JPH075314B2 - Bi-based oxide superconductor powder and method for producing the wire - Google Patents
Bi-based oxide superconductor powder and method for producing the wireInfo
- Publication number
- JPH075314B2 JPH075314B2 JP1341238A JP34123889A JPH075314B2 JP H075314 B2 JPH075314 B2 JP H075314B2 JP 1341238 A JP1341238 A JP 1341238A JP 34123889 A JP34123889 A JP 34123889A JP H075314 B2 JPH075314 B2 JP H075314B2
- Authority
- JP
- Japan
- Prior art keywords
- based oxide
- temperature
- producing
- powder
- gas
- 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 - Lifetime
Links
- 239000000843 powder Substances 0.000 title claims description 23
- 239000002887 superconductor Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、Bi系酸化物超電導体の低Tc相の粉末と、そ
の粉末を用いての線材の製造方法に関するものである。
さらに詳しくは、この発明は、液体ヘリウム温度の高磁
界中において高い臨界電流密度を有する高磁界特性の優
れたBi系酸化物超電導線材を製造する方法に関するもの
である。Description: TECHNICAL FIELD The present invention relates to a low Tc phase powder of a Bi-based oxide superconductor, and a method for manufacturing a wire using the powder.
More specifically, the present invention relates to a method for producing a Bi-based oxide superconducting wire having a high critical current density and a high magnetic field characteristic in a high magnetic field at a liquid helium temperature.
（従来の技術とその課題） 研究開発の急速な進展によって、酸化物高温超電導体と
してすでにYBaCuO系、 BiSrCaCuO系およびTlBaCaCuO系の酸化物で、液体窒素温
度を超える高いTcを有するものが見出されている。ま
た、これらの高Tc酸化物超電導材料については、種々の
断面形状の長尺線材に加工し、核融合炉、磁気浮上列
車、加速器、磁気診断装置（MRI）などに有用な高磁界
超電導マグネットや超電導送電等の強電分野に利用する
ことが検討されており、すでに実用的利用も試みられて
いる。さらにSQIUD、超電導ドランジスターなどの薄膜
素子や、高速コンピューターをはじめ、超精密計測機器
などの広い分野での応用が考えられてもいる。(Prior art and its problems) Due to rapid progress in research and development, YBaCuO-based, BiSrCaCuO-based, and TlBaCaCuO-based oxides having high Tc exceeding liquid nitrogen temperature have been found as oxide high-temperature superconductors. ing. In addition, these high Tc oxide superconducting materials are processed into long wire rods with various cross-sectional shapes, and high magnetic field superconducting magnets useful for fusion reactors, magnetic levitation trains, accelerators, magnetic diagnostic equipment (MRI), etc. Utilization in the field of high electric power such as superconducting power transmission is under consideration, and practical use has already been attempted. Furthermore, application in a wide range of fields such as thin film elements such as SQIUD and superconducting transistors and high-speed computers, as well as ultra-precision measuring instruments, is being considered.
これら超電導材料のうち、高いTc、非希土類系の観点か
らBi系酸化物が注目されており、液体窒素温度において
これを利用できるように、Tcが110°Ｋの高Tc相Bi2Sr2C
a2 Cu3Ox）の酸化物についてその線材化の研究開発が
活発に進められている。この研究の進展にともなって実
用化にあたっての重要特性のひとつである臨界電流密度
（Jc）も急速に向上しつつある。Among these superconducting materials, Bi-based oxides are attracting attention from the viewpoint of high Tc and non-rare earth type, and high Tc phase Bi 2 Sr 2 C with Tc of 110 ° K can be used at liquid nitrogen temperature.
A 2 Cu 3 O x ) oxide is being actively researched and developed into a wire rod. Along with the progress of this research, the critical current density (Jc), which is one of the important characteristics for practical use, is also improving rapidly.
しかしながら、このBi系酸化物の線材は、液体窒素温度
領域において磁界がかかると臨界電流密度（Jc）が急激
に低下するため、液体窒素中において、高磁界で利用す
ることは極めて困難であるのが実情である。However, since the critical current density (Jc) of this Bi-based oxide wire drastically decreases when a magnetic field is applied in the liquid nitrogen temperature region, it is extremely difficult to use it in a high magnetic field in liquid nitrogen. Is the reality.
一方、酸化物系の超電導材料は、臨界磁界（Hc2）が従
来の金属系材料と比較した場合におよそ１桁高いので、
液体ヘリウム中での利用を考えると、高磁界中でも高い
臨界電流密度（Jc）特性が得られることが期待される。
実際に、最近の研究ではその事実が認められつつある。
この場合、使用するBi系酸化物は高Tc相（Tc110°
Ｋ）のものにとらわれる必要は全くなく、低Tc相（Jc
70〜90°Ｋ）であっても充分に利用可能であり、この低
Tc相は、高Tc相に比較して生成が容易であることから、
実用化するにあたって有利であるとも考えられる。On the other hand, the oxide-based superconducting material has a critical magnetic field (Hc 2 ) that is about an order of magnitude higher than that of conventional metal-based materials.
Considering its use in liquid helium, it is expected that high critical current density (Jc) characteristics can be obtained even in a high magnetic field.
In fact, recent research is recognizing that fact.
In this case, the Bi-based oxide used has a high Tc phase (Tc 110 °
K), there is no need to be obsessed with low Tc phase (Jc
Even if it is 70 to 90 ° K), it is fully usable and this low
Since the Tc phase is easier to generate than the high Tc phase,
It is also considered to be advantageous for practical application.
しかしながら、磁界電流密度（Jc）値が、なお実用化に
とって必要な２〜４×105A/cm2のレベルに比較して低い
ことが依然として問題となる。However, it is still a problem that the magnetic field current density (Jc) value is lower than the level of 2 to 4 × 10 5 A / cm 2 which is still necessary for practical use.
この発明は、以上の通りの事情に鑑みてなされたもので
あり、その利用が期待される低Tc相酸化物からの線材の
臨界電流密度（Jc）を向上するための新しい方法を提供
することを目的としている。The present invention has been made in view of the above circumstances, and provides a new method for improving the critical current density (Jc) of a wire from a low Tc phase oxide, which is expected to be used. It is an object.
（課題を解決するための手段） この発明は、蒸気の課題を解決するものとして、Bi系酸
化物超電導体の低Tc相の組成に略等しい構成比に配合さ
れた原料粉末を、酸素ガスの比がN2ガスおよび／または
不活性ガスに対して1/5〜1/100の減圧酸素雰囲気中、ま
たは150〜１×10-5Torrの真空中において、800〜880℃
の温度で加熱処理することを特徴とするBi系酸化物超電
導体用粉末の製造方法と、Bi系酸化物超電導体の低Tc相
の組成に略等しい構成比に配合された原料粉末を大気中
において800〜880℃の温度で１次加熱した後に、150〜
１×10-5Torrの真空中において400〜700℃の温度で、ま
たはH2ガスの比が不活性ガスに対して1/10〜1/100の水
素還元雰囲気中において300〜650℃の温度で２次加熱処
理することを特徴とするBi系酸化物超電導体用粉末の製
造方法とを提供する。(Means for Solving the Problem) As a solution to the problem of steam, the present invention provides a raw material powder mixed in a composition ratio substantially equal to the composition of the low Tc phase of a Bi-based oxide superconductor, in an oxygen gas. 800 to 880 ℃ in a depressurized oxygen atmosphere with a ratio of 1/5 to 1/100 to N 2 gas and / or an inert gas, or in a vacuum of 150 to 1 × 10 -5 Torr.
A method for producing a powder for a Bi-based oxide superconductor characterized by being heat-treated at a temperature of, and a raw material powder mixed in a composition ratio substantially equal to the composition of the low Tc phase of the Bi-based oxide superconductor in the atmosphere. After the primary heating at a temperature of 800-880 ℃ at
Temperature of 400-700 ℃ in vacuum of 1 × 10 -5 Torr, or 300-650 ℃ in hydrogen reducing atmosphere with H 2 gas ratio of 1/10 to 1/100 to inert gas. And a method for producing a powder for a Bi-based oxide superconductor, characterized in that the second heat treatment is performed.
この方法によって製造した低Tc相酸化物粉末は密度が向
上し、結晶粒間の電気的接続性が著しく改善され、金属
シース線材の製造に対して特に有効である。The low Tc phase oxide powder produced by this method has an improved density and significantly improved electrical connectivity between crystal grains, and is particularly effective for producing a metal sheath wire.
原料粉末としては、Bi系酸化物超電導体の低Tc相の組成
に対応した各酸化物の構成比とすればよく、Bi、Sr、C
a、Cu、さらにはPb、Ag、Ni、Co、Mn、Ｗ、Mo、Cr、Ti
等の金属の酸化物、もしくはその前駆体を用いることが
できる。構成比は、酸素を除いた組成で、BizSr2CaxCu2
My（Ｍは、Ag、Pb、Ni、Co、CrまたはMnの一種以上を示
し、0.5≦ｘ≦３、０≦ｙ≦１および1.5≦ｚ≦３であ
る。）で示されるものが好適なものとして例示される。As the raw material powder, the composition ratio of each oxide corresponding to the composition of the low Tc phase of the Bi-based oxide superconductor, Bi, Sr, C
a, Cu, and further Pb, Ag, Ni, Co, Mn, W, Mo, Cr, Ti
An oxide of a metal such as or a precursor thereof can be used. The composition ratio is the composition excluding oxygen, and Bi z Sr 2 Ca x Cu 2
The one represented by M y (M represents one or more of Ag, Pb, Ni, Co, Cr or Mn, and 0.5 ≦ x ≦ 3, 0 ≦ y ≦ 1 and 1.5 ≦ z ≦ 3) is preferable. It is exemplified as
減圧酸素雰囲気または真空中における800〜880℃の温度
での加熱は10分間〜200時間程度行うのが好ましい。The heating at a temperature of 800 to 880 ° C. in a reduced pressure oxygen atmosphere or vacuum is preferably performed for about 10 minutes to 200 hours.
また、大気中800〜880℃での１次加熱の場合には50分間
〜３時間、そして引続いての真空中400〜700℃の２次加
熱は10分間〜10間、水素還元雰囲気中300〜650℃の２次
加熱では10分間〜10時間の処理とするのが好ましい。Also, 50 minutes to 3 hours in the case of primary heating in the air at 800 to 880 ° C, and 10 minutes to 10 hours in the subsequent secondary heating at 400 to 700 ° C in vacuum, 300 times in the hydrogen reducing atmosphere. The secondary heating at 650 ° C. is preferably performed for 10 minutes to 10 hours.
また、この発明は、上記の方法により得た粉末を用いて
金属シース加工線材を作製するにあたり、本焼結工程に
おいて少なくとも１回以上室温で中間圧縮、すなわち、
プレス、ロール、伸線加工等することを特徴とするBi系
酸化物超電導線材の製造方法も提供する。この方法によ
って酸化物相の密度を上昇させ、結晶粒間の電気的接続
性の向上の他に、拡散反応の促進による非超電導析出物
の減少と微細化が達成される。しかも、臨界電流密度
（Jc）特性が著しく向上する。In addition, in the present invention, in producing a metal sheath processed wire using the powder obtained by the above method, at least one intermediate compression at room temperature in the main sintering step, that is,
Also provided is a method for producing a Bi-based oxide superconducting wire, which is characterized by performing pressing, rolling, wire drawing, and the like. By this method, the density of the oxide phase is increased, the electrical connectivity between the crystal grains is improved, and the non-superconducting precipitates are reduced and refined by promoting the diffusion reaction. Moreover, the critical current density (Jc) characteristics are significantly improved.
上記の中間圧縮工程の終了後に、酸素分圧が1/5以上の
雰囲気下において、880℃未満の温度で10分〜150時間の
後処理することも有効である。これにより特性はさらに
向上する。It is also effective to carry out a post-treatment at a temperature of less than 880 ° C. for 10 minutes to 150 hours in an atmosphere having an oxygen partial pressure of 1/5 or more after the completion of the intermediate compression step. This further improves the characteristics.
また、この発明の原料粉末を用いると、最終熱処理工程
をN2、Ar等の不活性ガス雰囲気中でも行えるので、Ag以
外の任意の金属シース材を使用することもできる。Further, when the raw material powder of the present invention is used, the final heat treatment step can be performed in an atmosphere of an inert gas such as N 2 or Ar, so that any metal sheath material other than Ag can be used.
次に、実施例を示し、さらに詳しくこの発明について説
明する。Next, the present invention will be described in more detail with reference to examples.
実施例 Bi2O3、SrCO3、CaCO3、CuOおよびAg2Oからなる原料粉末
を用いて、Bi系酸化物低Tc相の標準組成であるBi:Sr:C
a:Cuが2:2:1:2の試料（Ａ）と、これに銀を少量（Cu;Ag
＝2:0.8）を加えた試料（Ｂ）の２種類の混合粉を用意
した。この２種類の混合粉を１次加熱処理または、１次
加熱処理と２次加熱処理とを行い、室温まで冷却し、次
いで得られた焼結体を粉砕した。Bi系酸化物超電導体用
粉末を得た。Using a raw material powder consisting of Examples Bi 2 O 3, SrCO 3, CaCO 3, CuO and Ag 2 O, a standard composition of Bi-based oxide low Tc phase Bi: Sr: C
Sample with a: Cu of 2: 2: 1: 2 (A) and a small amount of silver (Cu; Ag
= 2: 0.8) was added to prepare two kinds of mixed powders of the sample (B). These two kinds of mixed powders were subjected to primary heat treatment or primary heat treatment and secondary heat treatment, cooled to room temperature, and then the obtained sintered body was pulverized. A Bi-based oxide superconductor powder was obtained.
この時の処理条件を第１表に示した。The processing conditions at this time are shown in Table 1.
これらの７種類の微粉末（試料6,7は比較例である。）
を、外径10mm、内径7mm、深さ25mmの銀の円筒に詰め
て、銀の栓をした複合体を、溝ロール、スウェージン
グ、伸線機を用いて、外形が約1mmの丸線に加工した。
この加工過程で、アルゴンガス中において870℃で、約1
0分問の焼鈍を数回繰り返した。 These 7 kinds of fine powders (Samples 6 and 7 are comparative examples)
Was packed in a silver cylinder with an outer diameter of 10 mm, an inner diameter of 7 mm, and a depth of 25 mm, and the composite with a silver plug was cut into a round wire with an outer diameter of about 1 mm using a groove roll, swaging, and wire drawing machine. processed.
During this process, the temperature was about 1 at 870 ° C in argon gas.
The 0 minute annealing was repeated several times.
この丸線を、さらに平ロール圧延により、厚さが約0.30
mm、幅約2mmのテープ状に加工後に、アルゴンガス雰囲
気で880℃で、約30時間の本焼結処理を行い、室温まで
冷却した。その後、さらに平ロール圧延を行い、厚さが
約0.20mm、幅約3mmのテープ状に加工後、再度アルゴン
ガス雰囲気中880℃で約50時間の２次本焼結を行った。This round wire is further flat-rolled to a thickness of approximately 0.30
After being processed into a tape having a width of about 2 mm and a width of about 2 mm, a main sintering process was performed at 880 ° C. for about 30 hours in an argon gas atmosphere and cooled to room temperature. Then, flat roll rolling was further performed to form a tape having a thickness of about 0.20 mm and a width of about 3 mm, and then secondary main sintering was performed again at 880 ° C. for about 50 hours in an argon gas atmosphere.
第１図は、4.2°Ｋ、磁場12Tまでの磁界中における上記
試料１〜７からの線材の臨界電流密度（Jc）を、比較例
とともに図示したものである。また、交流帯磁率法によ
って測定した試料番号１〜５からの線材の超電導開始点
（Tc）、遷移温度幅（△Tc）を比較例とともに示したも
のが次の第２表である。FIG. 1 shows the critical current density (Jc) of the wires from Samples 1 to 7 in a magnetic field up to 4.2 ° K and a magnetic field of 12 T, together with a comparative example. Table 2 below shows the superconducting start points (Tc) and transition temperature widths (ΔTc) of the wires from sample numbers 1 to 5 measured by the AC susceptibility method together with comparative examples.
第１図の結果からわかるように、仮焼時の酸素量の調整
を行うことにより、液体ヘリウム温度での臨界電流密度
（Jc）が飛躍的に向上する。また、第２表に示されてい
るように、超電導開始点（Tc）は、ほぼ同じであって
も、遷移温度幅（△Tc）が狭く、良質の超電導体が得ら
れる。 As can be seen from the results of FIG. 1, the critical current density (Jc) at the liquid helium temperature is dramatically improved by adjusting the oxygen amount during calcination. Further, as shown in Table 2, even if the superconducting starting points (Tc) are almost the same, the transition temperature width (ΔTc) is narrow and a good superconductor can be obtained.
また、この第１図から明らかなように、4.2°Ｋ、12Tで
約45,000A/cm2という極めて優れたJc特性を有するBi系
酸化物超電導体を製造することができる。Further, as is clear from FIG. 1, it is possible to manufacture a Bi-based oxide superconductor having an extremely excellent Jc characteristic of about 45,000 A / cm 2 at 4.2 ° K and 12T.
また、実施例と同じ混合比のものを従来通り、空気中で
仮焼しただけの原料粉末を用いて、実施例と同様な方法
で短尺試料とした比較例（試料6.7）の場合は、その遷
移温度幅（△Tc）は、実施例と比較して、２倍近く広い
ことが第２表からも明らかである。さらに、4.2°Ｋ、1
2Tでの臨界電流密度（Jc）は、約10,000A/cm2と低い値
しか得られないことが、第１図からも明らかである。In the case of a comparative example (sample 6.7), which was a short sample in the same manner as in the example, using a raw material powder that was simply calcined in air as in the case of the same mixing ratio as in the example, It is clear from Table 2 that the transition temperature width (ΔTc) is almost twice as wide as that of the example. Furthermore, 4.2 ° K, 1
It is clear from FIG. 1 that the critical current density (Jc) at 2T is as low as about 10,000 A / cm 2 .
なお、150Torr〜１×10-5Torrの真空中で、880℃、10分
間〜100時間程度の仮焼処理を行っても、試料番号１お
よび２とほぼ同じ特性が得られることもわかった。It was also found that even if the calcination treatment was performed at 880 ° C. for about 10 minutes to 100 hours in a vacuum of 150 Torr to 1 × 10 −5 Torr, almost the same characteristics as those of Sample Nos. 1 and 2 were obtained.
第２図は、Bi2Sr2Ca1Cu2Agyで示される酸化物のｙ＝０
とｙ＝0.8についてJcを示した実施例と比較例である。
原料粉末の仮焼条件もこの第２図に示した。断面が２×
0.28mmの線材をアルゴン中で880℃、30時間処理し、次
いで中間加工して断面が３×0.18mmの線材とし、880
℃、50時間の熱処理を行っている。ｙ＝0.8の場合で、A
r:0＝12:1および大気中と真空中で処理の場合は、臨界
電流密度（Jc）が極めて大きく向上している。FIG. 2 shows y = 0 of the oxide represented by Bi 2 Sr 2 Ca 1 Cu 2 Agy.
And Example where Yc is shown for y = 0.8 and Comparative Example.
The calcination conditions for the raw material powder are also shown in FIG. Cross section is 2 ×
A 0.28 mm wire is treated in argon at 880 ° C for 30 hours, then intermediate processed to form a wire with a cross section of 3 × 0.18 mm.
Heat treatment is performed at ℃ for 50 hours. When y = 0.8, A
The critical current density (Jc) is greatly improved in the case of r: 0 = 12: 1 and processing in air and vacuum.
また、第３図は、Bi2Sr2Ca1Cu2AgyOで示される酸化物の
ｙ＝０とｙ＝0.8についてアルゴン中880℃、50時間の熱
処理で断面３×0.3mmの線材を処理し、かつ中間加工を
行わない場合のJcを示した例である。仮焼条件を図中に
示したが、仮焼条件がAr:0＝12:1、大気中および真空中
の処理でｙ＝0.8の場合は磁界の高い場合でも高い臨海
電流密度（Jc）が得られることがわかる。In addition, FIG. 3 shows that for the oxides represented by Bi 2 Sr 2 Ca 1 Cu 2 AgyO, y = 0 and y = 0.8, a wire rod having a cross section of 3 × 0.3 mm was heat-treated in argon at 880 ° C. for 50 hours. And, it is an example showing Jc when the intermediate processing is not performed. The calcination conditions are shown in the figure. When the calcination conditions are Ar: 0 = 12: 1 and y = 0.8 in the atmosphere and vacuum, a high critical current density (Jc) is obtained even when the magnetic field is high. You can see that you can get it.
（発明の効果） この発明により、以上詳しく説明した通り、たとえば45
000A/cm2という高い臨界電流密度（Jc）特性が得られ、
Bi系酸化物の低Tc相から高い臨界電流密度（Jc）の超電
導線が製造可能となる。また、最終の熱処理工程を不活
性ガス中でも可能にさせ、外部から線材内部への酸素の
供給を行う必要がなく、多芯線の製造も容易となる。さ
らに、Ag以外の金属シース材をも使用できることから、
強度の補強や安定化材の付加も可能となり、実用線材化
が容易となる。金属系超電導線材を用いる場合にも発生
不可能であった22T以上の高磁界でも、臨界磁界（Hc2）
値が金属系超電動体に比較してほぼ１桁高い酸化物系超
電材料の特徴を生かすことで、今後の超電導応用が格段
に進展する可能性がある。(Effect of the Invention) According to the present invention, as described in detail above, for example, 45
High critical current density (Jc) characteristics of 000A / cm 2 are obtained,
Superconducting wire with high critical current density (Jc) can be manufactured from low Tc phase of Bi-based oxide. Further, the final heat treatment step can be performed even in an inert gas, and it is not necessary to supply oxygen from the outside to the inside of the wire, which facilitates the production of the multifilamentary wire. Furthermore, since metal sheath materials other than Ag can be used,
It is possible to reinforce the strength and add a stabilizing material, and it becomes easy to make a practical wire. Critical magnetic field (Hc 2 ) even at a high magnetic field of 22T or more, which could not be generated even when using a metal-based superconducting wire
By taking advantage of the characteristics of oxide-based superconducting materials whose values are about an order of magnitude higher than those of metallic superconductors, there is a possibility that future superconducting applications will make marked progress.
第１図は、この発明の実施例および比較例として、Agシ
ースのBi系酸化物超電導線材について、4.2゜Ｋにおけ
る臨界電流密度−磁界との特性を示した特性相関図であ
る。 第２図および第３図は、仮焼条件を変えて処理した場合
の磁界と磁界電流密度との関係を示した相関図である。FIG. 1 is a characteristic correlation diagram showing the characteristics of the critical current density at 4.2 ° K and the magnetic field for a Bi-based oxide superconducting wire having an Ag sheath as an example and a comparative example of the present invention. FIG. 2 and FIG. 3 are correlation diagrams showing the relationship between the magnetic field and the magnetic field current density when the treatment is performed under different calcination conditions.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｈ０１Ｌ 39/12 ＺＡＡ Ｃ 9276−4Ｍ (56)参考文献 特開 平２−30619（ＪＰ，Ａ) 特開 平２−120227（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // H01L 39/12 ZAA C 9276-4M (56) Reference JP-A-2-30619 (JP, JP, A) JP-A-2-120227 (JP, A)
Claims (6)
しい構成比に配合された原料粉末を、酸素ガスの比がN2
ガスおよび／または不活性ガスに対して1/5〜1/100の減
圧酸素雰囲気中、または150〜１×10-5Torrの真空中に
おいて、800〜880℃の温度で加熱処理することを特徴と
するBi系酸化物超電導体用粉末の製造方法。1. A raw material powder blended in a composition ratio substantially equal to the composition of a low Tc phase of a Bi-based oxide superconductor, wherein the oxygen gas ratio is N 2
Characterized by heat treatment at a temperature of 800 to 880 ° C in a reduced pressure oxygen atmosphere of 1/5 to 1/100 against a gas and / or an inert gas, or in a vacuum of 150 to 1 × 10 -5 Torr And a method for producing a powder for a Bi-based oxide superconductor.
しい構成比に配合された原料粉末を大気中において、80
0〜880℃の温度で１次加熱した後に、150〜１×10-5Tor
rの真空中において400〜700℃の温度で、またはH2ガス
の比が不活性ガスに対して1/10〜1/100の水素還元雰囲
気中において300〜650℃の温度で２次加熱処理すること
を特徴とするBi系酸化物超電導体用粉末の製造方法。2. A raw material powder mixed in a composition ratio substantially equal to the composition of a low Tc phase of a Bi-based oxide superconductor at 80% in air.
After primary heating at a temperature of 0-880 ℃, 150-1 × 10 -5 Tor
Secondary heat treatment at a temperature of 400 to 700 ° C in a vacuum of r, or at a temperature of 300 to 650 ° C in a hydrogen reducing atmosphere in which the H 2 gas ratio is 1/10 to 1/100 with respect to the inert gas. A method for producing a powder for a Bi-based oxide superconductor, comprising:
構成比に配合された請求項（１）または（２）記載のBi
系酸化物超電導体用粉末の製造方法。 BizSr2CaxCu2My （Ｍは、Ag、Pb、Ni、Co、CrまたはMnの一種以上を示
し、0.5≦ｘ≦３、０≦ｙ≦１および1.5≦ｚ≦３であ
る。）3. The Bi according to claim 1, wherein the raw material powder is blended in a constituent ratio represented by the following formula except oxygen.
Method for producing powder for oxide-based superconductor. Bi z Sr 2 Ca x Cu 2 M y (M represents Ag, Pb, Ni, Co, and one or more kinds of Cr or Mn, is 0.5 ≦ x ≦ 3,0 ≦ y ≦ 1 and 1.5 ≦ z ≦ 3 .)
り製造した粉末を用いて金属シース加工線材を作製する
にあたり、本焼結工程において少なくとも１回以上室温
で中間圧縮することを特徴とするBi系酸化物超電導線材
の製造方法。4. A metal sheath processed wire rod is produced by using the powder produced by the method according to claim 1 or 2, wherein at least one intermediate compression is performed at room temperature in the main sintering step. And a method for producing a Bi-based oxide superconducting wire.
分圧が1/5以上の雰囲気下において880℃未満の温度で後
処理する請求項（４）記載のBi系酸化物超電導線材の製
造方法。5. The production of a Bi-based oxide superconducting wire according to claim 4, wherein after the intermediate compression step at room temperature, post-treatment is performed at a temperature of less than 880 ° C. in an atmosphere having an oxygen partial pressure of 1/5 or more. Method.
スおよび／または不活性ガス雰囲気中において再度焼結
する請求項（４）記載のBi系酸化物超電導線材の製造方
法。6. The method for producing a Bi-based oxide superconducting wire according to claim 4, wherein after the intermediate compression step at room temperature, the sintering is performed again in an atmosphere of N 2 gas and / or an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1341238A JPH075314B2 (en) | 1989-12-28 | 1989-12-28 | Bi-based oxide superconductor powder and method for producing the wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1341238A JPH075314B2 (en) | 1989-12-28 | 1989-12-28 | Bi-based oxide superconductor powder and method for producing the wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03199124A JPH03199124A (en) | 1991-08-30 |
| JPH075314B2 true JPH075314B2 (en) | 1995-01-25 |
Family
ID=18344462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1341238A Expired - Lifetime JPH075314B2 (en) | 1989-12-28 | 1989-12-28 | Bi-based oxide superconductor powder and method for producing the wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075314B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4199820B2 (en) | 2005-06-01 | 2008-12-24 | フェトン株式会社 | Laser processing apparatus and laser processing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU589068B2 (en) * | 1987-08-10 | 1989-09-28 | Furukawa Electric Co. Ltd., The | Method of manufacturing oxide superconductor, and method of manufacturing composite oxide powder which is the precursor of the oxide superconductor |
| JPH02120227A (en) * | 1988-10-28 | 1990-05-08 | Fujikura Ltd | Production of bi-based oxide superconductor |
-
1989
- 1989-12-28 JP JP1341238A patent/JPH075314B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03199124A (en) | 1991-08-30 |
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