JP4120955B2 - Synthesis Method of Superconducting Boride MgB2 by Electrodeposition from Melt - Google Patents
Synthesis Method of Superconducting Boride MgB2 by Electrodeposition from Melt Download PDFInfo
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- JP4120955B2 JP4120955B2 JP2002163764A JP2002163764A JP4120955B2 JP 4120955 B2 JP4120955 B2 JP 4120955B2 JP 2002163764 A JP2002163764 A JP 2002163764A JP 2002163764 A JP2002163764 A JP 2002163764A JP 4120955 B2 JP4120955 B2 JP 4120955B2
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- mgb
- superconducting
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- wire
- electrodeposition
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- 238000004070 electrodeposition Methods 0.000 title claims description 7
- 238000001308 synthesis method Methods 0.000 title description 2
- 229910020073 MgB2 Inorganic materials 0.000 title 1
- 238000000034 method Methods 0.000 claims description 15
- 239000010409 thin film Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 magnesium halide Chemical class 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002659 electrodeposit Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002591 computed tomography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、超伝導ホウ化物ＭｇＢ2（Ｔｃ＝３９Ｋ）超伝導薄膜、及び超伝導線材の作製方法に関するものである。
【０００２】
【従来の技術】
超伝導薄膜は超伝導量子干渉素子（ＳＱＵＩＤ）として高感度な磁束計に用いられる。又、超伝導線材は超伝導電磁磁石として強磁場の発生に使われる。両者とも医療におけるＣＴスキャン装置の他、学術研究等で広く利用されている。
【０００３】
【発明が解決しようとする課題】
先頃、金属間化合物として最高のＴｃ＝３９Ｋを示すホウ化物ＭｇＢ２が発見され、従来のＡ１５型金属間化合物（Ｔｃ＝１５Ｋ程度）に代わるものとしてその応用が期待されている。
【０００４】
ＭｇＢ2は、しかし、構成元素ＭｇとＢの極端な蒸気圧の違いから、単相バルク試料の合成すら難しいのが現状である。超伝導体の実用に不可欠な線材作製技法、又は素子化に必要な薄膜作製技術は、現在まで得られていない。
【０００５】
【課題を解決するための手段】
本発明は、簡単な装置構成により、ＭｇＢ2を融液中から電気析出法（電析法）により薄膜状に合成する手法を提供するものである。この手法を最適化することにより、どのような形状の基板金属に対してもＭｇＢ2を一様な厚みで育成できる。
【０００６】
即ち、本発明は、マグネシウムハロゲン化物、フッ化ホウ化マグネシウム及びマグネシウムのホウ酸塩からなる粉体混合物を耐熱性ボートに充填し、この混合物中に負電極及び正電極を挿入し、これらを加熱炉中で不活性ガス雰囲気下で加熱してボート中の混合物を熔融して融液とした後、両電極間に直流電流を印加し、負電極上にＭｇＢ２を析出させることからなる超伝導ホウ化物ＭｇＢ２の融液からの電析法による合成方法である。
【０００７】
したがって、予め線状に成形した金属線上にＭｇＢ2をメッキすることにより、ＭｇＢ2の線材を作製することができる。又、平面基板上への育成も可能である。即ち、ＭｇＢ2を利用したジョセフソン素子等、薄膜構成を必要とする系の作製に対しても有力である。
【０００８】
【発明の実施の形態】
本発明は、新物質合成実験の途上、いくつかの合成方法を試みるなかで、電解法／電析法による難合成物質の合成法として開発されたものである。ＭｇＢ2は、非常に蒸気圧の高いＭｇと逆に非常に融点の高いホウ素の化合物であるが、そこで行われた一連の高蒸気圧物質合成の試行過程において、本発明は、電気析出法を使用してＭｇＢ2を合成する方法を見いだした。
【０００９】
又、本発明は、現在盛んに用いられている真空蒸着等の高度且つ高価な装置を用いた製膜法と違い、メッキ用の僅かな装置だけで簡単にＭｇＢ2の膜を作製することを可能にする。それだけでなく、真空蒸着では不可能な基板面への製膜も可能である。これは、例えば、初めからコイル状に成形した金属線にメッキを施すことにより、ＭｇＢ2超伝導体マグネットを作製することができることを意味している。
【００１０】
更に又、本発明においては、実施例に示されるように、ＭｇＣｌ2／Ｍｇ（ＢＦ4）2６Ｈ2Ｏ／ＭｇＢ2Ｏ4を混合系を用いることにおいて、ＭｇＢ2の合成が可能であった。融体の融点を下げる目的で、アルカリ金属ホウ酸塩の添加が有効である。電極材料としては、実施例ではＰｔ／Ａｕを使用したが、他の金属／導電性物質も使用可能である。
【００１１】
【実施例】
市販の試薬ＭｇＣｌ2、Ｍｇ（ＢＦ4）2６Ｈ2Ｏ、及びＭｇＢ2Ｏ4を重量比１０：１：１にて総量２．５ｇ秤量する（以下粉末試料と呼ぶ）。アルミナボートの一端に直径１ｍｍの白金線をボート底に這わせるように固定する。同様に、ボートの反対の端に同径の金を固定する。白金線及び金線それぞれに直径０．３ｍｍの金線（以下リード線と呼ぶ）を圧着する。
【００１２】
粉末試料をボートに満たした後、これを石英炉心管を備えた横型電気炉に入れる。炉心管の一端をふさぐゴム栓にチューブを取り付け、アルゴンガスラインにつなぐ。炉心管の他端のゴム栓には排気用のチューブに加え、二つ穴のガイシを挿入する。ガイシを介してリード線を炉心管外部に導き、直流電源に接続する。リード線が互いに触れないよう注意を払う。白金線を負極、金線を正極に結合する。
【００１３】
アルゴンガスを１リットル毎分程度流しながら炉温度を６００℃まで上げる。粉末試料は融体となる。リード線に４Ｖ直流電圧を印加、数百ミリアンペアの通電を確認したらそのまま数時間静置する。数時間後、炉温度を常温に戻し、ボートを取出す。フラックスを除くため、蒸留水にボートを浸ける。フラックス除去後、黒色物質（ＭｇＢ2）に被覆された白金線を得た。
【００１４】
白金線上に育成されたＭｇＢ2の磁化率・温度曲線を示すと図１のとおりである。測定磁場は２０ガウスで、無磁場中冷却（ＺＦＣ）、磁場中冷却（ＦＣ）それぞれの曲線を示している。磁気的特性として、３７Ｋにおいて磁化率曲線に特異点がみられるが、これがＭｇＢ2の超電導転換に対応している。
【００１５】
【発明の効果】
従来の真空蒸着装置を用いた大がかりな製膜処理に比べて、本発明の簡単な機構の装置を使用することにより、合成困難なＭｇＢ2の薄膜、線材の作製が極めて低コストで可能となる。
【００１６】
即ち、本発明により、現在盛んに用いられている真空蒸着等の高度且つ高価な装置を用いた製膜法と違い、メッキ用の僅かな装置だけで簡単にＭｇＢ2の膜を作成することを可能にする。それだけでなく、真空蒸着では不可能な基板面への製膜も可能である。これは、例えば、初めからコイル状に成形した金線にメッキを施すことにより、ＭｇＢ2超伝導マグネットを作製することができることを意味している。
【００１７】
又、ＭｇＢ2薄膜は超伝導量子干渉素子（ＳＱＵＩＤ）として高感度な磁束計に用いられる。その超伝導線材は超伝導電磁磁石として強磁場の発生に使用される。両者とも医療におけるＣＴスキャン装置の他、学術研究等で利用される。
【図面の簡単な説明】
【図１】 白金線上に育成されたＭｇＢ2の磁化率・温度曲線を示すと図１のとおりである。
【図２】 本発明の方法でＭｇＢ2を作製する装置の図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a superconducting boride MgB 2 (Tc = 39K) superconducting thin film and a method for producing a superconducting wire.
[0002]
[Prior art]
A superconducting thin film is used for a highly sensitive magnetometer as a superconducting quantum interference device (SQUID). The superconducting wire is used as a superconducting electromagnetic magnet to generate a strong magnetic field. Both are widely used in academic research in addition to medical CT scanning devices.
[0003]
[Problems to be solved by the invention]
Recently, a boride MgB 2 showing the highest Tc = 39K as an intermetallic compound was discovered, and its application is expected as an alternative to the conventional A15 type intermetallic compound ( Tc = about 15K).
[0004]
However, MgB 2 is difficult to synthesize even a single-phase bulk sample due to the extreme vapor pressure difference between the constituent elements Mg and B. A wire material manufacturing technique essential for practical use of a superconductor or a thin film manufacturing technique necessary for device formation has not been obtained so far.
[0005]
[Means for Solving the Problems]
The present invention provides a method for synthesizing MgB 2 from a melt into a thin film by an electrodeposition method (electrodeposition method) with a simple apparatus configuration. By optimizing this method, it is possible to grow MgB 2 with a uniform thickness for any shape of substrate metal.
[0006]
That is, the present invention fills a heat-resistant boat with a powder mixture comprising magnesium halide , magnesium fluoroborate and magnesium borate, and inserts a negative electrode and a positive electrode into the mixture and heats them. Superconducting boron consisting of heating in an inert gas atmosphere in a furnace to melt the mixture in the boat to form a melt, and then applying a direct current between both electrodes to deposit MgB 2 on the negative electrode This is a synthesis method by an electrodeposition method from a molten MgB 2 solution.
[0007]
Therefore, an MgB 2 wire can be produced by plating MgB 2 on a metal wire previously formed into a linear shape. It is also possible to grow on a flat substrate. That is, it is effective for the production of a system that requires a thin film structure, such as a Josephson element using MgB 2 .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention has been developed as a method for synthesizing hardly synthetic substances by electrolysis / electrodeposition, while trying several synthetic methods in the course of new substance synthesis experiments. MgB 2 is a compound of boron having a very high melting point, as opposed to Mg having a very high vapor pressure. In a series of trials for synthesizing a high vapor pressure material conducted there, the present invention is based on an electrodeposition method. A method for synthesizing MgB 2 was found.
[0009]
Further, the present invention is different from the film forming method using a high-priced apparatus such as vacuum deposition that is widely used at present, and can easily form a MgB 2 film with only a few apparatuses for plating. enable. In addition, it is possible to form a film on the substrate surface, which is impossible by vacuum deposition. This means that, for example, an MgB 2 superconductor magnet can be produced by plating a metal wire that has been formed into a coil shape from the beginning.
[0010]
Furthermore, in the present invention, as shown in the Examples, MgB 2 could be synthesized by using a mixed system of MgCl 2 / Mg (BF 4 ) 2 6H 2 O / MgB 2 O 4 . . Addition of an alkali metal borate is effective for the purpose of lowering the melting point of the melt. As the electrode material, Pt / Au is used in the embodiment, but other metal / conductive substances can also be used.
[0011]
【Example】
Commercially available reagents MgCl 2 , Mg (BF 4 ) 2 6H 2 O, and MgB 2 O 4 are weighed in a weight ratio of 10: 1: 1 in a total amount of 2.5 g (hereinafter referred to as a powder sample). A platinum wire having a diameter of 1 mm is fixed to one end of the alumina boat so as to run over the bottom of the boat. Similarly, fix the same diameter gold to the opposite end of the boat. A gold wire having a diameter of 0.3 mm (hereinafter referred to as a lead wire) is crimped to each of the platinum wire and the gold wire.
[0012]
After filling the boat with the powder sample, it is placed in a horizontal electric furnace equipped with a quartz furnace core tube. Attach the tube to a rubber stopper that plugs one end of the core tube and connect it to the argon gas line. In addition to the exhaust tube, a two-hole insulator is inserted into the rubber plug at the other end of the core tube. Lead wires are routed outside the core tube through insulators and connected to a DC power source. Be careful not to touch the leads together. The platinum wire is bonded to the negative electrode, and the gold wire is bonded to the positive electrode.
[0013]
The furnace temperature is raised to 600 ° C. while flowing argon gas for about 1 liter per minute. The powder sample becomes a melt. A 4V DC voltage is applied to the lead wire, and when energization of several hundred milliamperes is confirmed, the lead wire is left as it is for several hours. After a few hours, return the furnace temperature to room temperature and remove the boat. Soak the boat in distilled water to remove the flux. After removing the flux, a platinum wire coated with a black material (MgB 2 ) was obtained.
[0014]
A magnetic susceptibility / temperature curve of MgB 2 grown on a platinum wire is shown in FIG. The measurement magnetic field is 20 gauss, and shows the respective curves of cooling without magnetic field (ZFC) and cooling in magnetic field (FC). As a magnetic characteristic, a singular point is observed in the susceptibility curve at 37K, which corresponds to the superconducting conversion of MgB 2 .
[0015]
【The invention's effect】
Compared with the large-scale film forming process using the conventional vacuum vapor deposition apparatus, by using the apparatus of the simple mechanism of the present invention, it is possible to produce a MgB 2 thin film and a wire which are difficult to synthesize at an extremely low cost. .
[0016]
That is, according to the present invention, unlike the film forming method using a high-priced apparatus such as vacuum vapor deposition which is currently actively used, it is possible to easily form a MgB 2 film with only a few apparatuses for plating. enable. In addition, it is possible to form a film on the substrate surface, which is impossible by vacuum deposition. This means that, for example, an MgB 2 superconducting magnet can be produced by plating a gold wire that has been formed into a coil shape from the beginning.
[0017]
The MgB 2 thin film is used as a superconducting quantum interference device (SQUID) in a highly sensitive magnetometer. The superconducting wire is used to generate a strong magnetic field as a superconducting electromagnetic magnet. Both of them are used in academic research in addition to medical CT scanning devices.
[Brief description of the drawings]
FIG. 1 is a magnetic susceptibility / temperature curve of MgB 2 grown on a platinum wire, as shown in FIG.
FIG. 2 is a diagram of an apparatus for producing MgB 2 by the method of the present invention.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2002163764A JP4120955B2 (en) | 2002-06-05 | 2002-06-05 | Synthesis Method of Superconducting Boride MgB2 by Electrodeposition from Melt |
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| JP2002163764A JP4120955B2 (en) | 2002-06-05 | 2002-06-05 | Synthesis Method of Superconducting Boride MgB2 by Electrodeposition from Melt |
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| JP4120955B2 true JP4120955B2 (en) | 2008-07-16 |
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| JP4061576B2 (en) * | 2002-06-05 | 2008-03-19 | 独立行政法人 日本原子力研究開発機構 | Melt electrodeposition synthesis method of superconducting boride MgB2 |
| JP4811998B2 (en) * | 2005-11-22 | 2011-11-09 | 独立行政法人物質・材料研究機構 | Fabrication method of superconducting MgB2 film by electroplating |
| CN101864587B (en) * | 2009-04-20 | 2013-08-21 | 鸿富锦精密工业（深圳）有限公司 | Device and method for forming nanoscale metal particles/metal composite coatings |
| CN102242371A (en) * | 2011-06-24 | 2011-11-16 | 武汉大学 | Preparation method and application of superfine calcium hexaboride |
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| JP3774761B2 (en) * | 2001-04-26 | 2006-05-17 | 独立行政法人物質・材料研究機構 | Method for producing MgB2 superconductor |
| JP3764115B2 (en) * | 2002-02-21 | 2006-04-05 | 日本原子力研究所 | Synthesis method of superconducting boron compound MgB2. |
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