JPH04224662A - Production of copper material having high residual resistance ratio - Google Patents
Production of copper material having high residual resistance ratioInfo
- Publication number
- JPH04224662A JPH04224662A JP41432990A JP41432990A JPH04224662A JP H04224662 A JPH04224662 A JP H04224662A JP 41432990 A JP41432990 A JP 41432990A JP 41432990 A JP41432990 A JP 41432990A JP H04224662 A JPH04224662 A JP H04224662A
- Authority
- JP
- Japan
- Prior art keywords
- copper material
- rrr
- purity
- resistance ratio
- residual resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Conductive Materials (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高残留抵抗比銅材の製
造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper material with a high residual resistance ratio.
【０００２】0002
【従来の技術】金属系超電導線の安定化材として、通常
は９９．９９％純度の無酸素銅が使用されている。この
銅安定化材は、使用する際に何等かの原因によって超電
導状態が破れた場合に、発生するジュール熱をバイパス
させて、超電導線を保護しようとするものである。従っ
てできる限り抵抗の低い銅材が望まれている。2. Description of the Related Art Oxygen-free copper with a purity of 99.99% is normally used as a stabilizing material for metallic superconducting wires. This copper stabilizing material is intended to protect the superconducting wire by bypassing the Joule heat generated when the superconducting state is broken for some reason during use. Therefore, a copper material with as low resistance as possible is desired.
【０００３】しかしながら、現状は前述のように９９．
９９４％以上の無酸素銅（ＯＦＣ）が使用されており、
その抵抗率は数１で表される残留抵抗比（ＲＲＲ）で３
００〜５００程度である。[0003] However, as mentioned above, the current situation is 99.
More than 994% oxygen-free copper (OFC) is used,
Its resistivity is the residual resistance ratio (RRR) expressed by the formula 1, which is 3
It is about 00 to 500.
【０００４】0004
【数１】[Math 1]
【０００５】[0005]
【発明が解決しようとする課題】超電導線は、さらに高
性能化あるいは超電導ケーブルのコンパクト化のために
安定化材の量を少なくすることが望まれている。このた
めには、より高いＲＲＲの銅材とする必要があるが、現
状の９９．９９％純度のＯＦＣではＲＲＲ値は高々６０
０位が限界である。SUMMARY OF THE INVENTION In order to further improve the performance of superconducting wires or to make superconducting cables more compact, it is desired to reduce the amount of stabilizing material used in superconducting wires. For this purpose, it is necessary to use a copper material with a higher RRR, but with the current 99.99% purity OFC, the RRR value is at most 60.
0th place is the limit.
【０００６】そこで高純度銅材を応用することが考えら
れるが、純度が高くなるとコストが非常に高く、実用材
料としての使用は困難であった。しかし、近年９９．９
９９％以上の高純度銅材の量産方法も確立されて比較的
安価に利用できるようになっており、この場合ＲＲＲは
飛躍的に増加して５０００〜６０００にすることが可能
となった。[0006] Therefore, it has been considered to apply a high-purity copper material, but the higher the purity, the higher the cost, making it difficult to use it as a practical material. However, in recent years 99.9
A mass production method for high-purity copper material of 99% or more has been established and can be used at a relatively low cost, and in this case, the RRR can be dramatically increased to 5,000 to 6,000.
【０００７】本発明は以上の点に鑑みなされたものであ
り、高ＲＲＲの銅材料を提供することを可能とした高残
留抵抗比銅材の製造方法を提供することを目的とするも
のである。The present invention has been made in view of the above points, and an object of the present invention is to provide a method for manufacturing a high residual resistance ratio copper material that makes it possible to provide a high RRR copper material. .
【０００８】[0008]
【課題を解決するための手段】上記目的は、９９．９９
９％以上の純度を有する銅材を温度６５０〜８００℃、
不活性ガス雰囲気中で少なくとも３０分以上加熱して製
造することにより、達成される。[Means for solving the problem] The above purpose is 99.99
Copper material with a purity of 9% or more is heated at a temperature of 650 to 800°C.
This is achieved by heating in an inert gas atmosphere for at least 30 minutes.
【０００９】[0009]
【作用】上記手段を設けたので、ＲＲＲの高い銅材料が
得られるようになる。[Operation] Since the above means is provided, a copper material with high RRR can be obtained.
【００１０】0010
【実施例】次に本発明を実施例により具体的に説明する
。[Examples] Next, the present invention will be explained in detail with reference to Examples.
【００１１】〔実施例 １〕本実施例では９９．９９
９％以上の純度を有する銅材を温度６５０〜８００℃、
不活性ガス雰囲気中で少なくとも３０分以上加熱して製
造した。このようにすることによりＲＲＲの高い銅材料
が得られるようになり、高ＲＲＲの銅材料を提供するこ
とを可能とした高残留抵抗比銅材の製造方法を得ること
ができる。[Example 1] In this example, 99.99
Copper material with a purity of 9% or more is heated at a temperature of 650 to 800°C.
It was produced by heating in an inert gas atmosphere for at least 30 minutes. By doing so, a copper material with high RRR can be obtained, and a method for manufacturing a copper material with a high residual resistance ratio can be obtained, which makes it possible to provide a copper material with high RRR.
【００１２】すなわち再電解銅を帯溶精製により９９．
９９９％の高純度銅材を加工度８５〜９０％施した後に
、３５０℃中で中間焼鈍を行ってから、さらに８５〜９
５％範囲で加工し、５００〜９００℃でそれぞれ３０分
の熱処理後に残留抵抗比（ＲＲＲ）を測定した。That is, re-electrolyzed copper is purified by solution refining to achieve a purity of 99.9%.
After processing a 999% high purity copper material with a working degree of 85 to 90%, intermediate annealing is performed at 350°C, and then further annealing is performed at 85 to 90°C.
The residual resistance ratio (RRR) was measured after processing in a range of 5% and heat treatment for 30 minutes at 500 to 900°C.
【００１３】さらに帯溶精製した素材へ希土類元素を１
０ｐｐｍ添加して真空溶解で得られた銅材を上述と同様
の加工→中間焼鈍→加工を加えた後に５００〜９００℃
で３０分の熱処理後ＲＲＲを測定した。[0013] Furthermore, 1 rare earth element is added to the refined material.
Copper material obtained by vacuum melting with 0 ppm added was processed in the same manner as above → intermediate annealing → after processing at 500 to 900°C
RRR was measured after heat treatment for 30 minutes.
【００１４】表１は実施した材料の組成を示したもので
あり、図１は各温度で熱処理後のＲＲＲ値測定結果を示
したものである。Table 1 shows the composition of the materials used, and FIG. 1 shows the RRR value measurement results after heat treatment at various temperatures.
【００１５】[0015]
【表１】[Table 1]
【００１６】同図から明らかなように、この材料は加熱
温度の上昇とともにＲＲＲ値は高くなるが、６００℃以
下ではＲＲＲ＝７０００未満である。しかし６５０℃加
熱になるとＲＲＲ＝７５００以上となり、７００℃加熱
になると本実施例１（表１参照）の高純度ＣｕはＲＲＲ
＝８５００に到達し、本実施例２（表１参照）の希土類
入りＣｕはＲＲＲ＝９５００最大となる。しかしさらに
加熱温度が９００℃加熱になるとこれら両サンプルは急
激にＲＲＲ値は低下するようになる。従って本材料の加
熱温度条件としては、６５０〜８００℃が高ＲＲＲ値を
維持できる適正な温度である。なお、比較例１（表１参
照）の無酸素銅Ｃｕ（ＯＦＣ）はあまり加熱温度との対
応は見られずＲＲＲ＝４３５〜４６０である。As is clear from the figure, the RRR value of this material increases as the heating temperature increases, but RRR is less than 7000 at temperatures below 600°C. However, when heated to 650°C, RRR=7500 or more, and when heated to 700°C, the high purity Cu of Example 1 (see Table 1) has an RRR of
= 8500, and the rare earth-containing Cu of Example 2 (see Table 1) has a maximum RRR of 9500. However, when the heating temperature was further increased to 900° C., the RRR values of both these samples suddenly decreased. Therefore, as the heating temperature condition for this material, 650 to 800°C is an appropriate temperature at which a high RRR value can be maintained. In addition, the oxygen-free copper Cu (OFC) of Comparative Example 1 (see Table 1) does not show much correspondence with the heating temperature, and has an RRR of 435 to 460.
【００１７】このように本実施例によれば、次に述べる
ような効果を奏することができる。As described above, according to this embodiment, the following effects can be achieved.
【００１８】（１）本実施例の加熱処理方法によれば、
純度の指標であるＲＲＲを高い値でしかも安定的に管理
することができ、また工数も省略できる。(1) According to the heat treatment method of this example,
RRR, which is an indicator of purity, can be stably managed at a high value, and the number of man-hours can also be omitted.
【００１９】（２）応用対象としては超電導線の安定化
材および電子部品の例えば半導体装置のＳｉチップ発熱
防止用の冷却材がある。(2) Applications include stabilizing materials for superconducting wires and cooling materials for preventing heat generation of Si chips in electronic components such as semiconductor devices.
【００２０】なお、加熱温度および時間、加熱雰囲気、
希土類元素量については、次のようなことが云える。[0020]Heating temperature and time, heating atmosphere,
Regarding the amount of rare earth elements, the following can be said.
【００２１】（１）加熱温度および時間６５０℃以下で
は指標とするＲＲＲ値は望めず、９００℃以上ではやは
りＲＲＲ値は低下する。(1) Heating temperature and time At temperatures below 650°C, no RRR value can be expected, and at temperatures above 900°C, the RRR value decreases.
【００２２】加熱時間は３０分以下では効果がでない。[0022] If the heating time is less than 30 minutes, there will be no effect.
【００２３】（２）加熱雰囲気
Ｎ２ガスあるいはＡｒガス等の不活性ガス雰囲気を使用
し、ガス流量１リットル／ｍｉｎ以上とする。(2) Heating atmosphere: An inert gas atmosphere such as N2 gas or Ar gas is used, and the gas flow rate is 1 liter/min or more.
【００２４】真空雰囲気中の場合は１×１０のマイナス
５乗Ｔｏｒｒを確保する。In the case of a vacuum atmosphere, a Torr of 1×10 to the minus fifth power is ensured.
【００２５】上記以下の数値では微量の酸素が銅中に固
溶して、ＲＲＲ値を減少させる原因となる。[0025] If the value is less than the above value, a trace amount of oxygen will form a solid solution in the copper, causing a decrease in the RRR value.
【００２６】（３）希土類元素量
添加量が４ｐｐｍ以下ではＣｕ中の微量不純物の清浄抑
制効果がない。(3) Amount of rare earth element If the amount added is less than 4 ppm, there is no effect of suppressing the cleaning of trace impurities in Cu.
【００２７】逆に２０ｐｐｍ以上では不純元素として残
留し、混入量が多くなり、ＲＲＲ値を低下させる。On the other hand, if it is more than 20 ppm, it remains as an impurity element, increases the amount of contamination, and lowers the RRR value.
【００２８】[0028]
【発明の効果】上述のように本発明は、９９．９９９％
以上の純度を有する銅材を温度６５０〜８００℃、不活
性ガス雰囲気中で少なくとも３０分以上加熱して製造し
たので、ＲＲＲの高い銅材料が得られるようになって、
高ＲＲＲの銅材料を提供することを可能とした高残留抵
抗比銅材の製造方法を得ることができる。Effects of the Invention As mentioned above, the present invention achieves 99.999%
Since the copper material having the above purity is heated at a temperature of 650 to 800°C in an inert gas atmosphere for at least 30 minutes or more, a copper material with high RRR can be obtained.
A method for manufacturing a high residual resistance ratio copper material that makes it possible to provide a copper material with a high RRR can be obtained.
【図１】本発明の高残留抵抗比銅材の製造方法の一実施
例による加熱温度とＲＲＲとの関係を示す特性図である
。FIG. 1 is a characteristic diagram showing the relationship between heating temperature and RRR according to an embodiment of the method for manufacturing a high residual resistance ratio copper material of the present invention.
Claims (1)
材を温度６５０〜８００℃、不活性ガス雰囲気中で少な
くとも３０分以上加熱して製造したことを特徴とする高
残留抵抗比銅材の製造方法。1. A copper material with a high residual resistance ratio, which is produced by heating a copper material having a purity of 99.999% or more at a temperature of 650 to 800° C. in an inert gas atmosphere for at least 30 minutes. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41432990A JPH04224662A (en) | 1990-12-26 | 1990-12-26 | Production of copper material having high residual resistance ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41432990A JPH04224662A (en) | 1990-12-26 | 1990-12-26 | Production of copper material having high residual resistance ratio |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04224662A true JPH04224662A (en) | 1992-08-13 |
Family
ID=18522819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41432990A Pending JPH04224662A (en) | 1990-12-26 | 1990-12-26 | Production of copper material having high residual resistance ratio |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04224662A (en) |
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| CN112687789A (en) * | 2016-04-06 | 2021-04-20 | 三菱综合材料株式会社 | Superconducting stabilizing material |
| CN108603251B (en) * | 2016-04-06 | 2021-07-30 | 三菱综合材料株式会社 | Superconducting wire and superconducting coil |
| US11149329B2 (en) | 2016-04-06 | 2021-10-19 | Mitsubishi Materials Corporation | Stabilizer material for superconductor |
| JP2016156099A (en) * | 2016-05-26 | 2016-09-01 | 三菱マテリアル株式会社 | Superconducting wire and superconducting coil |
| JP2016156098A (en) * | 2016-05-26 | 2016-09-01 | 三菱マテリアル株式会社 | Superconduction stabilization material, superconducting wire, and superconducting coil |
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