JPH0465395A - Superconducting fibrous crystal and its production - Google Patents
Superconducting fibrous crystal and its productionInfo
- Publication number
- JPH0465395A JPH0465395A JP2177123A JP17712390A JPH0465395A JP H0465395 A JPH0465395 A JP H0465395A JP 2177123 A JP2177123 A JP 2177123A JP 17712390 A JP17712390 A JP 17712390A JP H0465395 A JPH0465395 A JP H0465395A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- fibrous
- fibrous crystal
- crystal
- powder
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 9
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 45
- 238000010438 heat treatment Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000002887 superconductor Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101150002998 LCAT gene Proteins 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、超電導繊維状結晶およびその製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a superconducting fibrous crystal and a method for producing the same.
従来技術とその問題点
近年酸化物高温超電導体が発見されて以来、種々の応用
分野において、その実用化への開発研究が盛んに行なわ
れている。Prior Art and its Problems Since the discovery of oxide high temperature superconductors in recent years, research and development efforts have been actively conducted to put them into practical use in various application fields.
より具体的には、例えば、Ｓ Ｑ Ｕ Ｉ Ｄ （Ｓｕ
ｐｅｒ−ｃｏｎｄｕｃｔｉｎｇ Ｑｕａｎｔｕｍ Ｉｎ
ｔｅｒｆｅｒｅｎｃｅ Ｄｅｖｉｃｅ）或いはジョセフ
ソン素子を使用するコンピューターなどのデイバイス、
素子類においては、酸化物超電導材料の薄膜化技術が必
要である。この薄膜化に関しては、スパッタリング法、
蒸着法、ＣＶＤ法などにより、臨界電流密度が１０６Ａ
／ｃＪを超える程度の十分実用化に供し得る特性を備え
た粒界の存在しない単結晶薄膜が製造可能であると報告
されている。More specifically, for example, S Q U I D (Su
per-conducting Quantum In
terference Device) or a device such as a computer that uses a Josephson element,
For devices, thin film technology for oxide superconducting materials is required. Regarding thinning, sputtering method,
Critical current density is 106A by vapor deposition method, CVD method, etc.
It has been reported that it is possible to produce a grain boundary-free single crystal thin film with characteristics that are sufficiently suitable for practical use, exceeding /cJ.
一方、酸化物超電導体の特性を利用する電力貯蔵、電力
輸送、強力な磁場発生などへの応用のためには、その線
材化を行なう必要があり、酸化物超電導体の仮焼粉末を
銀シースに詰めて再熱処理を行なう方法、ゾルゲル法、
酸化物超電導体の粉末を高分子溶液に懸濁させて線引き
する方法、酸化物超電導体の融液から線引きする方法な
どが試みられている。しかしながら、これらの方法によ
り得られた線材は、いずれも多結晶体であって、低密度
で且つ粒界を有しているため、実用化レベルの特性を有
するものは得られていない。また、この様な線材は、多
結晶体としての特性でもある脆さ、加工性の悪さ、曲げ
強度の低さなどの欠点を有している。On the other hand, in order to apply the properties of oxide superconductors to power storage, power transport, generation of strong magnetic fields, etc., it is necessary to make them into wires. sol-gel method,
Attempts have been made to draw wire by suspending oxide superconductor powder in a polymer solution, and to draw wire from a melt of oxide superconductor. However, the wire rods obtained by these methods are all polycrystalline, have low density, and have grain boundaries, and therefore have not been able to obtain wire rods with characteristics at a practical level. Further, such wire rods have drawbacks such as brittleness, poor workability, and low bending strength, which are characteristics of polycrystalline materials.
また、酸化物超電導体のある種のものの臨界温度が液体
窒素温度を越えることが報告されているが、このことは
、冷却コストと関連して大きな意義を有している。この
様な臨界温度か液体窒素温度よりも高い酸化物超電導体
としては、Ｂｉ系、Ｙ系、Ｔｌ系などが挙げられる。It has also been reported that the critical temperature of certain oxide superconductors exceeds the liquid nitrogen temperature, which has great significance in relation to cooling costs. Examples of such oxide superconductors having a critical temperature higher than the liquid nitrogen temperature include Bi-based, Y-based, Tl-based, and the like.
Ｂｉ系としては、Ｂｉ２Ｓｒ２Ｃｕｔ ０６相（２２０
１相） 、Ｂｉ２Ｓｒ２ＣａＣｕ２０ｓ相（２２１２相
）およびＢｉ２Ｓｒ２Ｃａ２ＣＬＩ３０１ｏ相（２２２
３相）の３種の相が存在しており、それぞれの臨界温度
から、２０に相、８０に相および１１０に相とも呼ばれ
ている。特に、臨界温度の最も高い２２２３相は、液体
窒素温度との間で大きな温度マージンがとれることなど
の点で、実用化に最も適した材料と考えられているが、
現実には、その単相化が困難であり、２２１２相または
２２０１相との混合相になりやすいという問題点がある
。固体反応法によれば、厳密な組成制御および焼成雰囲
気制御下に２２２３相の単相化が一応達成されるものの
、得られるのは、粉末或いは多結晶性の焼結体であり、
低密度で、多くの結晶粒界を有している。従って、すで
に大型の単結晶、単結晶性の繊維状結晶などが得られて
いる２２０１相および２２１２相の場合と同様に、２２
２３相の大型の単結晶、単結晶性の繊維状結晶などが得
られれば、極めて有用である。Bi-based Bi2Sr2Cut 06 phase (220
1 phase), Bi2Sr2CaCu20s phase (2212 phase) and Bi2Sr2Ca2CLI301o phase (222
There are three types of phases (3 phases), which are also called 20 phase, 80 phase, and 110 phase based on their respective critical temperatures. In particular, the 2223 phase, which has the highest critical temperature, is considered the most suitable material for practical use because it has a large temperature margin with the liquid nitrogen temperature.
In reality, it is difficult to convert it into a single phase, and there is a problem that it tends to become a mixed phase with the 2212 phase or the 2201 phase. According to the solid-state reaction method, although the 2223 phase can be made into a single phase under strict composition control and firing atmosphere control, what is obtained is a powder or polycrystalline sintered body,
It has low density and many grain boundaries. Therefore, as in the case of the 2201 phase and 2212 phase, for which large single crystals, single crystalline fibrous crystals, etc. have already been obtained, the 22
It would be extremely useful if large 23-phase single crystals, single crystalline fibrous crystals, etc. could be obtained.
問題点を解決するための手段
本発明者は、この様な技術の現状に鑑みて種々研究を重
ねた結果、Ｂｉ２Ｓｒ２Ｃｕｔ ｏ６構造またはＢｉ２
Ｓｒ２ Ｃａ、 Ｃｕ２０Ｂ構造を有する繊維状結晶
を、Ｂ１５Ｓｒ、Ｃａ、Ｃｕおよびｐｂを含む特定組成
の酸化物粉末中で特定の条件下に熱処理する場合には、
当初のｍ錐状結晶形態を保持した状態で、その結晶構造
がＢＬ＋ Ｓｒ２ Ｃａ２ＣＬＩ３０ ｒｏ構造に変化
し、臨界温度が液体酸素温度以上に上昇することを見出
した。Means for Solving the Problems The present inventor has conducted various studies in view of the current state of the technology, and as a result, has developed a Bi2Sr2Cut o6 structure or a Bi2Sr2Cut o6 structure.
When fibrous crystals having a Sr2Ca, Cu20B structure are heat-treated under specific conditions in an oxide powder with a specific composition containing B15Sr, Ca, Cu and pb,
It was found that the crystal structure changes to a BL+ Sr2 Ca2CLI30 ro structure while retaining the original m-pyramidal crystal morphology, and the critical temperature rises above the liquid oxygen temperature.
即ち、本発明は、下記の超電導繊維状結晶およびその製
造方法を提供するものである：■Ｂｉ、Ｓｒ、Ｃａ、Ｃ
ｕ、Ｐｂおよび０がらなり、その原子の組成比が
Ｂ１２−ｘ Ｐｂｘ ｓｒｌ、 ９−２． ｌ ｃａ、
、 ９−２．１ ＣＬＩ３０ｙ（０＜ｘ＜０゜４．１０
．０＜ｙ＜１１．０）であり、Ｂｉ２Ｓｒ２Ｃａ２Ｃｕ
：１０ ｔｏ構造（２２２３相）を有する超電導繊維状
結晶。That is, the present invention provides the following superconducting fibrous crystals and a method for producing the same: ■Bi, Sr, Ca, C
It consists of u, Pb and 0, and the atomic composition ratio is B12-x Pbx srl, 9-2. l ca,
, 9-2.1 CLI30y (0<x<0゜4.10
．． 0<y<11.0), and Bi2Sr2Ca2Cu
:10 Superconducting fibrous crystal with to structure (2223 phase).
■Ｂｉ、Ｓｒ、Ｃａ、Ｃｕおよび０がらなり、Ｂｉ２Ｓ
ｒ、、 Ｃａｔ ＣＬＩ２０ｇ構造（２２１２相）を有
する繊維状結晶、または、
Ｂ１５Ｓｒ、Ｃｕおよび０がらなり、
Ｂｂ ５ｒ２Ｃｕ０６構造（２２０１相）を有する繊維
状結晶を、原子の組成比が
Ｂ１−１．０
Ｓｒ＝０． ５〜１． ５
Ｃａ＝１． ０〜３． ０
Ｃｕ＝１． ０〜５． ０
Ｐｂ＝０．２〜１．０
である酸化物粉末中に埋め込み、８３０〜８６０°Ｃで
熱処理することを特徴とする、原子の組成比が
Ｂ１２−ｘ Ｐｂｘ Ｓｒ１．９〜２． ｌ Ｃａ］９
−２． ］ Ｃｕ３０ ｙ（Ｑ＜ｘ＜０．４．１０．０
＜ｙ＜１１．０）であり、Ｂｉ２Ｓｒ２Ｃａ２Ｃｕ３０
＋ｏ構造（２２２３半目）を有する超電導繊維状結晶
の製造方法。■Bi, Sr, Ca, Cu and 0, Bi2S
r,, A fibrous crystal having a Cat CLI20g structure (2212 phase), or a fibrous crystal consisting of B15Sr, Cu and 0 and having a Bb5r2Cu06 structure (2201 phase) with an atomic composition ratio of B1-1.0 Sr=0. 5-1. 5 Ca=1. 0-3. 0 Cu=1. 0-5. 0 Pb=0.2-1.0, and heat-treated at 830-860°C, with an atomic composition ratio of B12-x Pbx Sr1.9-2. lCa]9
-2. ] Cu30y(Q<x<0.4.10.0
<y<11.0), and Bi2Sr2Ca2Cu30
A method for producing a superconducting fibrous crystal having a +o structure (2223rd half).
本発明で熱処理の対象となる材料は、（イ）Ｂｉ、Ｓｒ
、Ｃａ、ＣｕおよびＯ力１らなり、Ｂｉ２Ｓｒ２Ｃａｘ
Ｃｕ２Ｏ３構造（２２１２キ目）を有する繊維状結晶
、および（ロ）Ｂｉ、Ｓｒ、ＣｕおよびＯからなり、Ｂ
ｉ２Ｓｒ２ Ｃｕｂ６構造（２２０１相）を有する繊維
状結晶を含む材料である。これら（イ）および（ロ）の
繊維状結晶にお０ては、２２１２相および２２０１相の
Ｂｉサイトがｐｂにより一部置換されていても良い。こ
れら（イ）および（ロ）の繊維状結晶は、いずれも公知
のもノテあり、（イ）のＢｉｚ ５ｒ２Ｃａ１Ｃｕ２０
Ｂ構造（２２１２相）を有する繊維状結晶は、本発明者
により、Ｊａｐａｎｅｓｅ ｊｏｕｒｎａｌ ｏｆ Ａ
ｐｐｌｉｅｄ ＰｈｙｓｉｃｓＶｏｌ 、２ｇ（１９８
９）Ｌ１１２１に開示されている。また、（ロ）のＢｉ
２Ｓｒ２Ｃｕ１０６構造（２２０１相）を有する繊維状
結晶は、本発明者により、日本セラミックス協会１９９
０年会講演予稿集４４３頁に開示されている。The materials to be heat treated in the present invention are (a) Bi, Sr
, Ca, Cu and O force 1, Bi2Sr2Cax
Fibrous crystals having a Cu2O3 structure (2212th hole), and (b) consisting of Bi, Sr, Cu and O, B
It is a material containing fibrous crystals having an i2Sr2 Cub6 structure (2201 phase). In these fibrous crystals (a) and (b), the Bi sites of the 2212 phase and 2201 phase may be partially substituted with pb. These (a) and (b) fibrous crystals are all known, and (a) Biz 5r2Ca1Cu20
The fibrous crystal having the B structure (2212 phase) was published by the present inventor in the Japanese journal of A
pplied Physics Vol, 2g (198
9) Disclosed in L1121. Also, Bi of (b)
A fibrous crystal having a 2Sr2Cu106 structure (2201 phase) was developed by the present inventor in the Japanese Ceramic Society 199
It is disclosed on page 443 of the 0th year meeting lecture proceedings.
本発明の超電導繊維状結晶の製造に際しては、まず、原
子組成比で、Ｂｉ＝１．００として、５ｒ＝０．５〜１
．５、Ｃａ＝１． ０〜３． ０１Ｃｕ＝１．０〜５．
０． Ｐｂ＝Ｏ，，２〜１．０となる様に原料物質を混
合した後、焼成する。原料物質は、焼成により酸化物を
形成し得るものであれば、特に限定されず、金属単体、
酸化物、各種の化合物（炭酸塩など）が使用できる。原
料物質とし２ては、上記の原子を２種以上含む化合物を
使用しても良い。溶融を大気中などの酸素雰囲気下で行
なう場合および原料物質自体が十分量の酸素を含んでい
る場合には、酸素源となる原料物質を使用する必要はな
い。焼成温度および時間は、使用する原料物質の種類、
組成比などにより異なるが、通常８００〜８６０℃程度
で、５〜１００時間程度の範囲内にあり、−例として、
８４０℃程度で２０時間程度である。焼成手段も特に限
定されず、電気加熱炉、ガス加熱炉など任意の手段を採
用し得る。次いで、形成された焼成物を十分に粉砕し、
粉末化する。When producing the superconducting fibrous crystal of the present invention, first, the atomic composition ratio is Bi=1.00, 5r=0.5 to 1
．． 5, Ca=1. 0-3. 01Cu=1.0-5.
0. After mixing the raw materials so that Pb=O, 2 to 1.0, it is fired. The raw material is not particularly limited as long as it can form an oxide upon firing, and may include an elemental metal,
Oxides and various compounds (carbonates, etc.) can be used. As the raw material 2, a compound containing two or more of the above atoms may be used. When melting is carried out in an oxygen atmosphere such as in the air, and when the raw material itself contains a sufficient amount of oxygen, there is no need to use a raw material as an oxygen source. The firing temperature and time depend on the type of raw material used,
Although it varies depending on the composition ratio, etc., it is usually within the range of about 800 to 860 ° C. for about 5 to 100 hours.
It takes about 20 hours at about 840°C. The firing means is not particularly limited either, and any means such as an electric heating furnace or a gas heating furnace may be employed. Next, the formed fired product is thoroughly crushed,
Powder.
次いで、前記（イ）または（ロ）の繊維状結晶を上記で
得られた酸化物粉末（以下埋込み粉末ということがある
）中に埋め込み、熱処理する。熱処理温度および時間は
、使用する埋込み粉末の組成比、熱処理される繊維状結
晶の大きさなどにより異なるが、通常８３０〜８６０℃
程度で５０〜２００時間程度の範囲内にあり、−例とし
て、８４０℃程度で１２０時間程度である。熱処理手段
も特に限定されず、電気加熱炉、ガス加熱炉、光加熱炉
などの任意のものを採用し得る。Next, the fibrous crystals of (a) or (b) are embedded in the oxide powder obtained above (hereinafter sometimes referred to as embedding powder) and heat treated. The heat treatment temperature and time vary depending on the composition ratio of the embedding powder used, the size of the fibrous crystals to be heat treated, etc., but are usually 830 to 860 °C.
The heating time is within the range of about 50 to 200 hours, for example, about 120 hours at about 840°C. The heat treatment means is not particularly limited either, and any means such as an electric heating furnace, a gas heating furnace, a light heating furnace, etc. can be employed.
熱処理終了後、埋込み粉末から被加熱物を取り出すこと
により、
Ｂｉ；＋−３Ｐｂｘ Ｓｒ３．９−２． ｌ Ｃａｔ、
９−２． ｔ Ｃｕ３０ ｙ（Ｑ＜ｘ＜０．４．１０
．０＜ｙ＜１１．０）なる組成比を有し、Ｂｉ２Ｓｒ２
Ｃａ２ Ｃｕ３０ 】ｏ構造（２２２３相）を有する超
電導繊維状結晶を得る。After the heat treatment is completed, the object to be heated is taken out from the embedded powder to obtain Bi;+-3Pbx Sr3.9-2. lCat,
9-2. tCu30y(Q<x<0.4.10
．． 0<y<11.0), and Bi2Sr2
A superconducting fibrous crystal having a Ca2Cu30]o structure (2223 phase) is obtained.
この繊維状結晶の長さ、形状などは、熱処理前のそれら
と変わりない。The length, shape, etc. of these fibrous crystals are the same as those before heat treatment.
本発明方法においては、下記の（ａ）乃至（ｂ）の条件
を充足することを必須とする。In the method of the present invention, it is essential to satisfy the following conditions (a) and (b).
（ａ）特定組成範囲の成分比を有する埋込み粉末を使用
すること；埋込みに使用する酸化物粉末の組成が、仮に
一種でも規定範囲外となった場合には、繊維状単結晶の
２２２３相化は、困難乃至不可能となる。(a) Use a embedding powder with a component ratio within a specific composition range; if the composition of the oxide powder used for embedding is outside the specified range, the 2223-phase fibrous single crystal would be difficult to impossible.
（ｂ）特定の温度範囲で熱処理すること；繊維状結晶お
よび埋込み粉末の全ての組成が、規定範囲内であっても
、熱処理温度が規定範囲外となる場合には、繊維状結晶
の２２２３相化は、やはり困難乃至不可能となる。(b) Heat treatment in a specific temperature range; Even if all the compositions of the fibrous crystal and embedded powder are within the specified range, if the heat treatment temperature is outside the specified range, the 2223 phase of the fibrous crystal It will still be difficult or impossible to convert.
本発明方法において、２２０１相繊維状結晶或いは２２
１２相繊維状結晶が２２２３相化する機構は、未だ十分
に解明されていないが、以下のようなものであろうと推
考される。２２０１相繊維状結晶或いは２２１２相繊維
状結晶の２２２３相化には、ＣａおよびＣｕ（これらの
繊維状結晶がｐｂを含まない場合には、さらにｐｂ）の
供給が必要である。本発明方法において、埋込みに使用
する酸化物粉末中での繊維状結晶の熱処理温度（８３０
〜８６０℃）は、粉末の部分溶融温度に対応している。In the method of the present invention, 2201 phase fibrous crystals or 22
Although the mechanism by which a 12-phase fibrous crystal becomes 2223-phase has not yet been fully elucidated, it is presumed to be as follows. To convert a 2201-phase fibrous crystal or a 2212-phase fibrous crystal into a 2223-phase, it is necessary to supply Ca and Cu (if these fibrous crystals do not contain PB, further PB). In the method of the present invention, the temperature for heat treatment of the fibrous crystals in the oxide powder used for embedding (830
~860°C) corresponds to the partial melting temperature of the powder.
熱処理温度が高すぎる場合には、酸化物粉末の液相部分
が多くなり、繊維状結晶と酸化物粉末とが融着するので
、繊維状結晶を酸化物粉末から分離して、取り出すこと
が困難となる。If the heat treatment temperature is too high, the liquid phase portion of the oxide powder will increase and the fibrous crystals and oxide powder will fuse together, making it difficult to separate the fibrous crystals from the oxide powder and take them out. becomes.
一方、熱処理温度が酸化物粉末の部分溶融温度よりも低
い場合には、繊維状結晶と酸化物粉末との間で相互作用
が生じないので、２２２３相化は達成されない。しかる
に、上記の温度範囲で熱処理を行なう場合には、繊維状
結晶の近辺に適度な液相か存在し、この液相を介して埋
込み用の酸化物粉末から繊維状結晶にＣａおよびＣｕが
供給され、２２２３相化が達成されるものと考えられる
。On the other hand, when the heat treatment temperature is lower than the partial melting temperature of the oxide powder, no interaction occurs between the fibrous crystals and the oxide powder, so that 2223 phase formation is not achieved. However, when heat treatment is performed in the above temperature range, a suitable liquid phase exists near the fibrous crystal, and Ca and Cu are supplied from the embedding oxide powder to the fibrous crystal through this liquid phase. It is thought that 2223 phases can be achieved.
発明の効果
本発明によれば、
Ｂ１２−ｘ Ｐｂｘ Ｓｒ＋ ９−２． ｌ Ｃａｔ
９−２． ） Ｃｕ１３０ｙ（Ｑ＜ｘ＜Ｑ、４．１０．
Ｑ＜ｙ＜１１．Ｏ）なる組成を有し、Ｂｉｚ ５ｒ２Ｃ
ａ２ＣＬＩ３０１０構造（２２２３相）を有する超電導
繊維状結晶が得られる。Effects of the Invention According to the present invention, B12-x Pbx Sr+ 9-2. l Cat
9-2. ) Cu130y (Q<x<Q, 4.10.
Q<y<11. Biz 5r2C
A superconducting fibrous crystal having a2CLI3010 structure (2223 phase) is obtained.
本発明の超電導繊維状結晶は、１００Ｋを超える臨界温
度を有するので、液体窒素中で使用可能である。また、
曲げることが可能であるという特性をも有している。従
って、レーザー光などを使用するスポット溶接で線材化
することにより、液体窒素中で使用できる高温超電導材
料として、磁場発生用マグネット材料、電力貯蔵用およ
び電力輸送用の線材製造材料への応用、さらには先端形
状を利用したポイントコンタクトのジョセフソン素子用
材料などの広範囲の分野での利用が期待される。The superconducting fibrous crystals of the present invention have a critical temperature of over 100K, so they can be used in liquid nitrogen. Also,
It also has the property of being bendable. Therefore, by forming wires by spot welding using laser light, etc., it can be used as a high-temperature superconducting material that can be used in liquid nitrogen, and can be applied to magnet materials for magnetic field generation, wire manufacturing materials for power storage and power transport, and furthermore. The material is expected to be used in a wide range of fields, including materials for point-contact Josephson elements that utilize the tip shape.
実施例
以下に実施例を示し、本発明の特徴とするところをより
一層明確にする。EXAMPLES Examples will be shown below to further clarify the features of the present invention.
実施例１
下記第１表に示す原子組成比となる様に出発原料を十分
に混合した後、その１５ｇをアルミナルツボに入れ、電
気炉中で８４０°Ｃで２０時間焼成し、得られた焼成物
を十分に粉砕して、埋込み用酸化物粉末を得た。Example 1 After thoroughly mixing the starting materials so as to have the atomic composition ratio shown in Table 1 below, 15 g of the starting materials were placed in an alumina crucible and fired at 840°C for 20 hours in an electric furnace. The material was sufficiently ground to obtain an oxide powder for embedding.
次いで、第１図に模式的な断面図として示す様に、アル
ミナボート（３）上に置かれた上記埋込み用酸化物粉末
（２）中に予め調製しておいたＢｉ２Ｓｒ２Ｃａｔ Ｃ
ｕ２０ｇ構造（２２１２相）を有する繊維状結晶（１）
５０本を埋込み、電気炉中８４０℃で１２０時間熱処理
した。Next, as shown in a schematic cross-sectional view in FIG.
Fibrous crystals with u20g structure (2212 phase) (1)
Fifty pieces were embedded and heat treated in an electric furnace at 840°C for 120 hours.
熱処理終了後、繊維状結晶と埋込み粉末とを分離した。After the heat treatment was completed, the fibrous crystals and the embedded powder were separated.
第２図に回収した繊維状結晶のＸ線回折パターンを示す
。このＸ線回折パターンから、熱処理後の繊維状結晶が
、Ｂｉ２Ｓｒ２Ｃａ２Ｃｕ３ｏ１０構造（２２２３相）
を有していることが確認された。FIG. 2 shows the X-ray diffraction pattern of the recovered fibrous crystals. From this X-ray diffraction pattern, the fibrous crystals after heat treatment have a Bi2Sr2Ca2Cu3o10 structure (2223 phase).
It was confirmed that it has.
また、直流四端子法で測定したこの繊維状結晶の電気抵
抗と絶対温度との関係は、第３図に示す通りであった。Furthermore, the relationship between the electrical resistance and absolute temperature of this fibrous crystal measured by the DC four-terminal method was as shown in FIG.
また、電気抵抗がゼロとなる温度は、１０７にであった
。Further, the temperature at which the electrical resistance became zero was 107.
なお、本実施例および以下の実施例において使用した埋
込み用酸化物粉末の製造原料は、下記のものであった。The raw materials for producing the embedding oxide powder used in this example and the following examples were as follows.
＊Ｂｉ源・・・酸化ビスマス（Ｂｉ２０３）＊Ｓｒ源・
・・炭酸ストロンチウム（ＳｒＣＯ３）＊Ｃａ源・・・
炭酸カルシウム（Ｃａ Ｃ０３）＊Ｃｕ源・・・酸化胴
（Ｃｕ Ｏ）
＊Ｐｂ源・・・酸化鉛（Ｐ ｂ Ｏ）
実施例２〜６
実施例１の手法に準じて、第１表に示す２２１２相構造
または２２０１相構造の繊維状結晶を酸化物粉末に埋込
み、電気炉中所定の温度で１２０時間熱処理した。*Bi source...Bismuth oxide (Bi203) *Sr source...
...Strontium carbonate (SrCO3) *Ca source...
Calcium carbonate (Ca C03) *Cu source...Oxide shell (CuO) *Pb source...Lead oxide (PbO) Examples 2 to 6 According to the method of Example 1, as shown in Table 1 Fibrous crystals having a 2212 phase structure or a 2201 phase structure were embedded in oxide powder and heat treated at a predetermined temperature in an electric furnace for 120 hours.
これらの熱処理後の繊維状結晶は、いずれも実施例１の
ものと同様の結晶構造および超電導性を有していること
が確認された。It was confirmed that all of these heat-treated fibrous crystals had the same crystal structure and superconductivity as those of Example 1.
実施例１〜６に関して、第１表に熱処理前の繊維状結晶
の相構造および酸化物粉末の組成を示し、第２表に熱処
理温度、熱処理後の繊維状結晶の構造および臨界温度を
示す。Regarding Examples 1 to 6, Table 1 shows the phase structure of the fibrous crystal and the composition of the oxide powder before heat treatment, and Table 2 shows the heat treatment temperature, the structure of the fibrous crystal after heat treatment, and the critical temperature.
第１表
０．２５
０．５
０．２
０．２５
第２表
実施例 熱処理温度 繊維状結晶構造 臨界温度（’
Ｃ） 熱処理後 （Ｋ）絶対温変と電気抵
抗との関係を示す図面である。Table 1 0.25 0.5 0.2 0.25 Table 2 Examples Heat treatment temperature Fibrous crystal structure Critical temperature ('
C) After heat treatment (K) It is a drawing showing the relationship between absolute temperature change and electrical resistance.
（以 上）(that's all)
Claims (2)
、その原子の組成比が Ｂｉ＿２＿−＿ｘＰｂ＿ｘＳｒ＿１＿．＿９＿〜＿２＿
．＿１Ｃａ＿１＿．＿９＿〜＿２＿．＿１Ｃｕ＿３Ｏ＿
ｙ（０＜ｘ＜０．４、１０．０＜ｙ＜１１．０）であり
、Ｂｉ＿２Ｓｒ＿２Ｃａ＿２Ｃｕ＿３Ｏ＿１＿０構造（
２２２３相）を有する超電導繊維状結晶。(1) Consisting of Bi, Sr, Ca, Cu, Pb and O, the atomic composition ratio is Bi_2_-_xPb_xSr_1_. ＿9＿〜＿２＿
．． _1Ca_1_. ＿9＿～＿2＿. _1Cu_3O_
y (0<x<0.4, 10.0<y<11.0), and Bi_2Sr_2Ca_2Cu_3O_1_0 structure (
2223 phase) superconducting fibrous crystals.
＿２Ｓｒ＿２Ｃａ＿１Ｃｕ＿２Ｏ＿８構造（２２１２相
）を有する繊維状結晶、または、 Ｂｉ、Ｓｒ、ＣｕおよびＯからなり、 Ｂｉ＿２Ｓｒ＿２Ｃｕ＿１Ｏ＿６構造（２２０１相）を
有する繊維状結晶を、原子の組成比が Ｂｉ＝１．０ Ｓｒ＝０．５〜１．５ Ｃａ＝１．０〜３．０ Ｃｕ＝１．０〜５．０ Ｐｂ＝０．２〜１．０ である酸化物粉末中に埋め込み、８３０〜８６０℃で熱
処理することを特徴とする、原子の組成比が Ｂｉ＿２＿−＿ｘＰｂ＿ｘＳｒ＿１＿．＿９＿〜＿２＿
．＿１Ｃａ＿１＿．＿９＿〜＿２＿．＿１Ｃｕ＿３Ｏ＿
ｙ（０＜ｘ＜０．４、１０．０＜ｙ＜１１．０）であり
、Ｂｉ＿２Ｓｒ＿２Ｃａ＿２Ｃｕ＿３Ｏ＿１＿０構造（
２２２３相）を有する超電導繊維状結晶の製造方法。(2) Consisting of Bi, Sr, Ca, Cu and O, Bi
A fibrous crystal having a _2Sr_2Ca_1Cu_2O_8 structure (2212 phase), or a fibrous crystal consisting of Bi, Sr, Cu, and O and having a Bi_2Sr_2Cu_1O_6 structure (2201 phase) with an atomic composition ratio of Bi=1.0 Sr=0 .5 to 1.5 Ca=1.0 to 3.0 Cu=1.0 to 5.0 Pb=0.2 to 1.0 Embedded in oxide powder and heat treated at 830 to 860°C. characterized by an atomic composition ratio of Bi_2_−_xPb_xSr_1_. ＿9＿〜＿２＿
．． _1Ca_1_. ＿9＿～＿2＿. _1Cu_3O_
y (0<x<0.4, 10.0<y<11.0), and Bi_2Sr_2Ca_2Cu_3O_1_0 structure (
2223 phase).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177123A JPH0745357B2 (en) | 1990-07-03 | 1990-07-03 | Superconducting fibrous single crystal and method for producing the same |
| US07/777,055 US5242896A (en) | 1990-03-07 | 1991-10-16 | Superconductor crystal and process for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177123A JPH0745357B2 (en) | 1990-07-03 | 1990-07-03 | Superconducting fibrous single crystal and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0465395A true JPH0465395A (en) | 1992-03-02 |
| JPH0745357B2 JPH0745357B2 (en) | 1995-05-17 |
Family
ID=16025571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2177123A Expired - Lifetime JPH0745357B2 (en) | 1990-03-07 | 1990-07-03 | Superconducting fibrous single crystal and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745357B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003010369A1 (en) * | 2001-07-25 | 2003-02-06 | Japan Science And Technology Agency | Oxide high-critical temperature superconductor acicular crystal and its production method |
| US8293862B2 (en) | 1999-08-24 | 2012-10-23 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and a process for producing polyester |
| CN107615879A (en) * | 2016-01-29 | 2018-01-19 | 株式会社美铃工业 | Heater and the fixing device, image processing system and heater for possessing the heater |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307115A (en) * | 1987-06-08 | 1988-12-14 | Agency Of Ind Science & Technol | Production of oxide superconductor |
| JPH0312313A (en) * | 1989-06-09 | 1991-01-21 | Sumitomo Electric Ind Ltd | Production of superconducting ceramic fiber |
| JPH03150208A (en) * | 1989-11-02 | 1991-06-26 | Chiyoudendou Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Preparation of oxide superconductive fiber |
| JPH0446050A (en) * | 1990-01-25 | 1992-02-17 | Osaka Prefecture | Production of bismuth-containing superconducting ceramics |
-
1990
- 1990-07-03 JP JP2177123A patent/JPH0745357B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63307115A (en) * | 1987-06-08 | 1988-12-14 | Agency Of Ind Science & Technol | Production of oxide superconductor |
| JPH0312313A (en) * | 1989-06-09 | 1991-01-21 | Sumitomo Electric Ind Ltd | Production of superconducting ceramic fiber |
| JPH03150208A (en) * | 1989-11-02 | 1991-06-26 | Chiyoudendou Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Preparation of oxide superconductive fiber |
| JPH0446050A (en) * | 1990-01-25 | 1992-02-17 | Osaka Prefecture | Production of bismuth-containing superconducting ceramics |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8293862B2 (en) | 1999-08-24 | 2012-10-23 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using the same, and a process for producing polyester |
| WO2003010369A1 (en) * | 2001-07-25 | 2003-02-06 | Japan Science And Technology Agency | Oxide high-critical temperature superconductor acicular crystal and its production method |
| US7008906B2 (en) | 2001-07-25 | 2006-03-07 | Japan Science And Technology Agency | Oxide high-critical temperature superconductor acicular crystal and its production method |
| CN107615879A (en) * | 2016-01-29 | 2018-01-19 | 株式会社美铃工业 | Heater and the fixing device, image processing system and heater for possessing the heater |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745357B2 (en) | 1995-05-17 |
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