JP2005529832A - 超伝導物質および合成方法 - Google Patents
超伝導物質および合成方法 Download PDFInfo
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- JP2005529832A JP2005529832A JP2004513209A JP2004513209A JP2005529832A JP 2005529832 A JP2005529832 A JP 2005529832A JP 2004513209 A JP2004513209 A JP 2004513209A JP 2004513209 A JP2004513209 A JP 2004513209A JP 2005529832 A JP2005529832 A JP 2005529832A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000001308 synthesis method Methods 0.000 title 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
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- 239000002887 superconductor Substances 0.000 claims abstract description 18
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 34
- 239000011777 magnesium Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007858 starting material Substances 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 10
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- 239000010949 copper Substances 0.000 claims description 5
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- 238000002156 mixing Methods 0.000 claims description 4
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- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
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- 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 abstract 1
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- PZKRHHZKOQZHIO-UHFFFAOYSA-N [B].[B].[Mg] Chemical compound [B].[B].[Mg] PZKRHHZKOQZHIO-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明は、超伝導化合物および超伝導化合物の合成方法、限定的ではないが特に、二ホウ化マグネシウム系超伝導化合物ならびにその合成方法に関する。
MgB2における超伝導性が発見されたため、この化合物の種々の形態における臨界電流密度(Jc)は著しく改善された[1]。MgB2は、例えば有意の同位体作用により立証されるように、BCS型LTS(低温超伝導体)物質の超伝導特質および物理的性質を示す[2]。しかしながら、その臨界温度(Tc)は、現在用いられている超伝導体Nb3SnおよびNb3Alの温度の2倍より高く、目下のLTSの一番手であるNbTiの温度の4倍より高い。MgB2の重要性は、その単純な結晶構造、高い臨界温度Tc、高い臨界電流密度(Jc)および長いコヒーレンス長(それゆえ、電流に対する粒界の透明度)にある。これらのMgB2の特性は、重要な大規模および電子装置用途に関する前途を有望なものにする。MgB2ワイヤに関する20K〜30Kでの105A/cm2〜106A/cm2のレベルでの高Jcが、いくつかのグループにより報告されている[3〜8]。しかしながら、Jcは磁場増大に伴って急速に低下する。MgB2から作られるワイヤおよびバルクに関する全ての研究において、この物質の不十分なピン止め能力のため、この温度範囲内の3Tで、Jcはそのゼロ磁場値の90%より多く減少した。MgB2が高磁場で有用であるべきものである場合、磁束ピン止め強度が改善されねばならない。磁束ピン止めを増強する試みは、MgB2薄膜中の酸素混和により[9、10]、ならびにMgB2粉末のプロトン照射により[11]、高磁場における不可逆磁場(Hirr)およびJc(H)性能の改善を促進した。
第1の態様によれば、本発明は、式MgBxSiyCz(式中、Xは0〜2の範囲の数であり、Yは0〜1の範囲の数であり、そしてZは0〜1の範囲の数であって、この場合、X、YおよびZの和は2以上である)の超伝導物質を提供する。
超伝導体として機能可能な物質の製造方法であって、
マグネシウム元素およびホウ素元素を、ある量の、炭化ケイ素および炭化チタンを含む群の1つ以上と混合する工程と、
粉末を加熱して、粉末を超伝導体として機能可能な物質に焼結する工程と
を包含する超伝導体として機能可能な物質の製造方法を提供する。
超伝導体として操作可能な物質の製造方法であって、
マグネシウム元素およびホウ素元素を、ある量の、ケイ素元素、チタン元素および炭素元素を含む群の1つ以上と混合する工程と、
混合物を加熱して、混合物を超伝導体として機能可能な物質に焼結する工程と
を包含する超伝導体として操作可能な物質の製造方法を提供する。
本発明の物質の超伝導組成物および合成方法は、Jcおよび磁束ピン止めを有意に増強し得る。本明細書中で以下に記載される結果は、化学的ドーピングが有効な磁束ピン止めを導入するための容易に達成可能且つ経済的に実行可能な手段であるので、高磁場用途のための超伝導体の二次加工のために特許請求された式が用いられ得る、ということを実証する。
反応in situ法により、(Mg+2B)1−x(SiC)x試料を調製した。マグネシウム(純度99%)および非晶質ホウ素(純度99%)の粉末を、それぞれ試料1〜5に関して(Mg+2B)1−x(SiC)x(式中、x=0、0.057、0.117、0.23および0.34)の原子量比を有するSiC添加剤と十分に混合した(表1)。混合粉末をFe管中に充填した。複合管をグルーブ−ロールして、Fe管中に密封し、次に、流動高純度Arの存在下で、設定温度で950℃に3時間直接加熱した。この後、これを液体窒素温度に急冷した。表1は、試料1、2および3がそれぞれドープされない、5重量%MgOでドープされる、および10重量%MgOドープされる情報を提供する。
反応in situ法により、MgB2−x(SiC)x試料を調製した。マグネシウム(純度99%)および非晶質ホウ素(純度99%)の粉末を、SiC添加剤を十分に混合して、以下の比の(Mg+2B)1−x(SiC)x(式中、x=0、0.02、0.05、0.1、0.15、0.2、0.5、1.0、1.5、および2.0を有する種々の試料を調製した。混合粉末をFe管中に充填した。複合管をグルーブ−ロールして、Fe管中に密封し、次に、流動高純度Arの存在下で、設定温度で900℃に3時間直接加熱した。この後、これを液体窒素温度に急冷した。
反応in situ法により、MgB2ペレット試料を調製した。マグネシウム(純度99%)および非晶質ホウ素(純度99%)の粉末を、Mg+B2−x(TiC)x(式中、x=0、0.02、0.05、0.1、0.15、0.2、0.5、1.0、1.5、および0.2)の比を有するSiC添加剤と十分に混合した。混合粉末をFe管中に充填した。複合管をグルーブ−ロールして、Fe管中に密封し、次に、流動高純度Arの存在下で、設定温度で900℃に3時間直接加熱した。この後、これを液体窒素温度に急冷した。
反応in situ法により、MgB2ペレット試料を調製した。マグネシウム(純度99%)および非晶質ホウ素(純度99%)の粉末を、Mg+B2−x(TiC)x(式中、x=0、0.05、0.1、0.15、0.2、0.5、1.0)の比を有するTiC添加剤と十分に混合した。混合粉末をFe管中に充填した。複合管をグルーブ−ロールして、Fe管中に密封し、次に、流動高純度Arの存在下で、設定温度で950℃に3時間直接加熱した。この後、これを室温に炉冷却した。
反応in situ法により、MgB2−xCxの多結晶試料を調製した。マグネシウム(純度99%)、非晶質ホウ素(純度99%)および炭素ナノ粒子(粒子サイズ約20nm)の高純度粉末を、MgB2−xCx(式中、x=0、0.05、0.1、0.2、0.3、0.4)の公称原子量比に従って検量して、磨砕により十分に混合した。水圧プレスを用いて、粉末を直径10mm、厚み3mmのペレットにプレスした。ペレットをFe管中に密封し、次に、流動高純度Arの存在下で、770℃で30分間熱処理した。この後、これを室温に炉冷却した。参照試料として用いるために、非ドープ化試料も同じ条件下で製造した。CuKα放射によるフィリップス(PW1730)回析計を用いて、X線回析(XRD)パターンから、全試料の相および結晶構造を得た。Si粉末を標準参照として用いて、格子パラメーターを算定した。結果は、a軸格子パラメーターおよびTcの両方がドーピングレベル増大に伴って単調に低減した、ということを示す。x=0.4の最高公称組成でドープされた試料に関しては、Tcは2.7Kだけ低下した。ナノCドープ化試料は、広範な温度範囲に亘って、非ドープ化試料に比してJcの磁場依存性改善を示した。Cドーピングによる増強はSiドーピングの場合と同様であるが、しかしナノSiCドープ化MgB2に関するものほど強力ではない。X線回析結果は、CがMgと反応して、ナノサイズのMg2C3およびMgB2C2粒子を形成する、ということを示す。透過型電子顕微鏡によりともに観察されるナノ粒子の含入および置換は、高磁場における磁束ピン止めの増強に寄与すると提案される。
反応in situ法により、MgB2−xCxの多結晶試料を調製した。マグネシウム(純度99%)、非晶質ホウ素(純度99%)および炭素ナノ粒子(粒子サイズ約20〜40nm)の高純度粉末を、MgB2−xCx(式中、x=0、0.05、0.1、0.2、0.3、0.4)の公称原子量比に従って検量して、磨砕により十分に混合した。水圧プレスを用いて、粉末を直径10mm、厚み3mmのペレットにプレスした。ペレットをFe管中に密封し、次に、流動高純度Arの存在下で、800〜900℃で30分間熱処理した。この後、これを室温に炉冷却した。参照試料として用いるために、非ドープ化試料も同じ条件下で製造した。
・上記のような前駆体物質の粉末を混合する。
・混合物をボールミルして、均質性を達成する。
・成形および造形のために金属または合金ダイ、容器、管中に混合物を充填する(金属としては、鉄、ステンレススチール、ニッケルおよび種々の合金が挙げられる)。
・機械的変形、例えばプレス、延伸、回転、スエージおよび成型等により、混合物または複合物をバルク、ワイヤ、テープおよび種々の形状の物品および装置に製造する。
・650℃〜1000℃の温度で10分間〜10時間、好ましくは800〜950℃で10分間〜3時間、複合物を焼結する。
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Claims (26)
- 式MgBxSiyCz(式中、Xは0〜2の範囲の数であり、Yは0〜1の範囲の数であり、そしてZは0〜1の範囲の数であって、この場合、X、YおよびZの和は2以上である)の超伝導物質。
- Xが1〜2の範囲であり、Yが0.05〜0.5の範囲であり、そしてZが0.1〜0.3の範囲である請求項1に記載の超伝導物質。
- Xが1.2〜1.8の範囲であり、Yが0.1〜0.3の範囲であり、そしてZが0.1〜0.3の範囲である請求項1に記載の超伝導物質。
- 請求項1、請求項2または請求項3の超伝導物質を組み入れる超伝導体。
- 請求項1に記載の超伝導物質の合成方法であって、出発物質Mg、B、SiおよびCを利用する工程を包含する前記合成方法。
- 前記出発物質が粉末形態である請求項5に記載の方法。
- 前記粉末がナノ粒子からなる請求項6に記載の方法。
- 請求項1に記載の超伝導物質の合成方法であって、出発物質Mg、B、およびSiCを利用する工程を包含する前記合成方法。
- 前記出発物質が粉末形態である請求項8に記載の方法。
- 前記粉末がナノ粒子からなる請求項9に記載の方法。
- 請求項1に記載の超伝導物質の合成方法であって、出発物質MgB2、ならびにSiCまたはSiおよびCを利用する工程を包含する前記合成方法。
- 前記出発物質が粉末形態である請求項11に記載の方法。
- 前記粉末がナノ粒子からなる請求項12に記載の方法。
- 超伝導物質の製造方法であって、炭化ケイ素を超伝導物質に付加する工程を包含する前記製造方法。
- 前記炭化ケイ素が置換により付加される請求項14に記載の方法。
- 前記炭化ケイ素が添加により付加される請求項14に記載の方法。
- 炭化ケイ素共ドーパントを含む超伝導物質。
- 式MgBxTiyCz(式中、Xは0〜2の範囲の数であり、Yは0〜1の範囲の数であり、そしてZは0〜1の範囲の数であって、この場合、X、YおよびZの和は2以上であり、そしてXは0より大きい)の超伝導物質。
- 超伝導体として機能可能な物質の製造方法であって、
マグネシウム元素およびホウ素元素を、ある量の、炭化ケイ素および炭化チタンを含む群の1つ以上と混合する工程と、
粉末を加熱して、該粉末を超伝導体として機能可能な物質に焼結する工程と
を包含する前記製造方法。 - 超伝導体として操作可能な物質の製造方法であって、
マグネシウム元素およびホウ素元素を、ある量の、ケイ素元素、炭素元素およびチタン元素を含む群の1つ以上と混合する工程と、
混合物を加熱して、該混合物を超伝導体として機能可能な物質に焼結する工程と
を包含する前記製造方法。 - 前記混合物が650℃〜2000℃の範囲の温度に加熱される請求項20に記載の方法。
- 混合物が900℃〜950℃の範囲の温度に加熱される請求項20に記載の方法。
- 前記元素が粉末形態で提供される請求項20に記載の方法。
- 前記粉末がナノ粒子からなる請求項23に記載の方法。
- 前記粉末が、前記混合物を加熱する前に、鉄(Fe)、銅(Cu)、ニッケル(Ni)およびステンレススチールを含む群の1つ以上の物質から製造される管にグルーブ−ロールされる請求項20に記載の方法。
- 得られる物質を液体窒素の温度に冷却して、前記物質を超伝導可能にさせる工程をさらに包含する請求項20に記載の方法。
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DE3822684A1 (de) | 1988-07-05 | 1990-01-11 | Asea Brown Boveri | Elektrischer leiter in draht- oder kabelform, bestehend aus einem ummantelten draht oder aus einem mehrfach-filmentleiter auf der basis eines keramischen hochtemperatur-supraleiters |
JPH02129812A (ja) | 1988-11-09 | 1990-05-17 | Jgc Corp | セラミックス超電導体製品の製造法 |
JPH07115924B2 (ja) | 1989-11-08 | 1995-12-13 | 財団法人国際超電導産業技術研究センター | 酸化物超電導体の製造方法 |
JPH06256018A (ja) | 1993-03-01 | 1994-09-13 | Hitachi Ltd | 酸化物系超電導体とその製法及びそれを用いたマグネット |
JP3575004B2 (ja) * | 2001-01-09 | 2004-10-06 | 独立行政法人 科学技術振興機構 | マグネシウムとホウ素とからなる金属間化合物超伝導体及びその金属間化合物を含有する合金超伝導体並びにこれらの製造方法 |
US20040116301A1 (en) * | 2001-02-28 | 2004-06-17 | Jeffery Tallon | Superconducting borides and wires made thereof |
DE50205344D1 (de) * | 2001-03-12 | 2006-01-26 | Leibniz Inst Fuer Festkoerper | Pulver auf magnesiumdiborid-basis für die herstellung von supraleitern, verfahren zu dessen herstellung und anwendung |
JP4762441B2 (ja) * | 2001-05-23 | 2011-08-31 | 古河電気工業株式会社 | MgB2超電導線及びその製造方法 |
WO2002098794A1 (en) * | 2001-06-01 | 2002-12-12 | International Superconductivity Technology Center, The Juridical Foundation | Mgb2 based superconductor having high critical current density and method for preparation thereof |
GB0129410D0 (en) * | 2001-12-07 | 2002-01-30 | Imp College Innovations Ltd | Magnesium diboride superconductors |
US6511943B1 (en) * | 2002-03-13 | 2003-01-28 | The Regents Of The University Of California | Synthesis of magnesium diboride by magnesium vapor infiltration process (MVIP) |
US6946428B2 (en) * | 2002-05-10 | 2005-09-20 | Christopher M. Rey | Magnesium -boride superconducting wires fabricated using thin high temperature fibers |
-
2002
- 2002-06-18 AU AUPS3057A patent/AUPS305702A0/en not_active Abandoned
-
2003
- 2003-06-18 EP EP03759789A patent/EP1534650A4/en not_active Withdrawn
- 2003-06-18 JP JP2004513209A patent/JP2005529832A/ja active Pending
- 2003-06-18 WO PCT/AU2003/000758 patent/WO2003106373A1/en active Application Filing
-
2004
- 2004-06-18 US US10/518,948 patent/US20050245400A1/en not_active Abandoned
-
2009
- 2009-09-03 US US12/553,778 patent/US7838465B2/en not_active Expired - Fee Related
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008091325A (ja) * | 2006-08-28 | 2008-04-17 | Bruker Biospin Ag | MgB2を含有する超伝導素子 |
JP2009175034A (ja) * | 2008-01-25 | 2009-08-06 | Kobe Univ | 液体水素用液面センサ及び液体水素用液面計 |
WO2014034295A1 (ja) * | 2012-08-29 | 2014-03-06 | 株式会社 日立製作所 | 伝導冷却式永久電流スイッチ、mri装置、nmr装置 |
JP2014045158A (ja) * | 2012-08-29 | 2014-03-13 | Hitachi Ltd | 伝導冷却式永久電流スイッチ、mri装置、nmr装置 |
US9887029B2 (en) | 2012-08-29 | 2018-02-06 | Hitachi, Ltd. | Conductive cooling-type persistent current switch, MRI apparatus and NMR apparatus |
WO2018159513A1 (ja) * | 2017-03-03 | 2018-09-07 | 株式会社日立製作所 | 超伝導体の製造方法 |
US11387017B2 (en) | 2017-03-03 | 2022-07-12 | Hitachi, Ltd. | Method of producing superconductor |
Also Published As
Publication number | Publication date |
---|---|
US7838465B2 (en) | 2010-11-23 |
WO2003106373A1 (en) | 2003-12-24 |
EP1534650A4 (en) | 2007-02-21 |
US20100081573A1 (en) | 2010-04-01 |
AUPS305702A0 (en) | 2002-07-11 |
EP1534650A1 (en) | 2005-06-01 |
US20050245400A1 (en) | 2005-11-03 |
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