JPS63292517A - Compound ceramic superconductor - Google Patents
Compound ceramic superconductorInfo
- Publication number
- JPS63292517A JPS63292517A JP62128734A JP12873487A JPS63292517A JP S63292517 A JPS63292517 A JP S63292517A JP 62128734 A JP62128734 A JP 62128734A JP 12873487 A JP12873487 A JP 12873487A JP S63292517 A JPS63292517 A JP S63292517A
- Authority
- JP
- Japan
- Prior art keywords
- elements
- group
- ceramic
- superconductor
- periodic table
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 70
- 239000002887 superconductor Substances 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title description 4
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 238000009413 insulation Methods 0.000 claims abstract description 15
- 230000000737 periodic effect Effects 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910001849 group 12 element Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000005245 sintering Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004804 winding Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000007751 thermal spraying Methods 0.000 description 6
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 description 5
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- LNSPFAOULBTYBI-UHFFFAOYSA-N [O].C#C Chemical group [O].C#C LNSPFAOULBTYBI-UHFFFAOYSA-N 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017532 Cu-Be Inorganic materials 0.000 description 1
- -1 NbTi Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は、複合セラミックス超電導体に関し、より詳
しくは、少なくともセラミックス超電導体からなる導電
体の表面の所定部に絶縁膜を形成した複合セラミックス
超電導体に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a composite ceramic superconductor, and more specifically, a composite ceramic superconductor in which an insulating film is formed on a predetermined part of the surface of a conductor made of at least a ceramic superconductor. Regarding the body.
〈従来の技術と発明が解決しようとする問題点〉従来よ
り、超電導体として、金属系（ＮｂＴｉ等の合金、Ｎｂ
２５ｎＳＶ３ Ｇａ等の金属間化合物）のものが提供さ
れているが、これらの超電導体は、臨界温度（Ｔｃ）が
非常に低く、冷却コストが高くなるため、高い臨界温度
を示す超電導体の開発が要望されていた。<Prior art and problems to be solved by the invention> Conventionally, metal-based materials (alloys such as NbTi, Nb
However, these superconductors have very low critical temperatures (Tc) and require high cooling costs, making it difficult to develop superconductors with high critical temperatures. It was requested.
このような要望を満たす超電導体として、近年、ペロブ
スカイト型の構造を有するセラミックス超電導体が開発
されており、このセラミックス超電導体については、３
０に以上の臨界温度を示している。In recent years, ceramic superconductors with a perovskite structure have been developed as superconductors that meet these demands.
It shows a critical temperature above 0.
これらセラミックス超電導体は、通常、原体粉末を金型
成形法等によって、所定形状に成形した後、焼結するこ
とによって製造されている。These ceramic superconductors are usually manufactured by molding raw powder into a predetermined shape using a molding method or the like, and then sintering it.
ところで、上記セラミックス超電導体を長尺の超電導線
として形成して、例えばコイル形状に巻回していく場合
、当該超電導線は、延性、可撓性に乏しく、加工性が極
めて悪いので、巻線加工を試みても、折れたりひび割れ
したりして、所望の形状に巻き取ることは困難である。By the way, when the above-mentioned ceramic superconductor is formed as a long superconducting wire and wound into a coil shape, for example, the superconducting wire has poor ductility and flexibility, and is extremely difficult to work with. Even if you try, it will break or crack, making it difficult to wind it into the desired shape.
そこで、焼結する前の可撓性を有する段階でコイル状に
成形しておき、成形後に焼結すれば、上記の問題を克服
することができる。しかしこの場合、いかにして外部と
の電気的接触、または隣り合う巻線同士の電気的接触を
防止するための絶縁被覆を施すかという新たな問題が生
じる。Therefore, the above-mentioned problem can be overcome by forming the coil into a coil shape at a stage where it has flexibility before sintering, and sintering it after forming. However, in this case, a new problem arises: how to apply an insulating coating to prevent electrical contact with the outside or between adjacent windings.
この点、従来の金、銅、アルミニウム線等の導線であれ
ば、導線の表面にエナメル、樹脂等を塗布して低温で焼
き付けるか、紙テープを巻回することによって絶縁すれ
ばよく、このようにして得られた絶縁導線をコイル形状
に巻き付けていけばよかった。In this regard, in the case of conventional conductors such as gold, copper, or aluminum wires, it is sufficient to insulate them by applying enamel, resin, etc. to the surface of the conductor and baking them at low temperatures, or by wrapping paper tape around them. All you had to do was wind the insulated conductor wire obtained by doing this into a coil shape.
しかし、セラミックス超電導線にあっては、予め絶縁被
覆を施してから焼結すると、当該焼結時において１００
０℃近い高温になるために、絶縁被覆材が溶融または燃
焼してしまう。また、焼結後の超電導線に絶縁膜を電着
法、含浸法、塗布法等により形成することも考えられる
が、上記のように、隣り合う巻線同士が接触している場
合には、当該接触部分に絶縁被覆を施すことができない
ことになる。However, when ceramic superconducting wire is sintered after being coated with insulation in advance, the 100%
Because the temperature is close to 0°C, the insulation coating melts or burns. It is also possible to form an insulating film on the superconducting wire after sintering by electrodeposition, impregnation, coating, etc. However, as mentioned above, when adjacent windings are in contact with each other, This means that it is not possible to apply an insulating coating to the contact portion.
一方、より高い臨界温度と安定的な超電導特性を示すセ
ラミックス超電導体を得るためには、焼結工程終了後に
所定温度で熱処理を施すことが好ましいのであるが、当
該熱処理を施す前に上記の絶縁被覆材により絶縁被覆を
施しておくと、絶縁被覆が溶融してしまうことから、熱
処理後に絶縁被覆を施す必要があり、この場合にも、上
記と同様、隣り合う巻線同士の接触部分に絶縁被覆を施
すことができないことになる。On the other hand, in order to obtain a ceramic superconductor that exhibits a higher critical temperature and stable superconducting properties, it is preferable to perform heat treatment at a predetermined temperature after the sintering process. If an insulating coating is applied with a covering material, the insulating coating will melt, so it is necessary to apply an insulating coating after heat treatment. In this case, as well, it is necessary to insulate the contact areas between adjacent windings. This means that no coating can be applied.
しかも、上記従来の絶縁被覆は、耐熱性はもとより耐水
性に劣り、絶縁被覆膜を通して被覆されたセラミックス
超電導線に湿気が入り込み、超電導特性が変化すること
がある。さらに、耐摩耗性、耐候性等の面においても難
点があり、超電導体を長期間に亘って確実に保護するこ
とができないという問題もあった。Furthermore, the conventional insulating coating described above has poor water resistance as well as heat resistance, and moisture may enter the coated ceramic superconducting wire through the insulating coating film, changing the superconducting properties. Furthermore, there are also drawbacks in terms of wear resistance, weather resistance, etc., and there is also the problem that the superconductor cannot be reliably protected for a long period of time.
く目的〉
この発明は上記問題点に鑑みてなされたものであり、耐
熱性、耐水性、耐摩耗性等の緒特性に優れ、長期間に亘
って安定した絶縁性を確保することができる複合セラミ
ックス超電導体を提供することにある。This invention was made in view of the above-mentioned problems, and is a composite material that has excellent properties such as heat resistance, water resistance, and abrasion resistance, and that can ensure stable insulation properties over a long period of time. Our objective is to provide ceramic superconductors.
く問題点を解決するための手段〉
上記の目的を達成するためのこの発明の複合セラミック
ス超電導体は、少なくとも下記一般式（Ｉ）で示される
組成のセラミックス超電導体からなる導電体の一部また
は全体が、セラミックス絶縁膜で被覆されていることを
特徴とする。Means for Solving the Problems> A composite ceramic superconductor of the present invention for achieving the above object comprises at least a part of a conductor made of a ceramic superconductor having a composition represented by the following general formula (I) or It is characterized by being entirely covered with a ceramic insulating film.
Ａ ａ Ｂ ｂ Ｃｃ （Ｉ）
上記式（Ｉ）中、Ａは周期律表Ｉａ族元素、ｎａ族元素
およびＨａ族元素より選択された少なくとも１種の元素
であり、Ｂは周期律表１ｂ族元素、ＩＩＩｂ族元素およ
びＩＩＩｂ族元素より選択された少なくとも１種の元素
であり、Ｃは酸素、窒素、フッ素、炭素および硫黄から
選択された少なくとも１種の元素である。A a B b Cc (I) In the above formula (I), A is at least one element selected from Group Ia elements, Na group elements, and Ha group elements of the periodic table, and B is an element selected from group 1b elements of the periodic table. C is at least one element selected from elements, group IIIb elements, and group IIIb elements, and C is at least one element selected from oxygen, nitrogen, fluorine, carbon, and sulfur.
ただし、式（１）中のＡとしては、周期律表Ｉａ族元素
、ＩＩａ族元素およびＩＩＩａ族元素より選択された少
なくとも２種の元素であることが好ましい。However, A in formula (1) is preferably at least two elements selected from group Ia elements, group IIa elements, and group IIIa elements of the periodic table.
また、上記セラミックス絶縁膜は、Ａ Ｊ ２０３、Ｓ
ｉ０２ 、Ｓ ｉ３ Ｎ４のうち何れか１種からなる
ものであることが好ましい。Further, the ceramic insulating film is manufactured by A J 203, S
It is preferable that it is made of any one of i02, S i3 N4.
く作用〉
上記の構成の複合セラミックス超電導体であれば、表面
の少なくとも一部に被覆されたセラミツクス絶縁膜によ
って、導電体を電気的に絶縁することができる。また、
セラミックス絶縁膜を緻密に形成することにより、耐水
性を確保することができる。しかも、セラミックス絶縁
膜は、硬度が硬いことから導電体を外傷から有効に保護
することができる。また、セラミックス絶縁膜は、耐熱
性を有することから、セラミックス超電導体の熱処理に
際しても溶融、燃焼する虞れがない。Effect> In the composite ceramic superconductor having the above structure, the conductor can be electrically insulated by the ceramic insulating film covering at least a portion of the surface. Also,
Water resistance can be ensured by forming the ceramic insulating film densely. Moreover, since the ceramic insulating film has hardness, it can effectively protect the conductor from external damage. Further, since the ceramic insulating film has heat resistance, there is no risk of melting or burning during heat treatment of the ceramic superconductor.
特に、式（Ｉ）中のＡが、周期律表Ｉａ族元素、ＩＩａ
族元素およびＨａ族元素より選択された少なくとも２種
の元素である場合には、さらに優れた超電導特性を示す
複合セラミックス超電導体を得ることができる。In particular, A in formula (I) is an element of group Ia of the periodic table, IIa
When at least two elements selected from group elements and Ha group elements are used, a composite ceramic superconductor exhibiting even better superconducting properties can be obtained.
上記セラミックス絶縁膜がＡｌ２Ｏ２、ＳｉＯ２、Ｓｉ
３Ｎ４のうち何れか１種からなるものであれば、これら
の絶縁膜により、絶縁性および耐熱性に優れ、しかも硬
くて緻密な膜を容易に形成することができる。The ceramic insulating film is made of Al2O2, SiO2, Si
If the insulating film is made of any one of 3N4 and 3N4, it is possible to easily form a hard and dense film that has excellent insulation properties and heat resistance.
〈実施例〉
次いで、この発明の実施例について図を参照しながら以
下に説明する。<Example> Next, an example of the present invention will be described below with reference to the drawings.
第１図は、この発明の複合セラミックス超電導体を超電
導コイル（１）として構成した場合を示している。FIG. 1 shows a case where the composite ceramic superconductor of the present invention is configured as a superconducting coil (1).
上記超電導コイル（１）は、第２図に示すように、セラ
ミックス超電導体（３）の周囲を小径の円筒状金属パイ
プ（４）で包囲した導電体（Ａ）の表面に、セラミック
ス絶縁膜（５）を被覆して電線素材（２）とし、これを
コイル状に成形し焼成したものである。As shown in FIG. 2, the superconducting coil (1) has a ceramic insulating film ( 5) to form an electric wire material (2), which was formed into a coil shape and fired.
上記セラミックス超電導体（３）は、下記一般式（１）
で示される組成のものである。The above ceramic superconductor (3) is expressed by the following general formula (1)
It has the composition shown below.
Ａ ａ Ｂ ｂ Ｃｃ （１）
ただし、上記式（１）中、Ａは周期律表Ｉａ族元素、Ｉ
ａ族元素およびＨａ族元素より選択された少なくとも１
種の元素、より好ましくは２種の元素であり、Ｂは周期
律表Ｉｂ族元素、ＩＩｂ族元素およびＩＩＩｂ族元素よ
り選択された少なくとも１種の元素であり、Ｃは酸素、
窒素、フッ素、炭素および硫黄から選択された少なくと
も１種の元素である。A a B b Cc (1) However, in the above formula (1), A is an element of group Ia of the periodic table, I
At least one selected from group A elements and Ha group elements
B is at least one element selected from group Ib elements, group IIb elements, and group IIIb elements of the periodic table; C is oxygen;
At least one element selected from nitrogen, fluorine, carbon and sulfur.
上記周期律表Ｉａ族元素としては、Ｌｉ、Ｎａ。The Group Ia elements of the periodic table include Li and Na.
ＫＳＲｂＳＣｓ等が挙げられ、Ｉｂ族元素としては、Ｃ
ｕＳＡｇおよびＡｕが挙げられる。また、周期律表ＩＩ
ａ族元素としては、Ｂ ｅ ｓ Ｍ ｇ ＳＣａ ％Ｓ
ｒ、ＢａおよびＲａが挙げられ、ＩＩｂ族元素としては
、ＺｎＳＣｄ等が挙げられる。周期律表ＩＩＩａ族元素
としては、Ｓｃ、Ｙやランタノイド系元素であるＬａ、
Ｃｅ５ＧｄＳＬｕ等、アクチノイド系元素であるＡｃ５
Ｔｈｓ Ｐａ５Ｃｆ等が挙げられる。また、■ｂ族元索
としては、ＡＪ、Ｇａ。KSRbSCs, etc., and group Ib elements include C
Examples include uSAg and Au. Also, periodic table II
As group a elements, B e s M g SCa %S
Examples of the group IIb elements include ZnSCd and the like. Group IIIa elements of the periodic table include Sc, Y, and the lanthanoid elements La,
Ac5, which is an actinide element such as Ce5GdSLu
Examples include ThsPa5Cf. In addition, the original members of the ■b group include AJ and Ga.
Ｉｎ、ＴＪ等が挙げられる。Examples include In and TJ.
上記元素のうち、Ｉｂ族元素から選ばれた元素、ＩＩａ
族元素、ＩＩＩａ族元素およびランタノイド系元素から
選ばれた元素、並びに酸素およびフッ素から選ばれた元
素からなるセラミックス超電導体が、高い臨界温度を示
すことから好ましく、特にＩｂ族元素についてはＣｕお
よびＡｇが好ましい。Among the above elements, elements selected from group Ib elements, IIa
Ceramic superconductors consisting of elements selected from Group elements, Group IIIa elements, and lanthanide elements, as well as elements selected from oxygen and fluorine are preferred because they exhibit high critical temperatures. In particular, for Group Ib elements, Cu and Ag is preferred.
特に、式ｍ中のＡが、周期律表Ｉａ族元素、ＩＩａ族元
素およびＩＩＩａ族元素より選択された少なくとも２種
の元素である場合（例えば、ＹとＢａ。In particular, when A in formula m is at least two elements selected from Group Ia elements, Group IIa elements, and Group IIIa elements of the periodic table (for example, Y and Ba.
ＬａとＳ「等）には、さらに優れた超電導特性を示すセ
ラミックス超電導体を生成することができる。Ceramic superconductors exhibiting even better superconducting properties can be produced from La and S (etc.).
上記金属パイプ（４）を構成する金属としては、展性、
延性に富んだＣｕ−Ｂｅ系合金の他、ステンレス、ＡＪ
ＳＡ、ｆ合金等を例示できる。また、上記セラミックス
絶縁膜（５）の材料としては、絶縁性および耐熱性に優
れ、しかも硬くて緻密な膜が形成可能なＡＪ２０３ 、
Ｓ ｉ０２ 、Ｓ ｉ３ Ｎ４等を例示できる。The metal constituting the metal pipe (4) is malleable,
In addition to highly ductile Cu-Be alloys, stainless steel, AJ
Examples include SA and f alloy. In addition, the material for the ceramic insulating film (5) is AJ203, which has excellent insulation properties and heat resistance, and can form a hard and dense film.
Examples include S i02 , S i3 N4, and the like.
次に上記超電導コイル（１）の製造方法について説明す
ると、まず、金属パイプ（４）内にセラミックス超電導
体を構成する原料粉体を充填して、当該原料粉体と金属
パイプ（４）との複層体を得、金属の延性、展性を利用
して、複層体に押し出し加工、引き抜き加工、スウェー
ジング等の減面加工を施し、導電体（Ａ）を得る。Next, to explain the manufacturing method of the superconducting coil (1), first, a metal pipe (4) is filled with raw material powder constituting the ceramic superconductor, and the raw material powder and the metal pipe (4) are connected. A multilayer body is obtained, and the multilayer body is subjected to surface reduction processing such as extrusion processing, drawing processing, swaging, etc. using the ductility and malleability of metal to obtain a conductor (A).
そして、この表面に、イオンブレーティング法、プラズ
マＣＶＤ法、スパッタリング法、真空蒸着法または溶射
法等によって、セラミックス絶縁膜（５）を緻密に被覆
して電線素材（２）とし、その後、この電線素材（２）
をソレノイドコイル形状に巻回する。Then, this surface is densely coated with a ceramic insulating film (5) by an ion blasting method, a plasma CVD method, a sputtering method, a vacuum evaporation method, a thermal spraying method, etc. to form an electric wire material (2). Material (2)
Wind it into a solenoid coil shape.
こうして得たコイル状部材を超電導体が生成される温度
領域で所定時間焼結し、その後徐冷する。The coiled member thus obtained is sintered for a predetermined time in a temperature range where superconductors are produced, and then slowly cooled.
以上により、導電体（Ａ）の外周がセラミックス絶縁膜
（５）で被覆された超電導コイル（１）を得ることがで
きる。Through the above steps, it is possible to obtain a superconducting coil (1) in which the outer periphery of the conductor (A) is covered with a ceramic insulating film (5).
上記の超電導コイル（１）であれば、可撓性のある電線
素材（２）の段階でコイル形状に成形して、その後焼結
するので、セラミックス超電導体（３）に、ひび割れ等
の欠陥が生じるのを防止することができる。In the case of the above superconducting coil (1), since the flexible wire material (2) is formed into a coil shape and then sintered, there are no defects such as cracks in the ceramic superconductor (3). This can be prevented from occurring.
また、上記セラミックス絶縁膜（５）は、焼結後もその
まま超電導コイル（１）の表面に残留するので、外部と
の電気的絶縁を保つとともに、硬くて緻密な保護膜とし
ての機能を果たし、セラミックス超電導体を水分、外傷
等から有効に保護することができる。In addition, the ceramic insulating film (5) remains on the surface of the superconducting coil (1) even after sintering, so it maintains electrical insulation from the outside and functions as a hard and dense protective film. Ceramic superconductors can be effectively protected from moisture, external damage, and the like.
特に、第１図に示すように、超電導コイル（１）の隣り
合う巻線同士が接触するように密に巻かれている場合、
セラミックス絶縁膜（５）は、成形焼結後、隣り合う巻
線同士の接触面（Ｓ）にも介在するので、巻線後におけ
る電着法、含浸法、塗布法等では実現しにくい接触面同
士の絶縁を確保することができる。In particular, as shown in FIG. 1, when the adjacent windings of the superconducting coil (1) are tightly wound so that they are in contact with each other,
After forming and sintering, the ceramic insulating film (5) is also present on the contact surfaces (S) between adjacent windings, so it is difficult to achieve contact surfaces using electrodeposition, impregnation, coating, etc. methods after winding. It is possible to ensure insulation between the two.
第３図は、この発明の他の実施例を示す斜視図であり、
テープ状電線素材（７）を渦巻き状に巻回して焼結した
超電導コイル（６）を示す。上記テープ状電線素材（７
）は、第４図に示すように、長尺の金属テープ（９）の
−面にセラミックス超電導体（８）を積層して導電体（
Ａ′）となし、さらにその上からセラミックス絶縁膜（
１０）を被覆したものである。FIG. 3 is a perspective view showing another embodiment of the invention,
A superconducting coil (6) made by spirally winding and sintering a tape-shaped electric wire material (7) is shown. The above tape-shaped electric wire material (7
), as shown in Fig. 4, a conductor (
A') and then a ceramic insulating film (
10).
セラミックス絶縁膜（１０）および金属テープ（９）の
材質については、上記第１図に示す実施例の金属パイプ
（４）およびセラミックス絶縁膜（５）の材質と同様の
ものを用いることができる。Regarding the materials of the ceramic insulating film (10) and the metal tape (9), the same materials as those of the metal pipe (4) and the ceramic insulating film (5) in the embodiment shown in FIG. 1 can be used.
次に上記超電導コイル（６）の製造方法について説明す
ると、まず、金属テープ（９）上に、イオンブレーティ
ング法、プラズマＣＶＤ法、スパッタリング法、真空蒸
着法、溶射法等によりセラミックス皮膜を生成させて導
電体（Ａ′）を得る。Next, to explain the method for manufacturing the superconducting coil (6), first, a ceramic film is formed on the metal tape (9) by an ion blasting method, a plasma CVD method, a sputtering method, a vacuum evaporation method, a thermal spraying method, etc. A conductor (A') is obtained.
上記セラミックス皮膜を、溶射法により生成する場合に
は、溶射材として、前記式ｍ中のＡＳＢ。When the above-mentioned ceramic film is produced by a thermal spraying method, ASB in the above formula m is used as the thermal spraying material.
Ｃの単体、若しくはＡ、ＢおよびＣ成分を含む化合物、
またはＡ、ＢおよびＣからなる複合セラミックスの何れ
の形態でも使用することができる。A simple substance of C or a compound containing A, B and C components,
Alternatively, any form of composite ceramics consisting of A, B and C can be used.
上記ＡＳＢおよびＣ成分を含む化合物としては、酸化物
、炭酸塩、フッ化物等が例示される。また、Ａ、Ｂおよ
びＣからなる複合セラミックス超電導体は、ＡＳＢ、お
よびＣ成分を含む化合物を予備焼結すること等により得
られる。さらに、溶射方法としては、原料粉末を酸素−
アセチレン燃焼ガスによって溶融、噴射させるサーモス
プレィプロセス、原料焼結棒を酸素−アセチレン燃焼ガ
スによって溶融し、溶滴をエアージェットで噴射させる
ローカイロッドスプレィプロセス、高温高圧のプラズマ
ジェット中に、原料粉末を供給して溶融、噴射させるプ
ラズマプロセス等を適宜選択すればよい。Examples of compounds containing the above ASB and C components include oxides, carbonates, fluorides, and the like. Further, a composite ceramic superconductor consisting of A, B and C can be obtained by pre-sintering a compound containing ASB and C components. Furthermore, as a thermal spraying method, the raw material powder is
A thermospray process in which a raw material sintered rod is melted and injected with an oxygen-acetylene combustion gas, and a low-chirod spray process in which a raw material sintered rod is melted with an oxygen-acetylene combustion gas and the droplets are injected with an air jet.The raw material powder is A plasma process for supplying, melting, and spraying may be appropriately selected.
その後、上記導電体（Ａ′）の上面に、同じくイオンブ
レーティング法、プラズマＣＶＤ法、スパックリング法
、真空蒸着法、溶射法等の成膜法にてセラミックス絶縁
膜（１０）を堆積させる。このようにして得られたテー
プ状電線素材（７）を渦巻き形状に巻回する。そして、
超電導体が生成される温度領域で焼結し、その後徐冷す
ることにより、上記超電導コイル（６）を得ることがで
きる。Thereafter, a ceramic insulating film (10) is deposited on the upper surface of the conductor (A') using a film forming method such as an ion blasting method, a plasma CVD method, a spackling method, a vacuum evaporation method, or a thermal spraying method. The tape-shaped electric wire material (7) thus obtained is wound into a spiral shape. and,
The superconducting coil (6) can be obtained by sintering in a temperature range where superconductors are produced and then slowly cooling.
この超電導コイル（６）によれば、渦巻き形状に巻回し
た後に焼結しているので、第１図に示す実施例と同様、
超電導体（８）にひび割れ等の内部欠陥が生ずることが
ない。また、テープ状電線素材（７）の表面の一部（片
面）に予めセラミックス絶縁膜（１０）を被覆している
ので、渦巻き状に成形した後、テープ状電線素材（７）
同士の重ね合わせ面においてセラミックス絶縁膜（１０
）が介在する状態になる。According to this superconducting coil (6), since it is sintered after being wound into a spiral shape, similar to the embodiment shown in FIG.
Internal defects such as cracks do not occur in the superconductor (8). In addition, since a part of the surface (one side) of the tape-shaped electric wire material (7) is coated with the ceramic insulating film (10) in advance, after forming the tape-shaped electric wire material (7) into a spiral shape, the tape-shaped electric wire material (7)
Ceramic insulating film (10
) is present.
このセラミックス絶縁膜（１０）は焼結後も残留するの
で、互いに隣り合う巻線同士の絶縁性を保つことができ
る。さらに、セラミックス超電導体を水分、湿気、外傷
から保護する保護膜としての機能を果たすことができる
。Since this ceramic insulating film (10) remains even after sintering, the insulation between adjacent windings can be maintained. Furthermore, it can function as a protective film that protects the ceramic superconductor from water, moisture, and external damage.
なお、この発明の複合セラミックス超電導体は、上記実
施例に限定されるものでなく、例えば、複合セラミック
ス超電導体の形状としては、線状、テープ状に限らず、
基板状、シート状、あるいはブロック状等、超電導体の
用途等に応じて、種々の形態のものが使用できる。また
、導電体としては、セラミックス超電導体のみからなる
もであってもよい。その他この発明の要旨を変更しない
範囲内において、種々の設計変更を施すことが可能であ
る。Note that the composite ceramic superconductor of the present invention is not limited to the above embodiments, and for example, the shape of the composite ceramic superconductor is not limited to a linear shape, a tape shape,
Various forms can be used depending on the purpose of the superconductor, such as a substrate, a sheet, or a block. Further, the conductor may be made only of a ceramic superconductor. Various other design changes can be made without changing the gist of the invention.
く具体例１〉
Ｙ２０３１１２９ｇＳＢ ａ Ｃ０３３９００ｇ、およ
びＣｕ Ｏ２４００ｇを均一に混合し、９００℃で１２
時間熱処理して粉状の超電導原料を得、この混合粉体を
外径１５ｍｍ、内径９Ｉｎｍのステンレスパイプ中に充
填し、外径ｌｌｌ１ｍまで減面加工を施して伸線を行っ
た。Specific example 1> Y2031129gSB a C033900g and CuO2400g were uniformly mixed and heated at 900°C for 12
A powder superconducting raw material was obtained by heat treatment for a period of time, and this mixed powder was filled into a stainless steel pipe with an outer diameter of 15 mm and an inner diameter of 9 Inm, and the area was reduced to an outer diameter of 111 m, and wire drawing was performed.
そして、プラズマＣＶＤ炉内に、ＡＪＣＪ３をソースガ
スとし、Ｈ２ガスをキャリアガスとした混合ガスを流し
、平行平板電極に１３．５６ＭＨｚの高周波電圧を印加
してプラズマを発生させた。そして、このプラズマ中に
上記線状素材を配置し、５００℃の温度に保って表面に
３０μｍのＡｌ２Ｏ２膜を形成した。これを、コイル形
状に巻回し、大気中９４０℃で６時間熱処理した後徐冷
して、超電導コイルを得た。得られた超電導コイルを液
体チッ素で冷却して臨界電流を測定したところＩＯＡで
あり、Ａｌ２Ｏ２膜の絶縁耐圧を測定したところ５００
Ｖであった。なお、超電導体の組成分析を行ったところ
、Ｙｌ Ｂａ２ Ｃｕ３０７のペロブスカイト相であ
った。Then, a mixed gas containing AJCJ3 as a source gas and H2 gas as a carrier gas was flowed into the plasma CVD furnace, and a high frequency voltage of 13.56 MHz was applied to the parallel plate electrodes to generate plasma. The linear material was then placed in this plasma and kept at a temperature of 500° C. to form a 30 μm thick Al2O2 film on its surface. This was wound into a coil shape, heat-treated in the atmosphere at 940° C. for 6 hours, and then slowly cooled to obtain a superconducting coil. The obtained superconducting coil was cooled with liquid nitrogen and the critical current was measured to be IOA, and the dielectric strength voltage of the Al2O2 film was measured to be 500.
It was V. In addition, when the composition of the superconductor was analyzed, it was found to be a perovskite phase of Yl Ba2 Cu307.
く具体例２〉
Ｙ２０３１１２９ｇ５Ｂ ａ Ｃ０Ｃ０３３９Ｏ０およ
びＣｕ Ｏ２４００ｇを均一に混合し、９００℃で１２
時間熱処理して粉状の超電導原料を得、この混合粉体を
ステンレステープ上にプラズマ溶射して１００μｍ厚の
膜を積層した。この上から、上記と同じプラズマＣＶＤ
法により、１０μｍのＡｌ２Ｏ２膜を形成した。これを
、渦巻きコイル形状に巻回し、大気中９４０℃で６時間
熱処理した後徐冷して、超電導コイルを得た。得られた
超電導コイルの臨界温度は８８にであり、Ａｌ２Ｏ２膜
の絶縁耐圧を測定したところ１５０ｖであった。Specific example 2> Y2031129g5B a C0C0339O0 and CuO2400g were mixed uniformly and heated at 900°C for 12
A powder superconducting raw material was obtained by heat treatment for a period of time, and this mixed powder was plasma sprayed onto a stainless steel tape to form a 100 μm thick film. From above, the same plasma CVD as above
A 10 μm Al2O2 film was formed by the method. This was wound into a spiral coil shape, heat-treated in the atmosphere at 940° C. for 6 hours, and then slowly cooled to obtain a superconducting coil. The critical temperature of the obtained superconducting coil was 88, and the dielectric strength voltage of the Al2O2 film was measured to be 150V.
〈発明の効果〉
以上のように、この発明の複合セラミックス超電導体は
、表面にセラミックス絶縁膜が被覆されているものであ
るから、良好な絶縁性を確保することができるとともに
、耐熱性に優れることから、所望形状に成形した後、焼
結や熱処理を施すこともできる。しかも、表面のセラミ
ックス絶縁膜については、これを緻密に形成することも
容易であるから、導電体を湿気等から有効に保護するこ
とができるとともに、非常に硬いことから、導電体を外
傷から確実に保護することもできる。<Effects of the Invention> As described above, the composite ceramic superconductor of the present invention, whose surface is coated with a ceramic insulating film, can ensure good insulation properties and has excellent heat resistance. Therefore, after forming into a desired shape, sintering or heat treatment can be performed. Moreover, since the ceramic insulating film on the surface can be easily formed densely, it can effectively protect the conductor from moisture, etc., and since it is extremely hard, it can protect the conductor from external damage. It can also be protected.
したがって、任意の形状に形成することができるととも
に、耐熱性、耐水性等の緒特性に優れ、長期間に亘って
安定した絶縁性を確保することができる等、種々優れた
効果を奏する複合セラミ・ソクス超電導体を提供するこ
とができる。Therefore, composite ceramics can be formed into any shape, have excellent properties such as heat resistance and water resistance, and have various excellent effects such as being able to ensure stable insulation over a long period of time.・Can provide SOCS superconductors.
第１図は超電コイルの一実施例を示す正面図、第２図は
超電コイルを構成する電線素材の断面図、
第３図はテープ状電線素材を渦巻き状に巻回した超電導
コイルを示す斜視図、
第４図はテープ状電線素材の断面図。
（１）・・・複合セラミックス超電導体としての超電導
コイル、
（３） （８）・・・セラミックス超電導体、（５）（
１０）・・・セラミックス絶縁膜、（６）・・・複合セ
ラミックス超電導体としての超電導テープ、
（Ａ） 、 （Ａ’）・・・導電体
特許出願人 住友電気工業株式会社
代 理 人 弁理士 亀 井 弘 勝
（ほか３名）
第１図 第２図Fig. 1 is a front view showing an example of a superconducting coil, Fig. 2 is a cross-sectional view of the wire material constituting the superconducting coil, and Fig. 3 is a superconducting coil in which tape-shaped wire material is spirally wound. FIG. 4 is a sectional view of the tape-shaped electric wire material. (1)...Superconducting coil as composite ceramic superconductor, (3) (8)...Ceramic superconductor, (5)(
10) Ceramic insulating film, (6) Superconducting tape as composite ceramic superconductor, (A), (A') Conductor patent applicant Sumitomo Electric Industries Co., Ltd. Agent Patent attorney Hirokatsu Kamei (and 3 others) Figure 1 Figure 2
Claims (1)
セラミックス超電導体からなる導 電体の一部または全体が、セラミックス絶縁膜で被覆さ
れていることを特徴とする複合セラミックス超電導体。 ＡａＢｂＣｃ（ I ） （式中、Ａは周期律表 I ａ族元素、IIａ族元素および
IIIａ族元素より選択された少なくとも１種の元素であ
り、Ｂは周期律表 I ｂ族元素、IIｂ族元素およびIIIｂ
族元素より選択された少なくとも１種の元素であり、Ｃ
は酸素、窒素、フッ素、炭素および硫黄から選択された
少なくとも１種の元素である） ２、式（ I ）中のＡが、周期律表 I ａ族元素、IIａ族
元素およびIIIａ族元素より選択された少なくとも２種
の元素である上記特許請求の範囲第１項記載の複合セラ
ミックス超電導体。 ３、セラミックス絶縁膜が、Ａｌ＿２Ｏ＿３、ＳｉＯ＿
２、Ｓｉ＿３Ｎ＿４のうち何れか１種からなる上記特許
請求の範囲第１項記載の複合セラミックス超電導体。[Claims] 1. A composite characterized in that at least a part or the whole of a conductor made of a ceramic superconductor having a composition represented by the following general formula (I) is coated with a ceramic insulating film. Ceramic superconductor. AaBbCc (I) (wherein A is a group Ia element of the periodic table, a group IIa element, and
At least one element selected from group IIIa elements, and B is an element selected from group Ib elements, group IIb elements, and IIIb elements of the periodic table.
At least one element selected from group elements, C
is at least one element selected from oxygen, nitrogen, fluorine, carbon, and sulfur) 2. A in formula (I) is selected from group Ia elements, group IIa elements, and group IIIa elements of the periodic table. The composite ceramic superconductor according to claim 1, which is at least two types of elements. 3. Ceramic insulation film is Al_2O_3, SiO_
2. The composite ceramic superconductor according to claim 1, which is made of any one of Si_3N_4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62128734A JPS63292517A (en) | 1987-05-26 | 1987-05-26 | Compound ceramic superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62128734A JPS63292517A (en) | 1987-05-26 | 1987-05-26 | Compound ceramic superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63292517A true JPS63292517A (en) | 1988-11-29 |
Family
ID=14992130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62128734A Pending JPS63292517A (en) | 1987-05-26 | 1987-05-26 | Compound ceramic superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63292517A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064809A (en) * | 1988-12-23 | 1991-11-12 | Troy Investments, Inc. | Method of making a Josephson junction with a diamond-like carbon insulating barrier |
| JP2008511145A (en) * | 2004-08-23 | 2008-04-10 | シーメンス アクチエンゲゼルシヤフト | Rectangular coil made of strip superconductor having high TC superconductor material and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63259917A (en) * | 1987-04-17 | 1988-10-27 | Furukawa Electric Co Ltd:The | Superconductive moulded matter |
| JPS63281318A (en) * | 1987-05-12 | 1988-11-17 | Toshiba Corp | Manufacture of compound superconductive wire |
| JPS63284720A (en) * | 1987-05-14 | 1988-11-22 | Fujikura Ltd | Superconducting wire |
-
1987
- 1987-05-26 JP JP62128734A patent/JPS63292517A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63259917A (en) * | 1987-04-17 | 1988-10-27 | Furukawa Electric Co Ltd:The | Superconductive moulded matter |
| JPS63281318A (en) * | 1987-05-12 | 1988-11-17 | Toshiba Corp | Manufacture of compound superconductive wire |
| JPS63284720A (en) * | 1987-05-14 | 1988-11-22 | Fujikura Ltd | Superconducting wire |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064809A (en) * | 1988-12-23 | 1991-11-12 | Troy Investments, Inc. | Method of making a Josephson junction with a diamond-like carbon insulating barrier |
| JP2008511145A (en) * | 2004-08-23 | 2008-04-10 | シーメンス アクチエンゲゼルシヤフト | Rectangular coil made of strip superconductor having high TC superconductor material and use thereof |
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