JP3764115B2 - Synthesis method of superconducting boron compound MgB2. - Google Patents
Synthesis method of superconducting boron compound MgB2. Download PDFInfo
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- JP3764115B2 JP3764115B2 JP2002045018A JP2002045018A JP3764115B2 JP 3764115 B2 JP3764115 B2 JP 3764115B2 JP 2002045018 A JP2002045018 A JP 2002045018A JP 2002045018 A JP2002045018 A JP 2002045018A JP 3764115 B2 JP3764115 B2 JP 3764115B2
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- 150000001639 boron compounds Chemical class 0.000 title claims description 7
- 238000001308 synthesis method Methods 0.000 title description 2
- 229910020073 MgB2 Inorganic materials 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【０００１】
【発明の属する技術分野】
２００１年初頭発見された、超伝導転移温度３９Ｋを示すホウ素化合物
ＭｇＢ2は、超伝導線材などへの応用が期待されている。構成元素Ｍｇの高い蒸気圧のため、本系（ＭｇＢ2等）の合成には困難が伴う。
【０００２】
本発明は、塩化マグネシウム、塩化ナトリウム、塩化カリウム及びホウ酸マグネシウムの混合融液から、超伝導転移温度約３９Ｋ以下にゼロ抵抗値を示すホウ素化合物ＭｇＢ２を作製することが特徴である。
【０００３】
【従来の技術】
ＭｇＢ2の超伝導線材作成の手法および素子化に必要な薄膜作成技術に関しては、真空中におけるＭｇやＢなど固体試料の高温反応、あるいは真空封止やアルゴンなどの不活性ガスを充填した石英管やステンレス管内などの閉鎖系における同様の反応、また、真空中においてＭｇターゲットに対しＢを高温で蒸発させ蒸着・反応させる方法が知られている。
【０００４】
真空中加熱および真空封止加熱の際には真空ポンプ、および反応温度９００−１０００℃程度の高温加熱装置が必要である。又、不活性ガス下で反応させる場合には真空ポンプは必要ないが、この手法においても同様の加熱装置が必要となる。
【０００５】
【発明が解決しようとする課題】
真空ポンプには一般に二十万円程度以上の費用が掛かる。その他、固体混合試料を高温９００−１０００℃程度で反応させるための加熱装置が必要である。本発明では、真空ポンプを用いない４００℃以上での電気化学反応により、安価で電源利用効率の高いＭｇＢ2の合成法を提供する。
【０００６】
【課題を解決するための手段】
本発明は、アルゴンガスの不活性雰囲気下の４００℃以上において、塩化マグネシウム、塩化ナトリウム、塩化カリウム及びホウ酸マグネシウムの混合融液から、電気化学的手法によって超伝導ホウ素化合物ＭｇＢ2超伝導線材および超伝導薄膜を作製する。
【０００７】
即ち、本発明は、塩化マグネシウム、塩化ナトリウム、塩化カリウム及びホウ酸マグネシウムの混合粉末を不活性雰囲気下で４００℃以下の温度において電気的に加熱して乾燥処理した後、更に４００℃以上の温度で電気的に加熱溶融して化学反応させることにより超伝導ホウ素化合物ＭｇＢ２を合成する方法である。
【０００８】
上記をＭｇＢ2得るための反応温度は４００℃以上であるが、好ましくは４００〜８００℃、より好ましくは４００〜７００℃、そして最も好ましくは４００〜６００℃である。
【０００９】
【発明の実施の形態】
市販の粉末試薬である、塩化マグネシウム（ＭｇＣｌ2）、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）、及びホウ酸マグネシウム（ＭｇＢ2Ｏ4）をモル比１０：（１０−ｘ）：ｘ：２で総量２ｇ秤量し混合する。塩化カリウムの量（ｘ）は３から７の間である。以下、これを粉体試料と呼ぶ。
【００１０】
図１に示されるように、長さ１００ｍｍ、幅１０ｍｍ、高さ１０ｍｍ、厚み１ｍｍ程度の酸化アルミニウム製の箱型反応容器１に粉体試料を入れ、長手方向の一端に直径１ｍｍのプラチナ線２を反応容器の底に這わせ固定する。同様に、反対の一端に直径５ｍｍのカーボン棒３を固定する。プラチナ線・カーボン棒それぞれに直径０．３ｍｍの金線４を圧着する。
【００１１】
粉体試料および反応容器を直径４０ｍｍ程度の石英管内に入れ、アルゴンガス雰囲気下になるようにする。この石英管を電気炉に挿入する。直流電源を用意し、２本の金線のうち、プラチナ線からのものはマイナス極５に、また、カーボン棒からのものはプラス極６に接続する。アルゴンガスを１リットル毎分程度流しながら、粉体試料を４００℃以下に加熱し、１時間放置して粉体試料を乾燥させる。
【００１２】
その後、粉体試料を４００℃以上まで加熱すると試料は融けて融体となる。２本の金線に５Ｖ直流電圧を印加し、数十ミリアンペアの電流が流れることが確認できたら、そのまま１時間静置する。この後、粉体試料を室温に戻し、大気中に取り出す。プラチナ線に付着した黒色の析出物ＭｇＢ2が得られる。
【００１３】
反応容器内において、この析出物ＭｇＢ2が得られる反応は次のとおりである。
プラチナ極（マイナス極）：Ｍｇ2+＋２Ｂ3+＋８ｅ→ＭｇＢ2（ｅは電子）
カーボン極（プラス極） ：４Ｏ2-→２Ｏ2＋８ｅ
上記２式を足して、 ：ＭｇＢ2Ｏ4→ＭｇＢ2＋２Ｏ2
なお、その他の物質である、塩化マグネシウム、塩化カリウム、塩化ナトリウムについては、融点を下げる効果などの触媒効果がある。
【００１４】
【実施例】
塩化マグネシウム（ＭｇＣｌ2）、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）、及びホウ酸マグネシウム（ＭｇＢ2Ｏ4）をモル比１０：７：３：２で総量２ｇ秤量し混合した。その混合物を、図１の反応容器中でアルゴンガス雰囲気下で約４００℃で１時間乾燥した後、反応温度６００℃で１時間加熱し、黒色の析出物を得た。
【００１５】
得られた試料の電気抵抗を図２に示す。縦軸が電気抵抗値、横軸が温度である。測定電流は０．０１ミリアンペアである。温度を下げるとともに抵抗値が下がっており、金属的なＭｇＢ2の性質と一致する。さらに、約３９Ｋ以下で電気抵抗値がゼロに低下する超伝導転移が認められる。
【００１６】
【発明の効果】
塩化マグネシウム、塩化ナトリウム、塩化カリウム及びホウ酸マグネシウムを使用して超伝導を示す金属的ＭｇＢ２を合成することが可能となる。アルゴン雰囲気中での反応により、真空ポンプを使用する必要が無くなり、合成に必要な費用が低減される。また、反応温度が従来のものより下げられたため、電源利用に対する費用も低減される。
【図面の簡単な説明】
【図１】 本発明においてＭｇＢ２の析出に使用される反抗容器の構造を示す図である。
【図２】 塩化マグネシウム（ＭｇＣｌ2）、塩化ナトリウム（ＮａＣｌ）、塩化カリウム（ＫＣｌ）及びホウ酸マグネシウム（ＭｇＢ2Ｏ4）をモル比１０：７：３：２で総量２ｇ秤量し、上記に従って得られた試料の電気抵抗の温度依存性を示す図である（縦軸が電気抵抗値、横軸が温度である）。[0001]
BACKGROUND OF THE INVENTION
Boron compound MgB 2 having a superconducting transition temperature of 39 K, which was discovered in early 2001, is expected to be applied to superconducting wires. Due to the high vapor pressure of the constituent element Mg, it is difficult to synthesize this system (MgB 2 etc.).
[0002]
The present invention is characterized in that a boron compound MgB 2 exhibiting a zero resistance value at a superconducting transition temperature of about 39 K or less is produced from a mixed melt of magnesium chloride, sodium chloride, potassium chloride and magnesium borate.
[0003]
[Prior art]
Regarding the method of making a superconducting wire of MgB 2 and the thin film forming technology necessary for elementization, a high-temperature reaction of a solid sample such as Mg or B in a vacuum, or a quartz tube filled with an inert gas such as vacuum sealing or argon A similar reaction in a closed system such as in a stainless steel tube, or a method of evaporating and reacting B with Mg at a high temperature in a vacuum is known.
[0004]
For heating in vacuum and vacuum sealing heating, a vacuum pump and a high-temperature heating device with a reaction temperature of about 900 to 1000 ° C. are necessary. Further, when the reaction is performed under an inert gas, a vacuum pump is not necessary, but a similar heating device is also required in this method.
[0005]
[Problems to be solved by the invention]
A vacuum pump generally costs about 200,000 yen or more. In addition, a heating device for reacting the solid mixed sample at a high temperature of about 900 to 1000 ° C. is necessary. In the present invention, an inexpensive MgB 2 synthesis method with high power supply utilization efficiency is provided by an electrochemical reaction at 400 ° C. or higher without using a vacuum pump.
[0006]
[Means for Solving the Problems]
The present invention provides a superconducting boron compound MgB 2 superconducting wire and a superconducting boron compound MgB 2 by an electrochemical method from a mixed melt of magnesium chloride, sodium chloride, potassium chloride and magnesium borate at 400 ° C. or higher under an inert atmosphere of argon gas. A superconducting thin film is produced.
[0007]
That is, in the present invention, a mixed powder of magnesium chloride, sodium chloride, potassium chloride and magnesium borate is electrically heated and dried at a temperature of 400 ° C. or lower in an inert atmosphere, and then further heated to a temperature of 400 ° C. or higher. In this method, the superconducting boron compound MgB 2 is synthesized by electrically heating and melting to cause a chemical reaction.
[0008]
The reaction temperature for obtaining the above MgB 2 is 400 ° C. or more, preferably 400 to 800 ° C., more preferably 400 to 700 ° C., and most preferably 400 to 600 ° C.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Commercial powder reagents magnesium chloride (MgCl 2 ), sodium chloride (NaCl), potassium chloride (KCl), and magnesium borate (MgB 2 O 4 ) in a molar ratio of 10: (10−x): x: 2 Weigh 2 g in total and mix. The amount (x) of potassium chloride is between 3 and 7. Hereinafter, this is referred to as a powder sample.
[0010]
As shown in FIG. 1, a powder sample is put in an aluminum oxide box-type reaction vessel 1 having a length of 100 mm, a width of 10 mm, a height of 10 mm, and a thickness of about 1 mm, and a platinum wire 2 having a diameter of 1 mm at one end in the longitudinal direction. Is fixed to the bottom of the reaction vessel. Similarly, a carbon rod 3 having a diameter of 5 mm is fixed to the opposite end. Crimp a gold wire 4 with a diameter of 0.3 mm to each platinum wire and carbon rod.
[0011]
The powder sample and the reaction vessel are placed in a quartz tube having a diameter of about 40 mm so as to be in an argon gas atmosphere. This quartz tube is inserted into an electric furnace. A direct current power supply is prepared, and from two gold wires, one from the platinum wire is connected to the negative electrode 5, and one from the carbon rod is connected to the positive electrode 6. While flowing argon gas at a rate of about 1 liter per minute, the powder sample is heated to 400 ° C. or less and left for 1 hour to dry the powder sample.
[0012]
Thereafter, when the powder sample is heated to 400 ° C. or higher, the sample melts and becomes a melt. When a 5V DC voltage is applied to the two gold wires and it is confirmed that a current of several tens of milliamperes flows, the sample is left as it is for 1 hour. Thereafter, the powder sample is returned to room temperature and taken out into the atmosphere. A black precipitate MgB 2 adhering to the platinum wire is obtained.
[0013]
The reaction in which the precipitate MgB 2 is obtained in the reaction vessel is as follows.
Platinum electrode (minus electrode): Mg 2+ + 2B 3+ + 8e → MgB 2 (e is an electron)
Carbon electrode (plus electrode): 4O 2- → 2O 2 + 8e
The above two formulas are added: MgB 2 O 4 → MgB 2 + 2O 2
Other substances such as magnesium chloride, potassium chloride, and sodium chloride have a catalytic effect such as an effect of lowering the melting point.
[0014]
【Example】
Magnesium chloride (MgCl 2 ), sodium chloride (NaCl), potassium chloride (KCl), and magnesium borate (MgB 2 O 4 ) were weighed and mixed in a molar ratio of 10: 7: 3: 2. The mixture was dried at about 400 ° C. for 1 hour in an argon gas atmosphere in the reaction vessel of FIG. 1 and then heated at a reaction temperature of 600 ° C. for 1 hour to obtain a black precipitate.
[0015]
The electric resistance of the obtained sample is shown in FIG. The vertical axis is the electric resistance value, and the horizontal axis is the temperature. The measurement current is 0.01 milliamps. As the temperature is lowered, the resistance value is lowered, which is consistent with the metallic MgB 2 property. Furthermore, a superconducting transition is observed in which the electric resistance value drops to zero at about 39K or less.
[0016]
【The invention's effect】
It becomes possible to synthesize metallic MgB 2 exhibiting superconductivity using magnesium chloride, sodium chloride, potassium chloride and magnesium borate. Reactions in an argon atmosphere eliminate the need to use a vacuum pump and reduce the cost required for synthesis. In addition, since the reaction temperature is lower than the conventional one, the cost for using the power source is also reduced.
[Brief description of the drawings]
FIG. 1 is a view showing the structure of a resistance container used for MgB 2 precipitation in the present invention.
FIG. 2 Weighs 2 g of magnesium chloride (MgCl 2 ), sodium chloride (NaCl), potassium chloride (KCl) and magnesium borate (MgB 2 O 4 ) in a molar ratio of 10: 7: 3: 2 and according to the above It is a figure which shows the temperature dependence of the electrical resistance of the obtained sample (a vertical axis | shaft is an electrical resistance value and a horizontal axis is temperature).
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002045018A JP3764115B2 (en) | 2002-02-21 | 2002-02-21 | Synthesis method of superconducting boron compound MgB2. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002045018A JP3764115B2 (en) | 2002-02-21 | 2002-02-21 | Synthesis method of superconducting boron compound MgB2. |
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| Publication Number | Publication Date |
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| JP2003238144A JP2003238144A (en) | 2003-08-27 |
| JP3764115B2 true JP3764115B2 (en) | 2006-04-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| JP4120955B2 (en) * | 2002-06-05 | 2008-07-16 | 独立行政法人 日本原子力研究開発機構 | Synthesis Method of Superconducting Boride MgB2 by Electrodeposition from Melt |
| JP4792597B2 (en) * | 2008-01-11 | 2011-10-12 | 独立行政法人日本原子力研究開発機構 | Method for producing superconducting boron compound MgB2 thin film |
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| Onderka et al. | Oxygen potential and phase equilibria in the Te Sb2O3 Sb2O4 pseudoternary part of the Sb Te O system at elevated temperatures |
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