JPH01160861A - Anisotropic growth of superconducting ceramic - Google Patents
Anisotropic growth of superconducting ceramicInfo
- Publication number
- JPH01160861A JPH01160861A JP62322167A JP32216787A JPH01160861A JP H01160861 A JPH01160861 A JP H01160861A JP 62322167 A JP62322167 A JP 62322167A JP 32216787 A JP32216787 A JP 32216787A JP H01160861 A JPH01160861 A JP H01160861A
- Authority
- JP
- Japan
- Prior art keywords
- heat treatment
- raw material
- oxidizing atmosphere
- superconducting ceramic
- subjected
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 7
- 229910003097 YBa2Cu3O7−δ Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 abstract 1
- 159000000009 barium salts Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002887 superconductor Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は高い臨界電流密度を有する超電導セラミクス
の異方成長法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an anisotropic growth method for superconducting ceramics having a high critical current density.
最近、送電などの電力分野、磁気浮上列車、核磁気共鳴
装置、物性研究用などの分野において、運転コストの低
い超電導ケーブルが望まれているっ１９８７年になって
非常に高い臨界温度（Ｔｈ）を持った酸化物超電導体が
発見され、液体窒素温度（７７Ｋ）でも超電導性を示す
ようＫなった。この超電導体は、基本組成がＹ Ｅｈｚ
Ｑｉ３Ｏ７−δ（δは０〜ｌを中心とした値）で表わ
される酸化物であり、セラミクスとしてはＹ２Ｏ３、ｆ
ｍｃｏ３． （１１０各原料粉末を混合し、熱処理、粉
砕、成形後再度熱処理を施して作成されている。なおこ
の分野の技術については、例えば雑誌（Ｐｈｙｓ Ｒｅ
ｖ Ｌｅｔｔ ５８ （１９８７） Ｐ９０８〜９１Ｏ
）に記載されている。またこの酸化物結晶は例えば雑誌
（Ｊ、 Ｊ、 Ａ、 Ｐ、 Ｌｅｔｔ、 ２６（１９８
７） Ｌ６４９）に示されているように、構造上極めて
異方性が大きいことが知られている。それに伴い臨界電
流密度（Ｊｃ ）も結晶方位により異方性を示し、Ｃ軸
方向に、平行よりも垂直方向により大きなＪｃが得られ
ることが例えば雑誌（Ｊ、Ｊ、Ａ、Ｐ、 Ｌｅｔｔ、
２６ （１９８７） Ｌ １２４８ ）に報告されてい
る。Recently, superconducting cables with low operating costs have been desired in fields such as power transmission, magnetic levitation trains, nuclear magnetic resonance equipment, and physical property research. An oxide superconductor has been discovered that exhibits superconductivity even at liquid nitrogen temperatures (77 K). This superconductor has a basic composition of Y Ehz
It is an oxide represented by Qi3O7-δ (δ is a value centered around 0 to l), and as a ceramic, Y2O3, f
mco3. (110) It is made by mixing raw material powders, heat-treating, crushing, molding, and then heat-treating again.For technology in this field, for example, see the magazine (Phys Re
v Lett 58 (1987) P908-91O
)It is described in. In addition, this oxide crystal is described, for example, in a magazine (J, J, A, P, Lett, 26 (198
7) As shown in L649), it is known to have extremely large structural anisotropy. Accordingly, the critical current density (Jc) also exhibits anisotropy depending on the crystal orientation, and a larger Jc can be obtained in the C-axis direction than in the parallel direction, as reported in magazines (J, J, A, P, Lett,
26 (1987) L 1248).
従来、Ｙ Ｂａ２ Ｃｕ３Ｏ７−δ系超電導セラミクス
の製造法は通常Ｙ２Ｏ３、）ｍｃｏ３． Ｃｕ。各原料
粉末を所望組成比になる様秤量・混合され、電気炉によ
シ熱処理を施した後粉砕し粉末状にする。その後粉末を
金型に入れプレス成形し、最終的な熱処理を経て焼結さ
せ超電導特性を有するセラミクスを得る。しかしながら
この方法では、得られたセラミクスは個々の結晶粒の結
晶方位がそろい難く低い値のＪｃしか得られない。Conventionally, the manufacturing method of YBa2Cu3O7-δ-based superconducting ceramics usually uses Y2O3, )mco3. Cu. Each raw material powder is weighed and mixed to obtain a desired composition ratio, heat-treated in an electric furnace, and then ground into powder. Thereafter, the powder is put into a mold and press-molded, and is sintered through a final heat treatment to obtain ceramics with superconducting properties. However, with this method, the crystal orientations of the individual crystal grains of the obtained ceramics are difficult to align, and only a low value of Jc can be obtained.
この発明は上記の問題点を解決するためになされたもの
で、より高い値の臨界電流密度（Ｊｃ）を有する超電導
セラミクスを得る超電導セラミクスの異方成長法を得る
ことを目的とする。This invention was made to solve the above problems, and aims to provide an anisotropic growth method for superconducting ceramics that yields superconducting ceramics having a higher critical current density (Jc).
この発明の超電導セラミクスの異方成長法は、酸化性雰
囲気中における熱処理により超電導性を示す原料物質を
、酸化性雰囲気中で第１熱処理し、これを粉砕して粉砕
物を得、これを酸化性雰囲気中で第２熱処理してＹ Ｂ
ａ ２ Ｃｕ３Ｏ７−δを得るものにおいて、硫酸バリ
ウムが上記第１熱処理時の原料物質および第２熱処理時
の粉砕物の内の少なくとも一方に、合計０．５重量部以
下含有されていることを特徴とするものである。In the anisotropic growth method of superconducting ceramics of the present invention, a raw material that exhibits superconductivity by heat treatment in an oxidizing atmosphere is first heat-treated in an oxidizing atmosphere, and then pulverized to obtain a pulverized product, which is then oxidized. A second heat treatment is carried out in a positive atmosphere.
A 2 Cu3O7-δ is obtained, characterized in that barium sulfate is contained in at least one of the raw material during the first heat treatment and the pulverized material during the second heat treatment in a total of 0.5 parts by weight or less. That is.
この発明において、硫酸バリウムの含有によりセラミッ
ク結晶粒の成長方位がそろうことにより、より高いＪｃ
値を有する超電導セラミクスが得られる。In this invention, the growth direction of ceramic crystal grains is aligned due to the inclusion of barium sulfate, resulting in a higher Jc.
A superconducting ceramic having a high value is obtained.
以下この発明の実施例の超電導セラミクスの異方成長法
を、比較例および従来例と比較しながら具体的に説明す
る。Hereinafter, the anisotropic growth method of superconducting ceramics according to an embodiment of the present invention will be specifically explained while comparing it with a comparative example and a conventional example.
原料粉末Ｙ２Ｏ３，ＥｌｌＯ０３，ＯｕＯを各原子数比
が１：２：３になる様に秤量し、４時間アルコール中で
湿式ボールミル混合した。混合後泥しようを乾燥しライ
カイ機にて４０分さらに混合し均一混合粉末を得た。そ
の後粉末を高純度アルミナの容器に入れ、９５０°Ｃに
て１５時間酸化性雰囲気中で熱処理を施した後、スタン
プミルにて打砕後ライカイ機にてさらに粗粉砕をおこな
った。粗粉砕粉に対して硫酸バリウム（Ｈａｌｏ４）
ｆ夫々０（従来例）、０．１（実施例１）、０．３（実
施例２）、０．５（実施例３）、０．７（比較例）重量
部添加含有させ、１０時間アルコール中で湿式ボールミ
ルにて混合・粉砕をおこなった。Raw material powders Y2O3, EllO03, and OuO were weighed so that the atomic ratio of each was 1:2:3, and mixed in a wet ball mill in alcohol for 4 hours. After mixing, the slurry was dried and further mixed for 40 minutes using a Raikai machine to obtain a uniform mixed powder. Thereafter, the powder was placed in a high-purity alumina container, heat-treated at 950°C for 15 hours in an oxidizing atmosphere, crushed in a stamp mill, and further coarsely pulverized in a Raikai machine. Barium sulfate (Halo4) for coarsely ground powder
f respectively 0 (conventional example), 0.1 (example 1), 0.3 (example 2), 0.5 (example 3), 0.7 (comparative example) and added in parts by weight for 10 hours. Mixing and pulverization were performed in alcohol using a wet ball mill.
ボールミル容器より取り出し乾燥後さらにライカイ機に
て均一に混合し、成形助剤としてのポリビニルアルコー
ル水溶液を添加混合し、顆粒状となし、直径３Ｏｆｉφ
の金型に入れ、ｌ ／、！の圧力で加圧成形し、厚み
約１．５ Ｍの円板状成形品を得た。成形品を酸素雰囲
気中にて９８０°Ｃの温度で２時間熱処理を施し、外径
約２４器、厚み約Ｉｎの従来例、この発明の実施例およ
び比較例による焼結体を得た。第１図〜第５図は各々、
硫酸バリウム、の添加量が０．０．１ 、 ０．３ 、
０．５ 、 ０．７重量部添加含有させ、上記のよう
にして得られた各々、従来例、実施例１．実施例２．実
施例３．比較例による円板表面のＸ線回折パター〉の回
折角度（横軸：２θ）に対する代表的指数面（ｈ、に、
１）のＸ線相対強度比（タテ軸）を示したＸ線回折パタ
ーシ図であり、各図中、０内の数字は指数面を示す。After taking it out from the ball mill container and drying it, it was further mixed uniformly in a raikai machine, and an aqueous polyvinyl alcohol solution as a molding aid was added and mixed to make it into granules, with a diameter of 3Ofiφ.
Put it in the mold of l/,! A disk-shaped molded product with a thickness of about 1.5 M was obtained by pressure molding at a pressure of . The molded products were heat-treated at a temperature of 980° C. for 2 hours in an oxygen atmosphere to obtain sintered bodies having an outer diameter of about 24 mm and a thickness of about In according to the conventional example, the example of the present invention, and the comparative example. Figures 1 to 5 are each
The amount of barium sulfate added is 0.0.1, 0.3,
0.5, 0.7 parts by weight were added and obtained as above, Conventional Example, Example 1. Example 2. Example 3. Typical index plane (h, to,
1) is an X-ray diffraction pattern diagram showing the X-ray relative intensity ratio (vertical axis), and in each figure, the numbers inside 0 indicate the index plane.
次に円板状焼結試料を長さ約１５ｆｉ、巾約２ｎの短冊
状に加工し、長手方向にインジウム電極を付け、４端子
法にて超電導特性を測定した。表はその特性であり、抵
抗値の急激低下の始まる温度と抵抗が零になる濡面の中
間温度（Ｔｃｍ）と液体窒素温度での臨界電流密度（Ｊ
ｃ）を示す。Next, the disc-shaped sintered sample was processed into a strip shape with a length of about 15 fi and a width of about 2 n, an indium electrode was attached in the longitudinal direction, and the superconducting properties were measured using a four-probe method. The table shows its characteristics, including the temperature at which the resistance value starts to rapidly decrease, the intermediate temperature of the wetted surface where the resistance becomes zero (Tcm), and the critical current density at the liquid nitrogen temperature (J
c).
表
第１図〜第５図より明らかな様に硫酸バリウム無添加円
板（従来例）に較べ添加した円板（実施例１〜３．比較
例）はいづれもＣ軸配向した指数面（ｏｏｎ）に係る面
のＸ線相対強度比が大きくなっており円板面に平行に０
面がより成長し易くなったことを示している。それに伴
いＪＣ値も表にみる如く、無添加円板に較べ増加してい
ることが判る。しかしながら硫酸バリウム添加量が０．
７重置部（比較例）になるとその増加効果が殆んどみら
れない。従って結晶配向効果がＪｃ内向上有効に働くの
は、０５重量部以下の範囲に限定される。As is clear from Table 1 to 5, the barium sulfate-added disks (Examples 1 to 3. Comparative example) compared to the barium sulfate-free disks (conventional example) have C-axis oriented index planes (ooon ) is large, and the relative X-ray intensity ratio of the plane related to
This indicates that the surface has become easier to grow. Accordingly, as shown in the table, it can be seen that the JC value has increased compared to the non-additive disk. However, the amount of barium sulfate added is 0.
In the case of the 7-layered portion (comparative example), the increasing effect is hardly seen. Therefore, the crystal orientation effect is effective in improving Jc only within the range of 0.5 parts by weight or less.
他の実施例として原料配合時に前以って上記実施例と同
重量の硫酸バリウムを添加した試料および、原料配合時
に、上記実施例の硫酸バリウムの重量の一部を添加し、
粉砕物に残量を含有させた試料についても同様の結果が
得られた。Other examples include a sample in which the same weight of barium sulfate as in the above example was added in advance at the time of raw material blending, and a sample in which a part of the weight of barium sulfate in the above example was added at the time of raw material blending,
Similar results were obtained for the sample containing the residual amount in the pulverized material.
以上説明したとおり、この発明は酸化性雰囲気中におけ
る熱処理により超電導性を示す原料物質を、酸化性雰囲
気中で第１熱処理し、これを粉砕して粉砕物を得、これ
を酸化性雰囲気中で第２熱処理してＹ Ｂａｚ ０ｕ３
Ｏ？−δを得るものにおいて、硫酸バリウムが上記第１
熱処理時の原料物質および第２熱処理時の粉砕物の内の
少なくとも一方に、合計０．５重量部以下含有されてい
ることを特徴とする方法により、より高い臨界電流密度
（Ｊｃ）を有する超電導セラミクスの異方成長法を得る
ことができる。As explained above, the present invention subjects a raw material that exhibits superconductivity through heat treatment in an oxidizing atmosphere to a first heat treatment in an oxidizing atmosphere, pulverizes the material to obtain a pulverized material, and pulverizes the material in an oxidizing atmosphere. After second heat treatment, Y Baz 0u3
O? -δ, barium sulfate is the first
A superconductor having a higher critical current density (Jc) is produced by a method characterized in that a total of 0.5 parts by weight or less is contained in at least one of the raw material during heat treatment and the pulverized material during second heat treatment. An anisotropic growth method for ceramics can be obtained.
第１図は従来法による円板表面のＸ線回折パターン図、
第２図〜第４図はこの発明の実施例による円板表面のＸ
線回折パター５図、第５図は比較例による円板表面のＸ
線回折パターン図である。Figure 1 is an X-ray diffraction pattern diagram of the disk surface obtained by the conventional method.
Figures 2 to 4 show the X of the disk surface according to the embodiment of this invention.
Line diffraction pattern Figure 5, Figure 5 shows the X of the disk surface according to a comparative example.
It is a line diffraction pattern diagram.
Claims (1)
原料物質を、酸化性雰囲気中で第１熱処理し、これを粉
砕して粉砕物を得、これを酸化性雰囲気中で第２熱処理
してＹＢａ＿２Ｃｕ＿３Ｏ＿７＿−＿δを得るものにお
いて、硫酸バリウムが上記第１熱処理時の原料物質およ
び第２熱処理時の粉砕物の内の少なくとも一方に、合計
０．５重量部以下含有されていることを特徴とする超電
導セラミクスの異方成長法。A raw material that exhibits superconductivity by heat treatment in an oxidizing atmosphere is subjected to a first heat treatment in an oxidizing atmosphere, pulverized to obtain a pulverized product, and then subjected to a second heat treatment in an oxidizing atmosphere to produce YBa_2Cu_3O_7_-_δ A superconducting ceramic characterized in that barium sulfate is contained in at least one of the raw material in the first heat treatment and the pulverized product in the second heat treatment in a total of 0.5 parts by weight or less. Anisotropic growth method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322167A JPH01160861A (en) | 1987-12-17 | 1987-12-17 | Anisotropic growth of superconducting ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62322167A JPH01160861A (en) | 1987-12-17 | 1987-12-17 | Anisotropic growth of superconducting ceramic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01160861A true JPH01160861A (en) | 1989-06-23 |
Family
ID=18140683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62322167A Pending JPH01160861A (en) | 1987-12-17 | 1987-12-17 | Anisotropic growth of superconducting ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01160861A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0573798A2 (en) * | 1992-06-10 | 1993-12-15 | Hoechst Aktiengesellschaft | Process for producing high-temperature superconductor and shaped product thereof |
| US5294601A (en) * | 1991-07-26 | 1994-03-15 | Hoechst Aktiengesellschaft | High-temperature superconductor comprising barium sulfate, strontium sulfate or mixtures thereof and a process for its preparation |
-
1987
- 1987-12-17 JP JP62322167A patent/JPH01160861A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294601A (en) * | 1991-07-26 | 1994-03-15 | Hoechst Aktiengesellschaft | High-temperature superconductor comprising barium sulfate, strontium sulfate or mixtures thereof and a process for its preparation |
| EP0573798A2 (en) * | 1992-06-10 | 1993-12-15 | Hoechst Aktiengesellschaft | Process for producing high-temperature superconductor and shaped product thereof |
| EP0573798A3 (en) * | 1992-06-10 | 1995-02-08 | Hoechst Ag | Process for producing high-temperature superconductor and shaped product thereof. |
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