを0.3重量％、Ｉｎを0.6重量％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580℃とした。
(Comparative Example 13)
Using a copper base material containing a very small amount of oxygen that cannot be measured (a copper base material composed of oxygen-free copper) containing 0.3% by weight of Sn and 0.6% by weight of In, A copper alloy conductor was prepared. The final rolling temperature was 580 ° C.
実施例１〜２６及び比較例１〜１３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 26 and Comparative Examples 1 to 13.
次に、実施例１〜２６及び比較例１〜１３の銅合金導体を用い、図２に示した断面積が１７０ｍｍ2のトロリー線をそれぞれ作製した。各トロリー線の引張強度（ＭＰａ）、導電性、酸化物の割合、亜粒界の有無、結晶粒サイズ、表面品質、熱間圧延性、及び総合評価を表２に示す。 Next, using the copper alloy conductors of Examples 1 to 26 and Comparative Examples 1 to 13, trolley wires having a cross-sectional area of 170 mm 2 shown in FIG. Table 2 shows the tensile strength (MPa), conductivity, ratio of oxide, presence / absence of subgrain boundaries, crystal grain size, surface quality, hot rollability, and comprehensive evaluation of each trolley wire.
ここで、導電性については、導電率が６０〜９０％ＩＡＣＳのものを○、６０％ＩＡＣＳ未満のものを×とした。 Here, as for the conductivity, those having an electrical conductivity of 60 to 90% IACS were evaluated as ◯, and those having an electrical conductivity less than 60% IACS as ×.
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 ×.
亜粒界の有無については、結晶粒内に亜粒界が観察されるものを○、観察されないものを×とした。 With respect to the presence or absence of subgrain boundaries, the case where subgrain boundaries were observed in the crystal grains was marked with ◯, and the case where subgrain boundaries were not observed was marked with x.
結晶粒サイズについては、比較例１の銅合金導体を用いたトロリー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 1 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○、多いものを×とした。 As for the surface quality, the surface scratches after hot rolling were evaluated as “◯”, and the surface scratches as “×”.
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.
総合評価については、良好なものを○、不良を×とした。 For the comprehensive evaluation, “Good” indicates “good” and “Poor” indicates “poor”.
表２に示すように、実施例１〜２６の各銅合金導体を用いて作製した各トロリー線は、いずれも４２０ＭＰａ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、各トロリー線は、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、結晶粒内には亜粒界が観察され、結晶粒のサイズは０．５未満であった。さらに、各トロリー線は、いずれも表面傷が少なく表面品質は良好であり、熱間圧延性も良好であった。特に、添加元素であるＩｎを０．５重量％と多く含有する実施例２５，２６の場合、５００ＭＰａを超える高引張強度が得られた。以上より、総合評価も良好であった。 As shown in Table 2, each trolley wire produced using each copper alloy conductor of Examples 1 to 26 had a tensile strength of 420 MPa or more and a conductivity of 60% IACS or more. In each trolley wire, the ratio of oxides having an average grain size of 1 μm or less was 80% or more, subgrain boundaries were observed in the crystal grains, and the crystal grain size was less than 0.5. It was. Furthermore, each trolley wire had few surface scratches, good surface quality, and good hot rollability. In particular, in Examples 25 and 26 containing as much as 0.5% by weight of In as an additive element, a high tensile strength exceeding 500 MPa was obtained. From the above, the overall evaluation was also good.
これに対して、比較例１〜５の各銅合金導体を用いて作製した各トロリー線は、銅母材が添加元素を含有していないため、微小酸化物の割合が少なく、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、引張強度は比較例４，５以外は４２０ＭＰａ未満であった。特に、比較例１の場合、最終圧延温度が高すぎるため、圧延時に導入された転位が再配列せず、亜粒界が形成されなかった。よって、引張強度が比較例１〜５の中で最も小さかった。また、比較例５の場合、最終圧延温度が低すぎるため、トロリー線表面に多くの傷が発生してしまい、表面品質が悪かった。以上より、比較例１〜５の場合、総合評価はいずれも不良であった。 On the other hand, each trolley wire produced using each copper alloy conductor of Comparative Examples 1 to 5 has a small proportion of fine oxides and a large crystal because the copper base material does not contain an additive element. Only grains were obtained. Moreover, although electroconductivity was favorable, tensile strength was less than 420 Mpa except comparative examples 4 and 5. In particular, in the case of Comparative Example 1, since the final rolling temperature was too high, the dislocations introduced at the time of rolling did not rearrange and subgrain boundaries were not formed. Therefore, the tensile strength was the smallest among Comparative Examples 1-5. Moreover, in the case of the comparative example 5, since the final rolling temperature was too low, many damage | wounds generate | occur | produced on the trolley wire surface, and surface quality was bad. As mentioned above, in the case of Comparative Examples 1-5, all comprehensive evaluation was unsatisfactory.
また、比較例６〜１２の各銅合金導体を用いて作製した各トロリー線は、酸素含有量及びＳｎ含有量は本発明の範囲内であるものの、銅母材が添加元素を含有していないため、微小酸化物の割合が少なく、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、引張強度は比較例１１以外は４２０ＭＰａ未満であった。特に、比較例１２の場合、酸素含有量が多すぎるため、熱間圧延性が悪かった。以上より、比較例６〜１２の場合、総合評価はいずれも不良であった。 Moreover, although each trolley wire produced using each copper alloy conductor of Comparative Examples 6 to 12 has an oxygen content and a Sn content within the scope of the present invention, the copper base material does not contain an additive element. For this reason, the proportion of fine oxides was small and only large crystal grains were obtained. Moreover, although electroconductivity was favorable, tensile strength was less than 420 MPa except the comparative example 11. In particular, in the case of Comparative Example 12, the hot rolling property was poor because the oxygen content was too high. As mentioned above, in the case of Comparative Examples 6-12, all comprehensive evaluation was unsatisfactory.
さらに、比較例１３の銅合金導体を用いて作製したトロリー線は、Ｓｎ含有量及び最終圧延温度は本発明の範囲内であるものの、銅母材に含有させる添加元素の割合が多すぎるため高硬度であり、熱間圧延ロールに対する負荷が著しく大きくなってしまい、圧延材の製造ができなかった。 Furthermore, although the trolley wire produced using the copper alloy conductor of Comparative Example 13 has a Sn content and a final rolling temperature within the scope of the present invention, the ratio of the additive element contained in the copper base material is too high. This is the hardness, and the load on the hot rolling roll is remarkably increased, making it impossible to produce a rolled material.
［実施例１］における実施例２及び比較例１の各銅合金導体について、それぞれ組織観察を行った。組織観察は、光学顕微鏡、ＳＥＭ（走査型電子顕微鏡）、ＴＥＭ（透過型電子顕微鏡）を用いて行った。 The structure of each copper alloy conductor of Example 2 and Comparative Example 1 in [Example 1] was observed. Tissue observation was performed using an optical microscope, SEM (scanning electron microscope), and TEM (transmission electron microscope).
図５（ａ）に示す実施例２の銅合金導体における結晶組織５１の結晶粒サイズは、図５（ｂ）に示す比較例１の銅合金導体における結晶組織５２の結晶粒サイズと比較して微細であり、結晶組織５２の結晶粒の平均粒径を１とした時、結晶組織５１の結晶粒サイズは約０．５未満となっていた。また、図６（ｂ）に示す比較例１の銅合金導体における酸化物（ＳｎＯ2）は、平均粒径（又は長さ）が１μｍ以上の粗大酸化物６２が多く、中には１０μｍを超える粗大酸化物６３が生成していた。これに対して、図６（ａ）に示す実施例２の銅合金導体における酸化物（Ｉｎ2Ｏ3）は、平均粒径が１μｍ以下の微小酸化物６１がその殆どを占めていた。 The crystal grain size of the crystal structure 51 in the copper alloy conductor of Example 2 shown in FIG. 5 (a) is compared with the crystal grain size of the crystal structure 52 in the copper alloy conductor of Comparative Example 1 shown in FIG. 5 (b). When the average grain size of the crystal grain of the crystal structure 52 is 1, the crystal grain size of the crystal structure 51 is less than about 0.5. In addition, the oxide (SnO 2 ) in the copper alloy conductor of Comparative Example 1 shown in FIG. 6B has a large amount of coarse oxide 62 having an average particle size (or length) of 1 μm or more, and more than 10 μm. Coarse oxide 63 was produced. In contrast, most of the oxide (In 2 O 3 ) in the copper alloy conductor of Example 2 shown in FIG. 6A was fine oxide 61 having an average particle diameter of 1 μm or less.
ここで、実施例２の銅合金導体を更に詳しく観察すると、図７（ａ），図７（ｂ）に示すように、エッチングにより結晶粒界７１の表面が露出している箇所が認められ、そこに、微小酸化物（Ｉｎ2Ｏ3）７２が優先的に晶出している様子が観察された。また、図７（ｃ），図７（ｄ）に示すように、結晶組織内の結晶粒界７３，７４にも微小酸化物７６，７７が観察された。図７（ｃ）において認められる平均粒径が１μｍを超える酸化物７５は、Ｓｎ酸化物（ＳｎＯ2）であるが、その分散量は、微小酸化物７２，７６，７７の分散量と比較して著しく少ない。つまり、結晶組織内に分散する酸化物の大部分は、Ｓｎよりも酸素との親和力が大きなＩｎの酸化物（微小酸化物７２，７６，７７）であり、結晶粒界７１，７３，７４に分散していた。 Here, when the copper alloy conductor of Example 2 was observed in more detail, as shown in FIGS. 7 (a) and 7 (b), a portion where the surface of the crystal grain boundary 71 was exposed by etching was recognized, There, it was observed that the fine oxide (In 2 O 3 ) 72 was preferentially crystallized. Further, as shown in FIGS. 7C and 7D, fine oxides 76 and 77 were also observed at the crystal grain boundaries 73 and 74 in the crystal structure. The oxide 75 having an average particle diameter exceeding 1 μm recognized in FIG. 7C is Sn oxide (SnO 2 ), but its dispersion amount is compared with the dispersion amount of the fine oxides 72, 76, 77. Remarkably few. That is, most of the oxide dispersed in the crystal structure is an oxide of In (small oxides 72, 76, 77) having a larger affinity for oxygen than Sn. It was dispersed.
また、図８（ｂ）に示す比較例１の銅合金導体における結晶組織においては、結晶粒界８７のみが観察され、各結晶粒８４〜８６の粒内には亜粒界は観察されなかった。これに対して、図８（ａ）に示す実施例２の銅合金導体における結晶組織においては、各結晶粒８１，８２の粒内に、亜粒界８３が観察された。この亜粒界８３が存在することにより、実施例２と比較例１とでは硬さに約２倍の差が生じており、実施例２の方が高硬度であった。つまり、亜粒界８３による結晶粒の高硬度化が、銅合金導体の引張強度向上に寄与していると考えられる。 Moreover, in the crystal structure in the copper alloy conductor of Comparative Example 1 shown in FIG. 8B, only the crystal grain boundaries 87 were observed, and no subgrain boundaries were observed in the grains of the respective crystal grains 84 to 86. . On the other hand, in the crystal structure of the copper alloy conductor of Example 2 shown in FIG. 8A, subgrain boundaries 83 were observed in the grains 81 and 82. Due to the presence of the sub-grain boundaries 83, the difference between the hardness of Example 2 and Comparative Example 1 was about twice, and the hardness of Example 2 was higher. That is, it is considered that the increase in hardness of the crystal grains due to the subgrain boundaries 83 contributes to the improvement of the tensile strength of the copper alloy 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
１８ 銅合金導体
Ｆ１ 溶解工程
Ｆ２ 鋳造工程
Ｆ３ 熱間圧延工程
11 Copper base material 12 Sn
13 Additive element 14 Copper alloy molten metal 15 Cast material 16 Rolled material 18 Copper alloy conductor F1 Melting process F2 Casting process F3 Hot rolling process
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| CN105371000A (en) * | 2015-12-25 | 2016-03-02 | 苏州露宇电子科技有限公司 | Nuclear magnetic resonance scanner |
| ITUA20162023A1 (en) * | 2016-03-25 | 2017-09-25 | Giulio Properzi | PROCEDURE FOR TRANSFORMING VERGELLA OF NON-FERROUS METALS AND THEIR ALLOYS IN HIGH-STRETCH WIRE AND IN THE RICOTTO STATE. |
| CN105895188A (en) * | 2016-05-18 | 2016-08-24 | 安徽华通电缆集团有限公司 | High-performance cable core |
| CN109136636A (en) * | 2018-09-29 | 2019-01-04 | 上海工程技术大学 | A kind of copper alloy wire and preparation method thereof |
| CN111521287B (en) * | 2020-05-11 | 2022-03-15 | 国网北京市电力公司 | Method, device, storage medium and processor for calculating temperature of metal sleeve of cable |
| CN114480894B (en) * | 2022-01-21 | 2023-01-06 | 中铁建电气化局集团康远新材料有限公司 | Industrial production process of high-strength copper-tin alloy contact wire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61136648A (en) * | 1984-12-06 | 1986-06-24 | Kobe Steel Ltd | Corrosion resistant copper alloy pipe |
| JP2005029884A (en) * | 2003-06-20 | 2005-02-03 | Sumitomo Electric Ind Ltd | Wear resistant trolley wire, and its production method |
| JP3948451B2 (en) * | 2003-10-24 | 2007-07-25 | 日立電線株式会社 | Copper alloy material, method for producing copper alloy conductor using the same, copper alloy conductor obtained by the method, and cable using the same |
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| JPH0616523B2 (en) * | 1987-07-07 | 1994-03-02 | 日本鉱業株式会社 | Film carrier and manufacturing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61136648A (en) * | 1984-12-06 | 1986-06-24 | Kobe Steel Ltd | Corrosion resistant copper alloy pipe |
| JP2005029884A (en) * | 2003-06-20 | 2005-02-03 | Sumitomo Electric Ind Ltd | Wear resistant trolley wire, and its production method |
| JP3948451B2 (en) * | 2003-10-24 | 2007-07-25 | 日立電線株式会社 | Copper alloy material, method for producing copper alloy conductor using the same, copper alloy conductor obtained by the method, and cable using the same |
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