JPH01218765A - Oxide superconductor and joining method thereof - Google Patents
Oxide superconductor and joining method thereofInfo
- Publication number
- JPH01218765A JPH01218765A JP4204688A JP4204688A JPH01218765A JP H01218765 A JPH01218765 A JP H01218765A JP 4204688 A JP4204688 A JP 4204688A JP 4204688 A JP4204688 A JP 4204688A JP H01218765 A JPH01218765 A JP H01218765A
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- oxide
- temperature
- joining
- metal
- 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
- 239000002887 superconductor Substances 0.000 title claims abstract description 49
- 238000005304 joining Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 15
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910000679 solder Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 5
- 238000003303 reheating Methods 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims 3
- 238000005219 brazing Methods 0.000 abstract description 9
- 239000000945 filler Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 101100025832 Danio rerio nbas gene Proteins 0.000 description 1
- 229910020012 Nb—Ti Inorganic materials 0.000 description 1
- 239000000919 ceramic Chemical group 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Manufacturing Of Electrical Connectors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、酸化物系高温超電導体及びその接合方法に係
り、特に、酸化物系高温超電導体の超電導特性を損なわ
ない接合体を得ることができる、新規な接合方法に関す
る。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an oxide-based high-temperature superconductor and a method for joining the same, and in particular, to obtain a joined body that does not impair the superconducting properties of the oxide-based high-temperature superconductor. This invention relates to a new joining method that allows for
従来、Ｎｂ−Ｔｉ合金や、Ｎ ｂ ａｓ ｎ 、Ｎｂ５
Ａ Ｑ等の金属間化合物の接合方法として、溶接学会誌
ｖｏ１．５６ Ｎａ２（１９８７）に記載のように、
□はんだ付、圧接、超音波接合、抵抗加熱溶接、電子ビ
ーム溶接等、が試みられている。しかし、臨界温度が９
０に以上の特性を有する、ＹＢａ−Ｃｕ−Ｏ系の酸化物
高温超電導体の接合は、酸化物であること、超電導性が
組成によって大きく左右されること等により、非常に困
難である。このため、現在は金等を蒸着し、その上に、
はんだ等で接合しているが、接合強度が弱く、また耐熱
性も低い。Conventionally, Nb-Ti alloy, Nbas n, Nb5
As a method for joining intermetallic compounds such as A and Q, as described in Journal of the Welding Society vol. 1.56 Na2 (1987),
□ Soldering, pressure welding, ultrasonic bonding, resistance heating welding, electron beam welding, etc. have been tried. However, the critical temperature is 9
It is very difficult to bond YBa-Cu-O-based oxide high temperature superconductors, which have characteristics of 0.0 or higher, because they are oxides and their superconductivity is greatly influenced by their composition. For this reason, currently gold, etc. is deposited on top of it.
Although they are joined using solder, etc., the joint strength is weak and the heat resistance is also low.
更に蒸着等では真空チャンバ・−の大きさも限られ、被
接合体の大きさも限定される。Furthermore, in vapor deposition, etc., the size of the vacuum chamber is limited, and the size of the objects to be bonded is also limited.
一方、前記超電導体を線材化した場合の該超電導体を保
護するシース材は、銀または銅を使用することが公知で
ある。しかし、該超電導体とシース材は接触しているだ
けのため、両者の界面抵抗が大きく、電磁装置の入出力
端子に接合した場合、発熱が大きく、特に接合部の超電
導特性が損なわれるという問題がある。On the other hand, it is known that silver or copper is used as a sheath material for protecting the superconductor when the superconductor is formed into a wire. However, since the superconductor and sheath material are only in contact with each other, the interfacial resistance between the two is large, and when bonded to the input/output terminal of an electromagnetic device, a large amount of heat is generated, which particularly impairs the superconducting properties of the bonded portion. There is.
上記従来技術では、接合強度が弱いばかりでなく、酸化
物系高温超電導体が、接合過程で、超電導特性を失うと
いう問題があった。The above-mentioned conventional technology has the problem that not only the bonding strength is weak, but also the oxide-based high-temperature superconductor loses its superconducting properties during the bonding process.
本発明の目的は、酸化物系高温超電導体の超電導特性を
損なうことのない、超電導体と他の部材との接合方法及
び本発明の接合方法によって接合された酸化物系超電導
体にある。An object of the present invention is to provide a method for joining a superconductor and another member without impairing the superconducting properties of the oxide-based high-temperature superconductor, and an oxide-based superconductor joined by the joining method of the present invention.
上記目的は、酸化物系高温超電導体の被接合面に、銀と
銅の少なくとも１つを主成分とし、Ｔｉ。The above-mentioned object is to provide a bonded surface of an oxide-based high-temperature superconductor containing at least one of silver and copper as a main component, and Ti.
Ｚｒ、Ｈｆ・の中から選ばれる、少なくとも１種以上の
元素を（Ｌｌ〜１０重量％含む合金ろう材を配置し、前
記ろう材の融点以上に加熱後、酸素雰囲気中において、
４００〜９００℃の温度で１時間以上加熱し、２００℃
／ｈ以下の速度で冷却することにより達成される。An alloy brazing material containing at least one element selected from Zr, Hf.
Heat at a temperature of 400 to 900℃ for more than 1 hour, then heat to 200℃
This is achieved by cooling at a rate of less than /h.
本発明では、酸化物系高温超電導体を接合するろう材と
して、銀粉末、銅粉末又はそれらの混合粉末或いは銀と
銅の合金粉末に、ＩＶａ族元素（Ｔｉ、Ｚｒ、Ｈｆ）の
中の少なくとも１種以上の元素を０．１〜１０重量％添
加したものを用いる。それによって、前記超電導体への
ろう材のぬれ性は、著しく向上し、接合強度の大きい接
合体が得られる。ＩＶａ族元素の添加量が０．１ 重量
％以下では、ぬれ性に対する効果が小さく、また、１０
重量％以上では、超電導体の組成を大きく変化させ、超
電導特性を完全に無くしてしまうため、望ましくない。In the present invention, at least one of group IVa elements (Ti, Zr, Hf) is added to silver powder, copper powder, mixed powder thereof, or alloy powder of silver and copper as a brazing material for joining oxide-based high-temperature superconductors. One or more elements added in an amount of 0.1 to 10% by weight is used. As a result, the wettability of the brazing material to the superconductor is significantly improved, and a bonded body with high bonding strength can be obtained. If the amount of the IVa group element added is 0.1% by weight or less, the effect on wettability is small;
If it exceeds % by weight, the composition of the superconductor will be greatly changed and the superconducting properties will be completely lost, which is not desirable.
一方、前記ろう材によって接合する場合、加熱の過程で
、元素の移動、特に酸素の移動または損失で超電導特性
が損なわ九る。本発明では、接合後、酸素雰囲気中、４
００〜９００℃の温度で１時間以上加熱、２．Ｏ，Ｏ℃
／ｈ以下の速度で冷却する。On the other hand, when bonding is performed using the brazing filler metal, superconducting properties are impaired due to movement of elements, particularly movement or loss of oxygen, during the heating process. In the present invention, after bonding, 4
Heating at a temperature of 00 to 900°C for more than 1 hour, 2. O, O℃
/h or less.
４００〜６００℃は、酸化物系超電導体が、酸素をよく
取り込む温度である。また、９００℃以上に加熱すると
、前記超電導体の相転移や溶融が起こるだめ、超電導特
性を失う可能性が大きい。400 to 600°C is the temperature at which the oxide superconductor takes in oxygen well. Furthermore, if heated to 900° C. or higher, the superconductor undergoes phase transition or melting, and there is a high possibility that the superconducting properties will be lost.
酸素を十分に取り込ませるためには、４００〜９００℃
の温度範囲内で１時間以上加熱することが適当である。In order to incorporate enough oxygen, the temperature must be 400-900℃.
It is appropriate to heat within the temperature range of 1 hour or more.
さらに、６００〜９００℃以上に加熱した場合の酸素の
放出等を考慮して、酸素の十分な取り込みのため、２０
０℃／ｈ以下の速度での冷却が必要である。この結果、
前記超電導体中に、再び酸素が取り込まれ、超電導特性
を回復させることができる。Furthermore, in consideration of the release of oxygen when heated to 600 to 900 degrees Celsius or higher, we added a
Cooling at a rate of 0° C./h or less is required. As a result,
Oxygen is incorporated into the superconductor again, and the superconducting properties can be restored.
このようにして、酸化物系高温超電導体の超電導特性を
損なわずに、接合することができる。In this way, it is possible to bond the oxide-based high-temperature superconductor without impairing its superconducting properties.
更に本発明による接合部の電気抵抗は１３μΩ・■以下
で、接合部からの発熱は門めて少ない。Furthermore, the electrical resistance of the joint according to the present invention is 13 μΩ·■ or less, and the heat generated from the joint is extremely low.
実施例１
直径ＩＩＩｗＩＩのＹＢａ２Ｃｕａ０７−ｇ超電導体に
７２重量％Ａｇ−２８重量％Ｃｕの合金粉末中に５重量
％のＺｒ粉末を添加した、ペースト状の金属ろうを塗布
し、これをアルゴン雰囲気中で、９００℃、５分間加熱
して、銅線とのろう付を行った。これをいったん室温ま
で冷却してから、酸素雰囲気中、４００℃、１０時間加
熱した後、炉冷した。酸素雰囲気中での熱処理の前後で
、この接合体について、マイスナー効果を調べた。熱処
理前では、マイスナー効果は見られなかったが、熱処理
後の試験では、マイスナー効果が確認された。これによ
って、超電導特性を損なわずに、ＹＢａｚＣｕ３０７−
ｇと、金属との接合体を得ることができた。Example 1 A paste-like metal solder containing 5% by weight of Zr powder added to an alloy powder of 72% by weight Ag-28% by weight Cu was applied to a YBa2Cua07-g superconductor with a diameter of IIIwII, and this was applied in an argon atmosphere. Then, it was heated at 900°C for 5 minutes and brazed with copper wire. This was once cooled to room temperature, heated in an oxygen atmosphere at 400° C. for 10 hours, and then cooled in a furnace. The Meissner effect was investigated for this bonded body before and after heat treatment in an oxygen atmosphere. Although the Meissner effect was not observed before heat treatment, the Meissner effect was confirmed in the test after heat treatment. As a result, YBazCu307-
A bonded body of g and metal could be obtained.
実施例２
φ１．５側のＹＢａ２ＣｕｓＯｒ−ｓ超電導体に、９０
重量％Ａ ’ｇ、 −５重量％Ｔｉ−５重量％Ｐｌｄの
組成をもつ、ペースト状の金属ろうを塗布し、これをア
ルゴン雰囲気中で、９５０℃、５分間加熱して、銅線と
のろう付を行った。室温まで冷却してから、酸素雰囲気
中、４００℃、１０時間熱処理した後、炉冷した。マイ
スナー効果を調べたところ、実施例１と同様に、熱処理
後の試料で、マイスナー効果が確認された。Example 2 YBa2CusOr-s superconductor on the φ1.5 side was
A paste-like metal solder having a composition of wt%A'g, -5wt%Ti-5wt%Pld is applied and heated at 950°C for 5 minutes in an argon atmosphere to bond it to the copper wire. I did the brazing. After cooling to room temperature, it was heat-treated at 400° C. for 10 hours in an oxygen atmosphere, and then cooled in a furnace. When the Meissner effect was investigated, the Meissner effect was confirmed in the sample after heat treatment, as in Example 1.
実施例３
φ１．５ｍｍのＹＢａｚＣｕｓ０７−ｇ超電導体に、７
２重量％Ａｇ−２８重量％Ｃｕの合金粉末中に５重量％
のＴｉ粉末を添加したペースト状金属ろうを塗布し、こ
れをアルゴン雰囲気中で８５０℃、５分間加熱して、銅
線とのろう付を行った。室温まで冷却してから、酸素雰
囲気中で、４００℃、１０時間加熱した後、６０℃／ｈ
の速度で冷却した。Example 3 YBazCus07-g superconductor with a diameter of 1.5 mm,
5% by weight in alloy powder of 2% Ag-28% Cu
A paste-like metal solder containing Ti powder was applied, and this was heated at 850° C. for 5 minutes in an argon atmosphere to braze it with a copper wire. After cooling to room temperature, heating at 400°C for 10 hours in an oxygen atmosphere, and then heating at 60°C/h.
It was cooled at a rate of .
本発明によって接合された接合部の電気抵抗は１２μΩ
・σであり、また、９０Ｋにおける電流密度は５０００
Ａ／ｃｎＹであった。The electrical resistance of the joint joined according to the present invention is 12μΩ
・σ, and the current density at 90K is 5000
It was A/cnY.
また、この接合された超電導体を用いて、モーターを作
動させることができた。Furthermore, a motor could be operated using this bonded superconductor.
本発明によれば、酸化物系高温超電導体とろう材とのぬ
れ性が良く、しかも前記超電導体の超電導特性を損なわ
ない接合ができるので、前記超電導体を、金属や他のセ
ラミックス等と接合して用いることが可能となる。これ
によって、酸化物系高温超電導体の応用範囲を大きく拡
げることになる。According to the present invention, the oxide-based high-temperature superconductor and the brazing material have good wettability and can be bonded without impairing the superconducting properties of the superconductor, so the superconductor can be bonded to metals, other ceramics, etc. It becomes possible to use it as This will greatly expand the range of applications of oxide-based high-temperature superconductors.
更に本発明によって接合された接合部の抵抗は１３μΩ
・印と小さく、実用上問題なかった。Furthermore, the resistance of the joint joined according to the present invention is 13 μΩ.
・The mark was small and there was no problem in practical use.
Claims (1)
よりなる部材の接合方法において、前記超電導体の被接
合面に金属ろうを接触させ、前記金属ろうの融点以上に
加熱した後、酸素雰囲気中において、４００〜９００℃
で再加熱し、２００℃／ｈ以下の速度で冷却することを
特徴とする、酸化物系高温超電導体の接合方法。 ２、特許請求の範囲第１項記載の金属ろうが、銀または
銅のいずれか１種に、元素周期表のIVａ族（Ｔｉ，Ｚｒ
，Ｈｆ）から選ばれる少なくとも１種以上の元素を０．
１〜１０重量％含むことを特徴とする酸化物系高温超電
導体の接合方法。 ３、特許請求の範囲第１項記載の金属ろうが、銀または
銅のいずれか１種を主成分とする合金または混合粉末中
に、元素周期表のIVａ族（Ｔｉ，Ｚｒ，Ｈｆ）から選ば
れる少なくとも１種以上の元素を０．１〜１０重量％含
むことを特徴とする酸化物系高温超電導体の接合方法。 ４、特許請求の範囲第１項記載の金属ろうが、銀及び銅
を主成分とする合金または混合粉末中に、元素周期表の
IVａ族（Ｔｉ，Ｚｒ，Ｈｆ）の中から選ばれる少なくと
も１種以上の元素を０．１〜１０重量％含むことを特徴
とする酸化物系高温超電導体の接合方法。 ５、特許請求の範囲第１〜４項記載のいずれか１つの方
法によつて酸化物系超電導体の表面が、Ｔｉ，Ｚｒ，Ｈ
ｆの中から選ばれる少なくとも１種以上の元素を、０．
１〜１０重量％含む金属と接してなることを特徴とする
酸化物系超電導体。 ６、特許請求の範囲第１〜４項記載のいずれか１つの方
法により、酸化物系超電導体の表面が、Ｔｉ，Ｚｒ，Ｈ
ｆの中から選ばれる少なくとも１種以上の元素を、０．
１〜１０重量％含む金属よつて保護されていることを特
徴とする、酸化物系超電導体。 ７、特許請求の範囲第５項または第６項に記載の金属は
、銀または銅のいずれか１種以上を主成分とすることを
特徴とする酸化物系超電導体。 ８、特許請求の範囲第１〜４項記載のいずれか１つの方
法によつて、酸化物系超電導体が、装置の電気信号入出
力端子に接合されていることを特徴とする酸化物系超電
導体。[Claims] 1. In a method for joining members in which at least one of the materials to be joined is made of an oxide-based high-temperature superconductor, a metal solder is brought into contact with the surface of the superconductor to be joined, and the temperature is higher than the melting point of the metal solder. After heating, in an oxygen atmosphere, 400-900℃
1. A method for joining oxide-based high-temperature superconductors, which comprises reheating at a temperature of 200° C. and cooling at a rate of 200° C./h or less. 2. The metal solder according to claim 1 contains one of silver or copper and group IVa (Ti, Zr) of the periodic table of elements.
, Hf) at least one element selected from 0.
A method for joining an oxide-based high-temperature superconductor, characterized in that it contains 1 to 10% by weight. 3. The metal solder according to claim 1 contains a metal selected from group IVa of the periodic table of elements (Ti, Zr, Hf) in an alloy or mixed powder containing either silver or copper as a main component. A method for joining oxide-based high-temperature superconductors, characterized in that the oxide-based high temperature superconductor contains 0.1 to 10% by weight of at least one or more elements. 4. The metal solder according to claim 1 contains elements from the periodic table of elements in the alloy or mixed powder mainly composed of silver and copper.
A method for joining oxide-based high-temperature superconductors, comprising 0.1 to 10% by weight of at least one element selected from Group IVa (Ti, Zr, Hf). 5. The surface of the oxide superconductor is coated with Ti, Zr, H by the method according to any one of claims 1 to 4.
At least one element selected from f is 0.
An oxide-based superconductor formed in contact with a metal containing 1 to 10% by weight. 6. The surface of the oxide superconductor is coated with Ti, Zr, H by the method according to any one of claims 1 to 4.
At least one element selected from f is 0.
An oxide-based superconductor protected by a metal containing 1 to 10% by weight. 7. An oxide-based superconductor, wherein the metal according to claim 5 or 6 contains at least one of silver or copper as a main component. 8. An oxide-based superconductor characterized in that the oxide-based superconductor is bonded to an electrical signal input/output terminal of a device by the method according to any one of claims 1 to 4. body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4204688A JPH01218765A (en) | 1988-02-26 | 1988-02-26 | Oxide superconductor and joining method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4204688A JPH01218765A (en) | 1988-02-26 | 1988-02-26 | Oxide superconductor and joining method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01218765A true JPH01218765A (en) | 1989-08-31 |
Family
ID=12625178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4204688A Pending JPH01218765A (en) | 1988-02-26 | 1988-02-26 | Oxide superconductor and joining method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01218765A (en) |
-
1988
- 1988-02-26 JP JP4204688A patent/JPH01218765A/en active Pending
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