JP2685053B2 - Superconducting composite material - Google Patents
Superconducting composite materialInfo
- Publication number
- JP2685053B2 JP2685053B2 JP63022900A JP2290088A JP2685053B2 JP 2685053 B2 JP2685053 B2 JP 2685053B2 JP 63022900 A JP63022900 A JP 63022900A JP 2290088 A JP2290088 A JP 2290088A JP 2685053 B2 JP2685053 B2 JP 2685053B2
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- yttrium
- acid
- fluoride
- coating layer
- 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.)
- Expired - Fee Related
Links
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
- Physical Vapour Deposition (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Containers, Films, And Cooling For Superconductive Devices (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 〔概 要〕 本発明は、イットリウムとランタノイドとから成る群
から選択された少なくとも１種の元素を含有する超伝導
体を含んで成る超伝導複合材料に関し、 水中および酸中での超伝導体の溶解を防止することに
よって、損傷なしに種々の加工を施すことができる耐
水、耐酸性の優れた超伝導材料を提供することを目的と
し、 イットリウムとランタノイドとから成る群から選択さ
れた少なくとも１種の第１の元素を含有する超伝導体、
および該超伝導体の表面を覆った、イットリウムとタン
タノイドとから成る群から選択された少なくとも１種の
第２の元素のフッ化物の被覆層を含んで構成する。DETAILED DESCRIPTION OF THE INVENTION [Outline] The present invention relates to a superconducting composite material containing a superconductor containing at least one element selected from the group consisting of yttrium and lanthanoids. A group consisting of yttrium and lanthanoids for the purpose of providing a superconducting material excellent in water resistance and acid resistance that can be subjected to various processing without damage by preventing dissolution of the superconductor in A superconductor containing at least one first element selected from
And a coating layer of a fluoride of at least one second element selected from the group consisting of yttrium and tantanoide, covering the surface of the superconductor.
本発明は、イットリウムとランタノイドとから成る群
から選択された少なくとも１種の元素を含有する超伝導
体を含んで成る超伝導複合材料に関する。The present invention relates to a superconducting composite material containing a superconductor containing at least one element selected from the group consisting of yttrium and lanthanoids.
このような超伝導体としては、たとえばＹ−Ba−Cu−
O,La−Ba−Cu−O,La−Sr−Cu−Ｏ等のような、周期律表
III B族元素（あるいはランタノイド元素）−II A族元
素−Cu−Ｏからなる酸化物系セラミックスが最近開発さ
れている。これらの超伝導体は、それ以前に知られてい
た金属超伝導体の臨界温度が高々20K程度であったのに
対して、90K程度以上の高い臨界温度を有するため、超
伝導マグネット、超伝導配線、SQUID磁束計等として超
伝導体を実用化できる可能性が飛躍的に高まった。As such a superconductor, for example, Y-Ba-Cu-
O, La-Ba-Cu-O, La-Sr-Cu-O, etc.
Oxide-based ceramics composed of III group B element (or lanthanoid element) -II group A element-Cu-O have been recently developed. These superconductors have a high critical temperature of 90K or higher, whereas the previously known metal superconductor had a critical temperature of 20K at the highest. The possibility of practical application of superconductors as wiring and SQUID magnetometers has dramatically increased.
超伝導体を上記あるいはその他の用途で実用化するに
は、単体でおよび／または構成部材として組込まれた状
態で種々の加工を施す必要がある。特に、超伝導体を含
んだ素子等を洗浄等のために水および硝酸、塩酸、フッ
酸等の酸を用いて処理する加工は頻繁に行なわれる。そ
の際、前記のような超伝導体は多くの場合、水にも上記
のような酸にも容易に溶解するため、加工過程で著しい
損傷を受け、優れた超伝導特性が損なわれたり、超伝導
体全体が溶失したりする危険が極めて高い。In order to put the superconductor into practical use for the above purposes and other purposes, it is necessary to perform various processes as a single body and / or in a state of being incorporated as a constituent member. In particular, a process of treating an element containing a superconductor with water and an acid such as nitric acid, hydrochloric acid or hydrofluoric acid for cleaning is frequently performed. At that time, in many cases, the above-mentioned superconductors are easily dissolved in water and the above-mentioned acids, so that they are significantly damaged in the process of processing, and excellent superconducting properties are impaired. There is a very high risk of the entire conductor melting away.
超伝導体が水や上記の酸に容易に溶解することは、超
伝導体の組成・構造に基ずく固有の性質である。一方、
超伝導体の組成・構造は、最も優れた超伝導特性が得ら
れる最適範囲にあり、かつこの範囲が極めて狭いので、
耐水、耐酸性を高めるために組成・構造を調整すること
は実際上不可能である。そのため、用途に応じて必要な
加工を行なうことが極めて制約され、超伝導体の実用化
が阻害されるという問題があった。The fact that a superconductor easily dissolves in water or the above-mentioned acid is an inherent property based on the composition and structure of the superconductor. on the other hand,
The composition and structure of superconductors is in the optimum range where the best superconducting properties are obtained, and this range is extremely narrow, so
It is practically impossible to adjust the composition and structure to increase water resistance and acid resistance. Therefore, there is a problem in that the necessary processing is extremely restricted depending on the application and the practical use of the superconductor is hindered.
そこで本発明は、水中および酸中での超伝導体の溶解
を防止することによって、損傷なしに種々の加工を施す
ことができる耐水耐酸性の優れた超伝導材料を提供する
ことを目的とする。Therefore, an object of the present invention is to provide a superconducting material excellent in water resistance and acid resistance, which can be subjected to various processes without damage by preventing dissolution of the superconductor in water and acid. .
上記の目的は、本発明によって、イットリウムとラン
タノイドとから成る群から選択された少なくとも１種の
第１の元素を含有する超伝導体、および該超伝導体の表
面を覆った、イットリウムとランタノイドとから成る群
から選択された少なくとも１種の第２の元素のフッ化物
の被覆層を含んで成る超伝導複合材料によって達成され
る。According to the present invention, the above object is to provide a superconductor containing at least one first element selected from the group consisting of yttrium and lanthanoids, and yttrium and lanthanoids covering the surface of the superconductor. It is achieved by a superconducting composite material comprising a coating layer of at least one second element fluoride selected from the group consisting of:
本発明の超伝導複合材料においては、超伝導体中に含
有される上記第１の元素と、被覆層のフッ化物を形成す
る上記第２の元素とは必ずしも同一の元素である必要は
なく、それぞれイットリウムとランタノイドとから成る
群から選択された少なくとも１種の元素であればよい。In the superconducting composite material of the present invention, the first element contained in the superconductor and the second element forming the fluoride of the coating layer do not necessarily have to be the same element, At least one element selected from the group consisting of yttrium and lanthanoids may be used.
第１の元素と第２の元素とを同一の元素とすることは
有利である。これらが同一の元素であれば、超伝導体と
被覆層の界面で熱拡散や反応が起きても、界面付近の領
域での組成変動は最小限に抑制される。また、被覆層を
形成するための原料として超伝導体の原料と同一もしく
は類似の物質を用いることができるので、準備する原料
の種類を最小限にでき、更に、後に説明するように、被
覆層を超伝導体と同一もしくは類似の方法で形成するこ
とができる。It is advantageous to make the first element and the second element the same element. If these are the same element, even if thermal diffusion or reaction occurs at the interface between the superconductor and the coating layer, the composition variation in the region near the interface is suppressed to the minimum. Further, since the same or similar substance as the raw material of the superconductor can be used as the raw material for forming the coating layer, the type of raw material to be prepared can be minimized, and further, as will be described later, the coating layer Can be formed in the same or similar way as the superconductor.
超伝導体が第１の元素としてイットリウムを含有する
YBa2Cu3O7-X（０≦ｘ≦１）であり、被覆層が第１の元
素と同一の第２の元素Ｙのフッ化物YF3で形成されてい
ることが最も有利である。ここで、ｘが小さい程（７−
ｘが７に近い程）優れた超伝導特性が発揮される。Superconductor contains yttrium as the first element
It is YBa 2 Cu 3 O 7-X (0 ≦ x ≦ 1), and it is most advantageous that the coating layer is formed of the fluoride YF 3 of the second element Y which is the same as the first element. Here, the smaller x is (7-
(The closer x is to 7, the more excellent superconducting properties are exhibited.
本発明においては、イットリウムとランタノイドとか
ら成る群から選択された少なくとも１種の元素を含有す
る超伝導体の表面を、上記群から選択された同一もしく
は別の元素のフッ化物の層で被覆することによって、加
工に用いられる水および酸から超伝導体を保護する。In the present invention, the surface of a superconductor containing at least one element selected from the group consisting of yttrium and lanthanoids is coated with a layer of fluoride of the same or another element selected from the above group. This protects the superconductor from water and acids used in processing.
本発明者は、次に一例として説明する試験を行なった
結果、上記フッ化物の被覆層の保護作用について基礎的
な知見を得た。As a result of performing a test described below as an example, the present inventor obtained basic knowledge about the protective action of the above-mentioned fluoride coating layer.
たとえば、約1cm×1cm面積の基盤上に厚さ5000ÅのＹ
−Ba−Cu−Ｏ系超伝導体の膜を堆積させ、これを硝酸1:
水１の水溶液0.5ml中に浸漬すると、約30秒でこの膜は
完全に溶解した。次に、上記と同様の膜について酸を硝
酸＋フッ酸＋水（4:1:5）0.5mlに変えて同様の操作を行
うと、完全に溶解するには最も早い場合でも30分を要し
た。硝酸の一部をフッ酸に置きかえることにより、溶解
時間が60倍となり耐酸性が著しく向上した。これはフッ
酸中のフッ化物イオンがＹ−Ba−Cu−ＯのＹと反応して
フッ化イットリウム（YF3）を形成したためである。For example, Y of 5000 Å thickness on the base of about 1 cm x 1 cm area
A -Ba-Cu-O-based superconductor film was deposited and nitric acid 1:
When immersed in 0.5 ml of an aqueous solution of water 1, the film completely dissolved in about 30 seconds. Next, for the same membrane as above, changing the acid to 0.5 ml of nitric acid + hydrofluoric acid + water (4: 1: 5) and performing the same operation, it took 30 minutes at the earliest to completely dissolve it. did. By replacing part of the nitric acid with hydrofluoric acid, the dissolution time was 60 times longer and the acid resistance was significantly improved. This is because the fluoride ions in the hydrofluoric acid was reacted with Y-Ba-Cu-O of Y to form a yttrium fluoride (YF 3).
また、Ｙ−Ba−Cu−ＯのＹの原料である酸化イットリ
ウム（Y2O3）によりＹとＦとの反応生成物の不溶性試験
を行なった。Further, the insolubility test of the reaction product of Y and F was conducted using yttrium oxide (Y 2 O 3 ) which is a raw material of Y of Y-Ba-Cu-O.
酸化イットリウム（Y2O3）の粉末を圧縮整形してペレ
ットを作製し、これをフッ酸（１＋１）1ml中に２分間
浸した後洗浄し、洗液と溶液をあわせて定容後、ICP発
光分光分析装置でＹの発光強度を観測した。この同じY2
O3ペレットを再度フッ酸（１＋１）1mlに浸漬（２分
間）し、２回目の溶出量と１回目の溶出量をICPの発光
強度で比較した。その結果Ｙの発光強度は半減した。こ
れは１回目の浸漬によりペレットの表面にYF3が形成さ
れ２回目の浸漬での溶出を抑制したためである。Yttrium oxide (Y 2 O 3 ) powder is compressed and shaped to form pellets, which are immersed in 1 ml of hydrofluoric acid (1 + 1) for 2 minutes and then washed. The emission intensity of Y was observed with an emission spectroscopic analyzer. This same Y 2
The O 3 pellet was again immersed in 1 ml of hydrofluoric acid (1 + 1) (for 2 minutes), and the second elution amount and the first elution amount were compared by the emission intensity of ICP. As a result, the emission intensity of Y was halved. This is because YF 3 was formed on the surface of the pellet by the first immersion and the elution in the second immersion was suppressed.
ただし、この試験で用いたY2O3ペレットは粉末を圧縮
整形したままの状態であり粒界が粗いので、各粒子の表
面がYF3となっても、ペレット表面を覆う被覆層を形成
していなかった。そのため、ペレットの内部の未反応Y2
O3まで２回目のフッ酸が浸透してＹを溶出した。However, the Y 2 O 3 pellets used in this test are in the state where the powder is still compressed and shaped, and the grain boundaries are rough, so even if the surface of each particle becomes YF 3 , a coating layer that covers the pellet surface is formed. Didn't. Therefore, unreacted Y 2 inside the pellet
The second hydrofluoric acid penetrated to O 3 to elute Y.
本発明は上記知見に基ずいてなされた。本発明に従っ
たフッ化物の被覆層は水および硝酸、塩酸、フッ酸等に
対して保護作用を有する。加工に用いようとする酸に対
するフッ化物の保護作用の有無は、上に説明したように
原料である酸化物等のペレットのフッ酸中もしくはフッ
酸含有酸中での浸漬試験等によって予め判定することが
できる。The present invention was made based on the above findings. The fluoride coating layer according to the invention has a protective action against water and nitric acid, hydrochloric acid, hydrofluoric acid and the like. The presence or absence of the protective effect of fluoride against the acid to be used for processing is determined in advance by the immersion test or the like in the hydrofluoric acid or the hydrofluoric acid-containing acid of the pellets such as the oxide as the raw material as described above. be able to.
上記試験ではイットリウムを含有する超伝導体につい
ての例を説明したが、イットリウムの代りにまたはイッ
トリウムと共にランタノイドを含有する超伝導体、たと
えばLa−Ba−Cu−Ｏ系、La−Sr−Cu−Ｏ系等の超伝導体
の場合にも、化学的性質がイットリウムと極めて近いラ
ンタノイドのフッ化物が同様の保護作用を発揮する。In the above test, an example of a superconductor containing yttrium was explained, but a superconductor containing a lanthanoid instead of yttrium or together with yttrium, for example, La-Ba-Cu-O system, La-Sr-Cu-O. Also in the case of a superconductor such as a system, a lanthanide fluoride having a chemical property extremely similar to that of yttrium exhibits the same protective effect.
また、超伝導体中に含まれるイットリウムまたはラン
タノイドのフッ化物の保護作用について説明したが、超
伝導体中に含まれないイットリウムまたはランタノイド
のフッ化物にも同様の保護作用がある。たとえば、La−
Ba−Cu−Ｏ系の超伝導体の表面をYF3の層やLa以外のラ
ンタノイドのフッ化物の層で被覆してもよい。Further, the protective action of yttrium or lanthanoid fluoride contained in the superconductor has been described, but yttrium or lanthanoid fluoride not contained in the superconductor also has the same protective action. For example, La−
Ba-Cu-O system of the surface of the superconductor may be covered with a layer of a fluoride of a lanthanoid except YF 3 layers and La.
更に、イットリウムまたはランタノイドのうちの複数
の元素のフッ化物で被覆層を形成してもよい。Further, the coating layer may be formed of a fluoride of plural elements of yttrium or lanthanoid.
本発明の被覆層は、スパッタリング法、蒸着法、CVD
法等の通常、超伝導体の形成に用いられる方法によっ
て、超伝導体の表面に堆積・形成させられる。The coating layer of the present invention is formed by a sputtering method, a vapor deposition method, a CVD method.
It is deposited and formed on the surface of the superconductor by a method usually used for forming a superconductor such as a method.
本発明は、イットリウムとランタノイドとから成る群
から選択された少なくとも１種の第１の元素を含有する
超伝導体の表面を、上記群から選択された少なくとも１
種の第２の元素のフッ化物の層で被覆して、水および酸
に対するこのフッ化物の保護作用によって超伝導体の溶
解を防止する。したがって、水および／または酸を用い
る種々の加工において超伝導体が損傷を受けない。The present invention provides a surface of a superconductor containing at least one first element selected from the group consisting of yttrium and lanthanoids, at least 1 selected from the above group.
Coating with a layer of a fluoride of the second element of the seed prevents the dissolution of the superconductor by the protective action of this fluoride against water and acids. Therefore, the superconductor is not damaged in various processes using water and / or acid.
以下に添付図面を参照し、実施例によって本発明を更
に詳しく説明する。Hereinafter, the present invention will be described in more detail by way of examples with reference to the accompanying drawings.
〔実施例１〕 第１図に本発明の超伝導複合材料の一実施例を示す。Example 1 FIG. 1 shows an example of the superconducting composite material of the present invention.
サファイア基板11の上に、Y1Ba2Cu3O6.9の組成を有す
る超伝導体薄膜12（厚さ4000Å）を高周波マグネトロン
スパッタによって形成し、更にその上にYF3の被覆層13
（厚さ4000Å）をプラズマCVDによって形成した。A superconductor thin film 12 (thickness 4000 Å) having a composition of Y 1 Ba 2 Cu 3 O 6.9 is formed on a sapphire substrate 11 by high frequency magnetron sputtering, and a YF 3 coating layer 13 is further formed thereon.
(Thickness 4000Å) was formed by plasma CVD.
〔実施例２〕 実施例１と同様にサファイア基板11′の上にY1Ba2Cu3
O６・９の組成を有する超伝導体薄膜12′を形成した。
次にその上にLaF3の被覆層13′（厚さ6000Å）をエレク
トロンビーム蒸着法によって形成した。Example 2 Similar to Example 1, Y 1 Ba 2 Cu 3 was formed on the sapphire substrate 11 ′.
To form a superconductor film 12 'having a composition of O 6 · 9.
Next, a LaF 3 coating layer 13 ′ (thickness 6000Å) was formed thereon by electron beam evaporation.
実施例１および２で得られた超伝導体複合材料を硝
酸、フッ酸、塩酸（いずれも酸：水＝1:1）の溶液中に
それぞれ１時間浸漬した。浸漬後、光学顕微鏡および走
査型電子顕微鏡によって観察した結果、溶解による損傷
の発生は全く認められなかった。また、浸漬後の溶液に
ついてIPC分析を行なったが、超伝導体の元素は全く検
出されなかった。The superconductor composite materials obtained in Examples 1 and 2 were immersed in a solution of nitric acid, hydrofluoric acid and hydrochloric acid (both acid: water = 1: 1) for 1 hour. As a result of observation with an optical microscope and a scanning electron microscope after the immersion, no damage due to dissolution was observed. Moreover, IPC analysis was performed on the solution after immersion, but no element of the superconductor was detected.
比較として、実施例１と同様にサファイア基板上に超
伝導体薄膜を形成したまま、被覆層は形成しない試料に
ついて、上記と同様の溶液に浸漬した。いずれの溶液で
も浸漬後15〜30秒で超伝導体薄膜は完全に溶解した。For comparison, as in Example 1, a sample in which the coating layer was not formed while the superconductor thin film was formed on the sapphire substrate was immersed in the same solution as above. The superconductor thin film was completely dissolved within 15 to 30 seconds after dipping in any solution.
本発明の超伝導複合材料は水にも酸にも溶解しないの
で、超伝導体を損傷することなく必要な種々の加工を施
すことができるという効果を奏するため、広範な用途で
の超伝導体の実用化に多大な寄与をするものである。Since the superconducting composite material of the present invention is insoluble in water and acid, it has the effect that various necessary processes can be performed without damaging the superconductor. Will make a great contribution to the practical application of.
第１図は本発明の超伝導複合材料の実施例を示す断面図
である。 11,11′……サファイア基板、 12,12′……超伝導体薄膜、 13,13′……被覆層。FIG. 1 is a sectional view showing an embodiment of the superconducting composite material of the present invention. 11,11 '... Sapphire substrate, 12,12' ... Superconductor thin film, 13,13 '... Coating layer.
Claims (1)
から選択された少なくとも１種の第１の元素を含有する
超伝導体、および該超伝導体の表面を覆った、イットリ
ウムとランタノイドとから成る群から選択された少なく
とも１種の第２の元素のフッ化物の被覆層を含んで成る
超伝導複合材料。1. A superconductor containing at least one first element selected from the group consisting of yttrium and lanthanoids, and yttrium and lanthanoids covering the surface of the superconductor. A superconducting composite material comprising a coating layer of at least one selected second element fluoride.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63022900A JP2685053B2 (en) | 1988-02-04 | 1988-02-04 | Superconducting composite material |
| US08/261,246 US6238774B1 (en) | 1988-02-04 | 1994-06-14 | Protection of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63022900A JP2685053B2 (en) | 1988-02-04 | 1988-02-04 | Superconducting composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01198465A JPH01198465A (en) | 1989-08-10 |
| JP2685053B2 true JP2685053B2 (en) | 1997-12-03 |
Family
ID=12095522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63022900A Expired - Fee Related JP2685053B2 (en) | 1988-02-04 | 1988-02-04 | Superconducting composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2685053B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3017301B2 (en) * | 1991-02-18 | 2000-03-06 | 大阪酸素工業株式会社 | Method of forming passivation film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63241825A (en) * | 1987-03-30 | 1988-10-07 | Fujikura Ltd | Manufacture of superconductor |
| JPH01100813A (en) * | 1987-10-14 | 1989-04-19 | Fujikura Ltd | High temperature superconducting material |
-
1988
- 1988-02-04 JP JP63022900A patent/JP2685053B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01198465A (en) | 1989-08-10 |
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