JPH02215017A - Manufacture of oxide superconductor - Google Patents
Manufacture of oxide superconductorInfo
- Publication number
- JPH02215017A JPH02215017A JP3446789A JP3446789A JPH02215017A JP H02215017 A JPH02215017 A JP H02215017A JP 3446789 A JP3446789 A JP 3446789A JP 3446789 A JP3446789 A JP 3446789A JP H02215017 A JPH02215017 A JP H02215017A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- oxide superconductor
- superconductor
- porous
- superconducting
- 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.)
- Pending
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 239000004020 conductor Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 abstract description 12
- 238000005245 sintering Methods 0.000 abstract description 10
- 239000011812 mixed powder Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000008646 thermal stress Effects 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 238000007596 consolidation process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 230000003187 abdominal effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
「産業との利用分野」
本発明は、超電導マグネット用コイル、あるいは電力輸
送線などとしての応用開発が進められている酸化物超電
導導体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application in Industry] The present invention relates to a method for producing an oxide superconducting conductor, which is currently being developed for applications such as coils for superconducting magnets or power transmission lines.
「従来技術とその課題」
近年に至り、常電導状態から超電導状態に遷移する臨界
温度（’ｌ”ｃ）が液体窒素温度以との高い値を示す酸
化物系の超電導材料が種々発見されつつある。"Prior art and its challenges" In recent years, various oxide-based superconducting materials have been discovered that exhibit a critical temperature ('l'c) for transitioning from a normal conducting state to a superconducting state that is higher than the liquid nitrogen temperature. be.
そして、このような酸化物系の超電導材料からなる超電
導体を製造する方法として、例えば、Ｙ−Ｂａ−Ｃｕ−
０系の超電導体を製造する場合、Ｙ、０゜粉末とＢａＯ
粉末とＣｕＯ粉末とを混合した混合粉末を圧粉成形して
バルク状とし、次いでこのバルクに熱処理を施す方法が
知られている。As a method for manufacturing a superconductor made of such an oxide-based superconducting material, for example, Y-Ba-Cu-
When manufacturing a 0-based superconductor, Y, 0° powder and BaO
A method is known in which a mixed powder of powder and CuO powder is compacted into a bulk shape, and then this bulk is subjected to heat treatment.
また、この種の酸化物系超電導体を線材化する試みもな
されている。現在のところ、線材化するには、例えば、
銅、銀などの金属シース内に前記混合粉末を充填したの
ち、縮径加工を施して混合粉末を圧密し、更にこの圧密
体に熱処理を施して超電導物質を生成させ、酸化物超電
導線を得る方法が知ら°れている。Attempts have also been made to make wire rods from this type of oxide-based superconductor. Currently, in order to make wire rods, for example,
After filling the mixed powder into a metal sheath made of copper, silver, etc., the mixed powder is compacted by diameter reduction processing, and the compacted body is further heat-treated to generate a superconducting substance to obtain an oxide superconducting wire. The method is known.
しかしながら、このような方法では、熱処理に際し、金
属シースを構成する金属材料と酸化物超電導体との間の
熱膨張率の違いにより、金属シースと酸化物超電導体と
の間に熱応力が発生し、この熱応力によって酸化物超電
導体にクラックなどの欠陥部分を生じる問題があった。However, in such a method, thermal stress is generated between the metal sheath and the oxide superconductor during heat treatment due to the difference in coefficient of thermal expansion between the metal material constituting the metal sheath and the oxide superconductor. However, this thermal stress causes defects such as cracks in the oxide superconductor.
なお、本発明者らが、このように製造された超電導線と
前述のバルク状の超電導体の特性を臨界電流密度（Ｊｃ
）の面で比較してみたところ前者は後者のｌ／２〜１７
５程度の値しか示さないものがあるとの結果が得られた
。The present inventors have determined the characteristics of the superconducting wire manufactured in this way and the bulk superconductor described above by determining the critical current density (Jc
), the former is l/2~17 of the latter.
The results showed that some samples showed only a value of about 5.
したがって、従来より良好な超電導特性、特に臨界電流
値の高い酸化物超電導導体を製造できる技術の開発が望
まれている。Therefore, it is desired to develop a technique that can produce an oxide superconducting conductor with better superconducting properties than conventional ones, especially a high critical current value.
「課題を解決するための手段」
この発明では前記課題を解決するために、中空の金属シ
ースの内部あるいは基板上に酸化物超電導体の前駆体を
設け、この前駆体に熱処理を施して超電導体を生成する
酸化物超電導体の製造方法において、前記金属シースあ
るいは基板と、前駆体との間に、気化物質を含む多孔質
前駆体層を設け、酸化物超電導体の前駆体の熱処理とと
もに多孔質前駆体層の熱処理を行って気化物質を気化さ
せ、金属シースあるいは基板と、超電導体との間に多孔
質層を形成するものである。"Means for Solving the Problems" In order to solve the above problems, the present invention provides a precursor of an oxide superconductor inside a hollow metal sheath or on a substrate, and heat-treats this precursor to form a superconductor. In the method for producing an oxide superconductor, a porous precursor layer containing a vaporized substance is provided between the metal sheath or substrate and the precursor, and the porous The precursor layer is heat-treated to vaporize the vaporized substance, thereby forming a porous layer between the metal sheath or substrate and the superconductor.
以下に本発明の製造方法を超電導線（叩電導導体）の製
造方法に適用した例について図面を参照して詳細に説明
する。DESCRIPTION OF THE PREFERRED EMBODIMENTS An example in which the manufacturing method of the present invention is applied to a manufacturing method of a superconducting wire (beaten conductor) will be described below in detail with reference to the drawings.
この例において酸化物超電導線を製造するには、まず、
第１図に示すように、銅あるいは銅合金、または銀、金
、白金などの貴金属、あるいは貴金属の合金、アルミニ
ウム、ステンレスなどからなる金属管（金属シース）１
を用意する。In this example, to manufacture the oxide superconducting wire, first,
As shown in Figure 1, a metal tube (metal sheath) 1 made of copper or copper alloy, precious metals such as silver, gold, platinum, alloys of precious metals, aluminum, stainless steel, etc.
Prepare.
次にこの金属管１の内部の中心側に酸化物超電導体の前
駆体部２を設け、更に前駆体部２と金属管！の間に多孔
質前駆体層３を設けて複合体４を形成する。Next, a precursor section 2 of an oxide superconductor is provided on the center side inside this metal tube 1, and then the precursor section 2 and the metal tube! A porous precursor layer 3 is provided in between to form a composite 4.
前駆体部２としては、酸化物超電導体の構成元素を含む
原料粉末、あるいはその圧密体、または前記圧密”体の
仮焼物、前記圧密体を焼結して得た超電導体からなる材
料などを用いる。なお、この金属管ｉ内に収容する前駆
体部２は粉末状、粒状、圧密体あるいはこれらの混合物
などのいずれでも良い。前記酸化物系超電導体とは、Ａ
−Ｂ−Ｃ−Ｄ系（ただし、Ａは、Ｓｃ、Ｙ、Ｌａ、Ｃｅ
、Ｐｒ、Ｎｄ、Ｐａ。The precursor portion 2 may be a raw material powder containing constituent elements of the oxide superconductor, a compacted body thereof, a calcined product of the compacted body, a superconductor obtained by sintering the compacted body, or the like. The precursor portion 2 accommodated in the metal tube i may be in the form of powder, granules, a compact, or a mixture thereof.The oxide-based superconductor is
-B-C-D system (A is Sc, Y, La, Ce
, Pr, Nd, Pa.
Ｓｓ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｂｒ、Ｔｓ、Ｙ
ｂ、Ｌｕ等の周期律表第１１１ａ族元素とＴＩとＢｉの
うちＩＮあるいは２１１以上を表し、ＢはＳ ｒ、Ｂａ
、Ｃａ、Ｂｅ、Ｍｇ。Ss, Eu, Gd, Tb, Dy, Ho, Br, Ts, Y
Represents IN or 211 or more of Group 111a elements of the periodic table such as b, Lu, TI and Bi, and B is S r, Ba
, Ca, Be, Mg.
Ｒａ等の周期律表第Ｕａ族元素のうち１種あるいは２種
以上を表し、ＣはＣｕ、Ａｇ、Ａｕの周期律表第１ｂ族
元素およびＮｂのうちＣｕあるいはＣｕを含む２種以上
を表し、ＤはＯ，Ｓ、Ｓｅ等の周期律表第ｖｔｂ族元素
およびＦ、Ｃ１７，Ｂｒ等の周期律表第■ｂ族元素のう
ち０あるいは０を含む２ｉ１以、Ｊ＝を表す。Represents one or more types of elements of group Ua of the periodic table such as Ra, and C represents elements of group 1b of the periodic table such as Cu, Ag, and Au, and two or more types including Cu or Cu of Nb. , D represents 2i1 or more containing 0 or 0 of elements of group Vtb of the periodic table such as O, S, and Se, and elements of group 1b of the periodic table such as F, C17, and Br, and J=.
）などを示すものである。) etc.
また、この酸化物系超電導体用の原料粉末とは、前記へ
元素の酸化物とＢ元素の炭酸塩または酸化物とＣ元素の
酸化物との混合粉末か、あるいは、この混合粉末を仮焼
処理した後粉砕してなるものなどである。、またこの場
合、各元素からなる化合物の混合比は目的とする酸化物
超電導体の組成に応じて適宜決定されるものとする。The raw material powder for this oxide-based superconductor is a mixed powder of an oxide of the above-mentioned element B and a carbonate of the element B, or a mixed powder of an oxide and an oxide of the C element, or a calcined powder of this mixed powder. These include those that are processed and then crushed. In this case, the mixing ratio of the compounds made of each element shall be determined as appropriate depending on the composition of the intended oxide superconductor.
さらに、酸化物超電導体の粉末を用いる場合は、前記し
た原料粉末に加熱処理等を施し、これにより酸化物系超
電導体とした後、粉砕して粉末にしたものを用いる。さ
らにまた、成形体は、前記超電導体の粉末に仮焼処理、
圧粉処理等を施して線状などに成形したものとする。こ
こで仮焼処理温度として前記酸化物超電導体粉末の場合
、４００〜１０００℃程度とされる。また、圧粉処理に
は例えばラバープレス法等が採用される。Further, when using an oxide superconductor powder, the raw material powder described above is subjected to a heat treatment or the like to form an oxide superconductor, and then pulverized into a powder. Furthermore, the molded body may be formed by subjecting the powder of the superconductor to a calcination treatment.
It is formed into a linear shape by applying powder processing or the like. Here, in the case of the oxide superconductor powder, the calcination treatment temperature is about 400 to 1000°C. In addition, for example, a rubber press method or the like is employed for the powder compaction treatment.
一方、多孔質前駆体層３としては、前記のように用いら
れる酸化物超電導体の前駆体と同等あるいは近似した組
成の複合酸化物であって、後述する焼結処理後において
、その圧密塵が酸化物超電導体の部分よりも低くなるよ
うなものを用いる。On the other hand, the porous precursor layer 3 is a composite oxide having a composition equivalent to or similar to the precursor of the oxide superconductor used as described above, and after the sintering treatment described below, the consolidation dust is removed. Use something that is lower than the oxide superconductor part.
この例においては、目的とする酸化物超電導体がＹ ｔ
Ｂａｍｃ１１ｓｏｔ４なる組成のものである場合には、
Ｙ ＋Ｂ ａｒｃ ｕｓｏ 、−８なる組成になるよう
に調製した混合″粉末に有機バインダーを混合したもの
などを用いる。なお、目的とする酸化物超電導体が、口
ｉ＊Ｐ ｂ６．ｓｓ ｒ、Ｃａｍｃ ｕｓｏ ｘなる組
成である場合には、Ｂ ｉｔＰ ｔ）１．３Ｓ ｒ＊ｃ
ａｒｃ ｕｓｏ ｚなる組成になるように調製した混
合粉末に有機バインダーを混合したものなどを用いる。In this example, the target oxide superconductor is Y t
If the composition is Bamc11sot4,
A mixed "powder prepared to have a composition of Y +B arcuso, -8, mixed with an organic binder, etc. is used. Note that the target oxide superconductor is If the composition is uso x, B itP t)1.3S r*c
A mixed powder prepared to have a composition of arc uso z mixed with an organic binder is used.
金属管１の内部に酸化物超電導体の前駆体部２と多孔質
前駆体層３を形成して複合体４を形成するには、圧密加
工により、線状あるいは棒状に形成した前駆体部２を金
属管ｉの中心部に挿入した後に、この前駆体部２と金属
管１の内周面との間の隙間に有機バインダー入りの混合
粉末を充填すれば良い。また、有機バインダー入りの混
合粉末を予めパイプ状に成形して金属管１の内部に挿入
した後に、その内部に前駆体部を形成するための圧密体
などを充填する手段を用いても良い。In order to form the composite body 4 by forming the precursor part 2 of the oxide superconductor and the porous precursor layer 3 inside the metal tube 1, the precursor part 2 is formed into a linear or rod shape by consolidation processing. is inserted into the center of the metal tube i, and then the gap between the precursor portion 2 and the inner peripheral surface of the metal tube 1 may be filled with a mixed powder containing an organic binder. Alternatively, a method may be used in which a mixed powder containing an organic binder is previously formed into a pipe shape and inserted into the metal tube 1, and then a compacted body or the like for forming the precursor portion is filled inside the pipe.
なおまた、有機バインダー入りの混合粉末を用いること
なく本発明を実施する場合、多孔質前駆体層を焼結した
後の密度が、酸化物超電導体の前駆体部を焼結した後の
密度よりも低くなれば良いので、圧密加工の段階で圧密
度を調節し、金属管ｌに充填する段階の前駆体部２の密
度を多孔質前駆体層３の密度よりも高めておけば良い。Furthermore, when carrying out the present invention without using a mixed powder containing an organic binder, the density after sintering the porous precursor layer is lower than the density after sintering the precursor portion of the oxide superconductor. Therefore, the density of the precursor portion 2 at the stage of filling the metal tube 1 may be made higher than the density of the porous precursor layer 3 by adjusting the density at the stage of the consolidation process.
前述のように複合体４を作成したならば、複合体４に縮
径加工を施して所望の線径の線材を得る。Once the composite body 4 is created as described above, the composite body 4 is subjected to diameter reduction processing to obtain a wire rod having a desired wire diameter.
この場合に行う縮径加工としては、例えば線引き加工や
溝付きロールを用いて行う圧延加工あるいはロータリー
スウエージングによる鍛造加工などの縮径加工法が採用
される。In this case, diameter reduction processing methods such as wire drawing, rolling using a grooved roll, or forging using rotary swaging are employed.
次いで、前記線材に熱処理を施す。この場合の熱処理条
件としては、Ｙ系とＴＩ系の場合は好ましくは酸素雰囲
気中などにおいて、Ｂｉ系の場合は不活性ガスと酸素ガ
スの混合雰囲気中などにおいて、８００〜１０００℃の
温度の範囲で０，１時間〜敗１０時間程度加熱するらの
とする。Next, the wire is subjected to heat treatment. The heat treatment conditions in this case are preferably in an oxygen atmosphere for Y-based and TI-based products, and in a mixed atmosphere of inert gas and oxygen gas for Bi-based products at a temperature in the range of 800 to 1000°C. Heat for about 0.1 hour to 10 hours.
以との熱処理で前駆体部２を焼結することで第２図に示
すような酸化物超電導体５を生成する。By sintering the precursor portion 2 through the heat treatment described above, an oxide superconductor 5 as shown in FIG. 2 is produced.
また、この熱処理Ｉこよって多孔質前駆体層３において
は、有機バインダーが気化するので、酸化物超電導体５
よりら気孔率の高い、即ち密度の低い多孔質層″６が生
成され、第２図に示す超電導線７を得ることができる。Further, as a result of this heat treatment I, the organic binder is vaporized in the porous precursor layer 3, so that the oxide superconductor 5
A porous layer "6" having a higher porosity, that is, a lower density, is produced, and a superconducting wire 7 shown in FIG. 2 can be obtained.
なお、多孔質層６の厚さは、１００〜４００μｍ程度が
好ましい。多孔質層６の厚さが！００μ騰より薄い場合
は、クラック防止を十分に行うことができないので好ま
しくなく、４００μ騰より厚い場合は、特にクラック防
止という点からは問題はないが、バッファ層も含めて計
算した場合のオーバーオールでの臨界電流密度が小さく
なってしまうので好ましくない。また、熱処理後の酸化
物超電導体の密度が５．８〜６．３ｇ／ｃｓ”となる場
合に、多孔質層の密度は４．０〜５．０ｇ／ｃ鳳”程度
が好ましい。Note that the thickness of the porous layer 6 is preferably about 100 to 400 μm. The thickness of the porous layer 6! If it is thinner than 00 μm, it is not preferable because it cannot sufficiently prevent cracks, and if it is thicker than 400 μm, there is no problem in particular from the viewpoint of preventing cracks, but the overall value is calculated including the buffer layer. This is not preferable because the critical current density becomes small. Further, when the density of the oxide superconductor after heat treatment is 5.8 to 6.3 g/cs, the density of the porous layer is preferably about 4.0 to 5.0 g/cs.
なお、面記熱処理の終了とともに超電導線７が常温まで
冷却される過程において、金属管１と超電導体５との間
に熱膨張係数の差異があるので、金属管１の収縮率と酸
化物超電導体５の収縮率とが異なり、結果的に金属管！
側から酸化物超電導体５側に熱応力が作用しようとする
が、金属管量と酸化物超電導体５との間に設けた多孔質
層６がこの熱応力を吸収する。即ち、多孔質層６におい
て金属管１に近い部分に熱応力の集中がなされ、この部
分にクラックが選択的に生じて前記熱応力が解消される
。従って熱応力が酸化物超電導体５に作用することを防
止することができ、酸化物超電導体５のクラック発生を
防止することができる。In addition, in the process in which the superconducting wire 7 is cooled to room temperature upon completion of the surface heat treatment, there is a difference in thermal expansion coefficient between the metal tube 1 and the superconductor 5, so the shrinkage rate of the metal tube 1 and the oxide superconductor The shrinkage rate of body 5 is different, resulting in a metal tube!
Although thermal stress tends to act on the oxide superconductor 5 side from the side, the porous layer 6 provided between the metal tube and the oxide superconductor 5 absorbs this thermal stress. That is, thermal stress is concentrated in a portion of the porous layer 6 near the metal tube 1, and cracks are selectively generated in this portion, thereby eliminating the thermal stress. Therefore, thermal stress can be prevented from acting on the oxide superconductor 5, and cracks in the oxide superconductor 5 can be prevented from occurring.
従って臨界電流密度の高い優れた超電導線７を得ること
ができる。Therefore, an excellent superconducting wire 7 with a high critical current density can be obtained.
第３図は本発明方法を層状の超電導導体の製造方法に適
用した例を説明するためのものである。FIG. 3 is for explaining an example in which the method of the present invention is applied to a method for manufacturing a layered superconducting conductor.
この例では、基板ＩＯ上に多孔質ｆｉｌｌを介して酸化
物超電導層（Ｒ化物超電導体）！２を形成して酸化物超
電導導体１３が構成されている。In this example, an oxide superconducting layer (R-ride superconductor) is formed on the substrate IO via a porous fill! 2 to form an oxide superconducting conductor 13.
ｎη記構成の酸化物超電導導体１３を製造するには、基
板ｌの上面に前記の例で用いた多孔質前駆体層３と同等
の材料からなる多孔質前駆体層を形成し、その上に酸化
物超電導体の前駆体層を形成し、次いで全体を前記と同
等の条件で熱処理することにより製造することができる
。In order to manufacture the oxide superconducting conductor 13 having the structure nη, a porous precursor layer made of the same material as the porous precursor layer 3 used in the above example is formed on the upper surface of the substrate l, and then It can be manufactured by forming a precursor layer of an oxide superconductor and then heat-treating the entire structure under the same conditions as described above.
この場合の酸化物超電導導体１３においても先の例と同
等の効果を得ることができる。In this case, the oxide superconducting conductor 13 can also provide the same effects as in the previous example.
「実施例！」
本発明方法を実施して第４図に断面構造を示す超電導線
２０を製造するとともに、従来の方法を実施して第５図
に断面構造を示す超電導線３０を製造した。第４図に示
す超電導線２０においては、超電導導体部２Ｉの外周面
を多孔質層２２が覆い、多孔質！２２の外周面を金属シ
ース２３が覆った構造であり、超電導線３０においては
超電導導体部３Ｉの外周面を金属シース２３が覆った構
造となっている。"Example!" A superconducting wire 20 whose cross-sectional structure is shown in FIG. 4 was manufactured by implementing the method of the present invention, and a superconducting wire 30 whose cross-sectional structure is shown in FIG. 5 was manufactured by implementing the conventional method. In the superconducting wire 20 shown in FIG. 4, a porous layer 22 covers the outer peripheral surface of the superconducting conductor portion 2I, making it porous! In the superconducting wire 30, the outer circumferential surface of the superconducting conductor portion 3I is covered with the metal sheath 23.
超電導線２０を製造するには、まず、外径１０１１内径
６−−の鎖管を用意し、この鎖管の中心側にＹ ＩＢ
ａｔｃ Ｌ１３０ ｔ−８なる組成になるように調製し
た混合粉末の圧密体を挿入し、圧密体と鎖管との間の間
隙に、Ｙ ｒ Ｂ ａｔ Ｃｕ３０ ？−８なる組成の
混合粉末とポリビニルアルコール（ＰＶＡ）を混入して
なる混合粉末を充填し、全体を縮径して線材を得た。縮
径加工後の鎖管の外径は５ ａｍ、多孔質前駆体層の部
分の外径は３ｍｍ、酸化物超電導体の面駆体部分の直径
は２．４ｍｍとなった。In order to manufacture the superconducting wire 20, first, a chain tube with an outer diameter of 1011 and an inner diameter of 6 is prepared, and a YIB is placed on the center side of the chain tube.
A compacted body of mixed powder prepared to have a composition of atc L130 t-8 was inserted, and Y r Bat Cu30 ? A mixed powder obtained by mixing a mixed powder with a composition of -8 and polyvinyl alcohol (PVA) was filled, and the diameter of the whole was reduced to obtain a wire rod. After diameter reduction processing, the outer diameter of the chain tube was 5 am, the outer diameter of the porous precursor layer portion was 3 mm, and the diameter of the surface precursor portion of the oxide superconductor was 2.4 mm.
次にこの線材を酸素ガス雰囲気中において８９０℃で１
２時間加熱した後に徐冷する熱処理を施して酸化物超電
導線を得た。Next, this wire was heated at 890°C for 1 hour in an oxygen gas atmosphere.
A heat treatment of heating for 2 hours and then slow cooling was performed to obtain an oxide superconducting wire.
この酸化物超電導線の臨界電流密度（Ｊｃ）は液体窒素
温度において２８００ Ａ／ａｍ”を示した。また、焼
結後の超電導導体部の密度は６ 、１ ｇ／ ａｍ”、
多孔質層の密度は４ 、５ ｇ／ ａｍ”であった。The critical current density (Jc) of this oxide superconducting wire was 2800 A/am'' at liquid nitrogen temperature.The density of the superconducting conductor after sintering was 6.1 g/am'',
The density of the porous layer was 4.5 g/am''.
一方、比較のために第５図に示す酸化物超電導線３０を
製造した。この場合、外径１０５ｍ、内径６ｍｓの鎖管
にＹ ＩＢ ａｒｃ ｕａＯｔ−６なる組成になるよう
に調製した混合粉末を充填し、縮径加工を施して金属シ
ースの外径が５ｊＩＩ＋１前駆体部の直径が３ｍｍの線
材を得、この線材を前記と同等の条件で熱処理して酸化
物超電導線３０を得た。On the other hand, for comparison, an oxide superconducting wire 30 shown in FIG. 5 was manufactured. In this case, a chain tube with an outer diameter of 105 m and an inner diameter of 6 ms is filled with a mixed powder prepared to have a composition of YIB arc uaOt-6, and the diameter is reduced so that the outer diameter of the metal sheath is 5jII + 1 of the precursor part. A wire rod with a diameter of 3 mm was obtained, and this wire rod was heat-treated under the same conditions as described above to obtain an oxide superconducting wire 30.
この酸化物超電導線の臨界電流密度は液体窒素温度にお
いて６４０Ａ／ｃｇ＋”を示した。The critical current density of this oxide superconducting wire was 640 A/cg+'' at liquid nitrogen temperature.
なお、酸化物超電導線２０と３０の各々について、焼結
後において金属シースを溶解除去してみたが、超電導線
２０の超電導導体部２１には超電導部にはクラックが生
じていなかったのに対し、超電導線３０の超電導導体部
３１には微細なりラックが生じていた。In addition, we tried dissolving and removing the metal sheaths of each of the oxide superconducting wires 20 and 30 after sintering, but while no cracks were found in the superconducting conductor portion 21 of the superconducting wire 20, , fine racks were generated in the superconducting conductor portion 31 of the superconducting wire 30.
「実施例２」
前記と同等の手順を行うとともに、鎖管に充填する混合
粉末としてＢ ｉ、Ｐ ｂｏ、ｓＳ ｒ、Ｃａ、Ｃｕｓ
Ｏｘなる組成の混合粉末を用い、第４図に示す断面構造
の酸化物超電導線と、第５図に示す断面構造の酸化物超
電導線を製造した。この例の場合、熱処理は、７％Ｏ，
ガス雰囲気中において８６０℃で１２時間加熱した後に
徐冷する条件とした。"Example 2" The same procedure as above was carried out, and B i, P bo, sS r, Ca, Cu were used as the mixed powder to be filled in the chain tube.
An oxide superconducting wire having a cross-sectional structure shown in FIG. 4 and an oxide superconducting wire having a cross-sectional structure shown in FIG. 5 were manufactured using a mixed powder having a composition of Ox. In this example, the heat treatment consisted of 7% O,
The conditions were such that it was heated at 860° C. for 12 hours in a gas atmosphere and then slowly cooled.
第４図に示す構造の酸化物超電導線の臨界電流密度（Ｊ
ｃ）は、液体窒素温度において、Ｉ２５０Ａ／ａｍ”を
示した。また、焼結後において超電導導体部の密度は５
、７ ｇ／ ａｍ”、多孔質層の密度は４ 、０ ｇ
／ ａｍ”であった。The critical current density (J
c) showed I250A/am" at liquid nitrogen temperature. Also, the density of the superconducting conductor part after sintering was 5
, 7 g/am”, the density of the porous layer is 4,0 g
/am”.
この酸化物超電導線の臨界電流密度は液体窒素温度にお
いて３１０Ａ／ｃｍ”を示した。The critical current density of this oxide superconducting wire was 310 A/cm'' at liquid nitrogen temperature.
なお、この実施例で製造した２つの酸化物超電導線の各
々について、焼結後において金属シースを溶解除去して
みたが、本発明の方法を適用して製造した酸化物超電導
線の超電導導体部にけクラックが生じていなかったのに
対し、従来の方法で製造された酸化物超電導線の超電導
導体部には微細なりラックが生じていた。Note that the metal sheaths of each of the two oxide superconducting wires manufactured in this example were melted and removed after sintering, but the superconducting conductor portion of the oxide superconducting wire manufactured by applying the method of the present invention was While no cracks were observed, fine racks were observed in the superconducting conductor portion of the oxide superconducting wire manufactured by the conventional method.
「発明の効果」
以上説明したようにこの発明は、酸化物超電導体と、金
属シースあるいは基板との間に多孔質層を設けたので、
熱処理後の冷却時に金属シースあるいは基板と酸化物超
電導体との熱膨張差に起因して熱応力が作用した場合で
あっても、多孔質層がこの熱応力を緩和するので酸化物
超電導体にクラックを生じることがない。従ってクラッ
クの生じていない臨界電流密度の高い酸化物超電導導体
を製造することができる。"Effects of the Invention" As explained above, the present invention provides a porous layer between the oxide superconductor and the metal sheath or substrate.
Even if thermal stress is applied due to the difference in thermal expansion between the metal sheath or substrate and the oxide superconductor during cooling after heat treatment, the porous layer relieves this thermal stress and the oxide superconductor No cracks will occur. Therefore, it is possible to produce an oxide superconducting conductor with no cracks and a high critical current density.
第１図と第２図は本発明の一実施例を説明するためのも
ので、第重図は複合体の断面図、第２図は超電導線の断
面図、第３図は本発明の他の実施例を説明するための断
面図、第４図は実施例において製造した酸化物超電導線
の断面図、第５図は実施例に°おいて製造した従来の酸
化物超電導線の断面図である。
！・・・金属管（金属シース）、２・・・面部体部、３
・・・多孔質前駆体層、４・・・腹合体、５・・・酸化
物超電導体、６・・・多孔質層、７・・・超電導線（超
電導導体）、ＩＯ・・・基板、１１・・・多孔質層、！
２・・・酸化物超電導層（酸化物超電導体）、！３・・
・酸化物超電導導体、２０・・・超電導線（酸化物超電
導導体）、２Ｉ・・・超電導体、２２・・・多孔質層、
２３・・・金属シース。FIGS. 1 and 2 are for explaining one embodiment of the present invention. The second figure is a sectional view of a composite, FIG. 2 is a sectional view of a superconducting wire, and FIG. 3 is a sectional view of a superconducting wire. FIG. 4 is a cross-sectional view of the oxide superconducting wire manufactured in the example, and FIG. 5 is a cross-sectional view of the conventional oxide superconducting wire manufactured in the example. be. ! ...Metal tube (metal sheath), 2...Face body part, 3
... Porous precursor layer, 4... Abdominal coalescence, 5... Oxide superconductor, 6... Porous layer, 7... Superconducting wire (superconducting conductor), IO... Substrate, 11...Porous layer!
2...Oxide superconducting layer (oxide superconductor),! 3...
- Oxide superconducting conductor, 20... superconducting wire (oxide superconducting conductor), 2I... superconducting conductor, 22... porous layer,
23...Metal sheath.
Claims (1)
体の前駆体部を設け、この前駆体部に熱処理を施して酸
化物超電導体を生成させ、酸化物超電導導体を製造する
方法において、 前記金属シースあるいは基板と、前駆体との間に、多孔
質前駆体層を設け、酸化物超電導体の前駆体の熱処理と
ともに多孔質前駆体層の熱処理を行い、金属シースある
いは基板と、酸化物超電導体との間に多孔質層を形成す
ることを特徴とする酸化物超電導導体の製造方法。[Claims] A precursor portion of an oxide superconductor is provided inside a hollow metal sheath or on a substrate, and the precursor portion is heat-treated to generate an oxide superconductor to produce an oxide superconductor. In the method of A method for producing an oxide superconducting conductor, comprising forming a porous layer between the oxide superconductor and the oxide superconductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3446789A JPH02215017A (en) | 1989-02-14 | 1989-02-14 | Manufacture of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3446789A JPH02215017A (en) | 1989-02-14 | 1989-02-14 | Manufacture of oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02215017A true JPH02215017A (en) | 1990-08-28 |
Family
ID=12415053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3446789A Pending JPH02215017A (en) | 1989-02-14 | 1989-02-14 | Manufacture of oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02215017A (en) |
-
1989
- 1989-02-14 JP JP3446789A patent/JPH02215017A/en active Pending
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