CN1377044A - 基于化合物MgB2的超导线和带的生产方法 - Google Patents
基于化合物MgB2的超导线和带的生产方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 11
- 229910020073 MgB2 Inorganic materials 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 25
- PLUDBJRFRHMTGA-UHFFFAOYSA-N n,n-bis(2-chloroethyl)-4-[3-[6-[6-(4-methylpiperazin-1-yl)-1h-benzimidazol-2-yl]-1h-benzimidazol-2-yl]propyl]aniline;trihydrochloride Chemical compound Cl.Cl.Cl.C1CN(C)CCN1C1=CC=C(N=C(N2)C=3C=C4NC(CCCC=5C=CC(=CC=5)N(CCCl)CCCl)=NC4=CC=3)C2=C1 PLUDBJRFRHMTGA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 239000002887 superconductor Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract 2
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 6
- 238000003801 milling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MEOSMFUUJVIIKB-UHFFFAOYSA-N [W].[C] Chemical compound [W].[C] MEOSMFUUJVIIKB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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Abstract
本发明的任务是给出一种生产方法,采用该法可生产基于MgB2的,长的,具有高电流载荷的超导线和带。本发明是基于已知的“粉末-在-管-技术”,在此通过重新成型和热处理步骤将一普通导电材料的外管和一含有超导体的粉末或该化合物的初产品结合,生产出超导线和带。按照本发明该加工会产生一结合物,该结合物在外管内含有一粉状的超导性的MgB2-化合物或一粉状的超导性的MgB2-化合物初产品,这里作为机械合金粉末仅部分地被反应为MgB2-化合物的粉状的初产品,或作为由所期望的MgB2-化合物的单组份组成的粉混合物被送入到外管中。采用本发明的方法可生产高技术标准的基于MgB2化合物的超导线和带,它们可在能源技术领域被用作超导体。
Description
技术领域
本发明涉及一种基于化合物MgB2的超导线和带的生产方法。该线和带特别适合于在能源技术领域用作超导体。
技术背景
最近在二元合金MgB2中首次证实了具有Tc=38K至40K的超导体(J.Nagamatsu,N.Nagakawa,T.Muranaka,Y.Zenitani和J。Akamitsu,自然410(2001),63)。
在一项实验中,借助在石英安培瓶中,在Mg-粉的存在时通过对硼-线进行热处理所产生的Mg向硼-线中的扩散,也生产出了一种MgB2-线(Canfield等人,在致密MgB2线中的超导性,Publ.Cond-matHomepage vom 15.02.01:cond-mat/0102289)。该方法不适合工业技术类线材的生产。
另外的MgB2-线的生产方法,例如采用一种紧密的材料,由于MgB2太脆看来也不可能。
发明的描述
本发明的任务是给出一种生产方法,采用该法可生产基于MgB2的,长的,具有高电流密度载荷的超导线和带。
该任务可通过按照本发明专利权利要求中所叙述的生产方法加以解决。
本发明是基于已知的“粉末-在-管-技术”,在此通过重新成型和热处理步骤将一普通导电材料的外管和一含有超导体的粉末或该化合物的初产品结合,生产出超导线和带。
按照本发明该加工会产生一结合物,该结合物在外管内含有一粉状的超导性的MgB2-化合物,或一粉状的超导性的MgB2-化合物初产品,这里作为机械合金粉末的仅部分地被反应为MgB2-化合物的粉状的初产品,或作为由所期望的MgB2-化合物的单组份组成的粉末混合被送入到外管中。
优点是,在使用一完全反应的MgB2-化合物或MgB2-初产品时,在它的晶格中会嵌入Al、Ag、Cu、Au、Sc、Y、Dy、Gd、Hf、Ti、Zr、Ta、V、Nb、Cr、Mo、Mn、Os、Ru、C、Si、N和/或O。
也可使用一仅由Mg-粉和B-粉组成的单组份的粉末混合。
也可以使用由Mg-粉和B-粉以及一种或多种由Al、Ag、Cu、Au、Sc、Y、Dy、Gd、Hf、Ti、Zr、Ta、V、Nb、Cr、Mo、Mn、Os和Ru金属粉组成的单组份的粉末混合。
按照本发明最好使用粉末,该粉末应具有一窄的平均粒子大小d<10μm的颗粒分布,或应使用这样的粉末,该粉末平均颗粒大小的区别为5-10因数。
外管可由Cu、Ag、Ta、Nb、Mo、W、Fe或Mg或它们的合金构成。
在使用Mg-外管时,最好是将其用一个其它的由Fe,Nb或Ta构成的外管套起来。
按照本发明,为在结合物重新成型范围内对外管软化和/或由MgB2-初产品形成超导MgB2-化合物和/或超导MgB2-化合物在紧密的结合物中烧结,将在带微量氧分压或少量还原的添加物,如H2的惰性气体中进行一次或多次温度介于300℃和1100℃间的热处理。
对外管软化的热处理在温度介于300℃和1100℃间进行。
对由一仅部分地被反应为MgB2-化合物的机械合金粉末构成的粉状初产品形成超导MgB2-化合物的热处理将在温度介于300℃和700℃间进行。
对由所期望MgB2-化合物的单组份粉末混合物构成的MgB2-初产品形成超导MgB2-化合物的热处理将在温度介于400℃和1000℃间进行。
超导MgB2-化合物在紧密的结合物中的烧结将在温度介于500℃和1000℃间进行。
对结合物的紧密化可使用温度>500℃和压力>2巴的热均质压缩(HIP-过程)。
采用本发明的方法可生产高技术标准的基于MgB2化合物的超导线和带,它们可在能源技术领域被用作超导体。
本发明的实施方法
下面借助实施例子更详细的阐明本发明的生产方法。例1
纯度为98%的MgB2粉在240Mpa的压力下冷均质压缩成一直径为8mm的圆杆。该杆放入一一端封闭的,内径为10mm壁厚为1mm的钽管中。再将该和钽管套在一起的MgB2杆插入一一端封闭的,内径为11mm壁厚为1mm的铜管中,它们的开口端在真空下同样进行封闭。然后借助锤子,轧辊和平辊将该制成的物体变形为一0.45mm厚和5.7mm宽的Cu/Ta/MgB2条,并将其在一Ar气-环境下900℃温度热处理一小时。该带的一块样品被测出具有一临界温度为33K和当外界电场为1.5T和4.2K时临界电流密度为5.1KA/cm2,当在自身场和4.2K时临界电流密度为20KA/cm2。例2
为生产一机械合金Mg-B-粉,将一纯度为99.8%的Mg-粉和纯度为99.9%的非结晶硼粉按照化合物MgB2的化学计量成分比例混合,于一钨碳(WC)碾磨容器中在极纯Ar气-环境下,使用WC-球作为碾磨体在行星球磨中碾磨20个小时。所得到的粉末如例1所述制成一Cu/Ta/MgB2条。将该条在700℃ Ar气-环境下热处理20分钟。该带的一块样品被测出具有一临界温度为34K和当在自身场和4.2K时临界电流密度为25KA/cm2。
Claims (14)
1.以“粉末-在-管-技术”生产超导线和带的方法,在此通过重新成型和热处理步骤将一普通导电材料的外管和一在其中含有超导体化合物的粉末或该化合物的初产品结合,生产出超导线和带,其特征是生产出一结合物,该结合物在外管中含有的一粉状的超导MgB2-化合物或一粉状的超导MgB2-化合物的初产品,其中该粉状的初产品作为机械合金粉,仅部分地反应为MgB2-化合物,或作为粉混合物,其由所期望的MgB2-化合物单组份构成,被送入外管中。
2.按照权利要求1的方法,其特征是使用了一完全反应的MgB2-化合物或MgB2-初产品,在它的晶格中会嵌入Al、Ag、Cu、Au、Sc、Y、Dy、Gd、Hf、Ti、Zr、Ta、V、Nb、Cr、Mo、Mn、Os、Ru、C、Si、N和/或O。
3.按照权利要求1的方法,其特征是使用一由Mg-粉和B-粉组成的单组份-粉末混合。
4.按照权利要求1的方法,其特征是使用一由Mg-粉和B-粉以及一种或多种由Al、Ag、Cu、Au、Sc、Y、Dy、Gd、Hf、Ti、Zr、Ta、V、Nb、Cr、Mo、Mn、Os和Ru金属粉组成的单组份-粉末混合。
5.按照权利要求1的方法,其特征是所使用的粉末应具有一窄的平均粒子大小d<10μm的颗粒分布。
6.按照权利要求1的方法,其特征是所使用的粉末应具有两种窄的颗粒带,该颗粒带平均颗粒大小的区别为5-10因数。
7.按照权利要求1的方法,其特征是所使用的外管由Cu、Ag、Ta、Nb、Mo、W、Fe或Mg或它们的合金构成。
8.按照权利要求1的方法,其特征是在使用Mg-外管时,是将其用一个其它的外管套起来,最好是由Fe,Nb或Ta构成的外管。
9.按照权利要求1的方法,其特征是为在结合物重新成型范围内对外管软化和/或由MgB2-初产品形成超导MgB2-化合物和/或超导MgB2-化合物在紧密的结合物中烧结,将在带微量氧分压或少量还原的添加物,如H2的惰性气体中进行一次或多次温度介于300℃和1100℃间的热处理。
10.按照权利要求9的方法,其特征是对外管软化的热处理在温度介于300℃和1100℃间进行。
11.按照权利要求9的方法,其特征是对由一仅部分地被反应为MgB2-化合物的机械合金粉末构成的粉状初产品形成超导MgB2-化合物的热处理将在温度介于300℃和700℃间进行。
12.按照权利要求9的方法,其特征是对由所期望MgB2-化合物的单组分粉末混合物构成的MgB2-初产品形成超导MgB2-化合物的热处理将在温度介于400℃和1000℃间进行。
13.按照权利要求9的方法,其特征是超导MgB2-化合物在紧密的结合物中的烧结将在温度介于500℃和1000℃间进行
14.按照权利要求1的方法,其特征是对结合物的紧密化可使用HIP-过程,在温度>500℃和压力>2巴下进行。
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DE10114934A DE10114934A1 (de) | 2001-03-22 | 2001-03-22 | Verfahren zur Herstellung von supraleitenden Drähten und Bändern auf Basis der Verbindung MgB¶2¶ |
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US7018954B2 (en) * | 2001-03-09 | 2006-03-28 | American Superconductor Corporation | Processing of magnesium-boride superconductors |
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-
2001
- 2001-03-22 DE DE10114934A patent/DE10114934A1/de not_active Withdrawn
-
2002
- 2002-03-13 DE DE10211538A patent/DE10211538B4/de not_active Expired - Fee Related
- 2002-03-15 DK DK200200409A patent/DK200200409A/da not_active Application Discontinuation
- 2002-03-19 JP JP2002076878A patent/JP4259806B2/ja not_active Expired - Fee Related
- 2002-03-21 CN CNB021077843A patent/CN1290124C/zh not_active Expired - Fee Related
- 2002-03-21 US US10/103,312 patent/US20020164418A1/en not_active Abandoned
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DE10114934A1 (de) | 2002-09-26 |
DK200200409A (da) | 2002-09-23 |
US20020164418A1 (en) | 2002-11-07 |
DE10211538B4 (de) | 2007-06-21 |
DE10211538A1 (de) | 2003-05-08 |
JP2002343162A (ja) | 2002-11-29 |
CN1290124C (zh) | 2006-12-13 |
JP4259806B2 (ja) | 2009-04-30 |
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