JPS63230522A - Production of superconductive material - Google Patents
Production of superconductive materialInfo
- Publication number
- JPS63230522A JPS63230522A JP6250587A JP6250587A JPS63230522A JP S63230522 A JPS63230522 A JP S63230522A JP 6250587 A JP6250587 A JP 6250587A JP 6250587 A JP6250587 A JP 6250587A JP S63230522 A JPS63230522 A JP S63230522A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- powder
- excimer laser
- raw material
- superconductive material
- 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
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000007789 gas Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012159 carrier gas Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/121—Coherent waves, e.g. laser beams
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
Ｃ発明の目的〕
（産業上の利用分野）
本発明は液体水素温度より高い温度で臨界温度を有し、
特性の優れた超伝導セラミック材料をエキシマレーザに
より合成した超伝導材料の製造方法に関する。[Detailed Description of the Invention] CObject of the Invention] (Industrial Application Field) The present invention has a critical temperature at a temperature higher than the liquid hydrogen temperature,
This invention relates to a method for producing superconducting ceramic materials with excellent properties synthesized using excimer laser.
（従来の技術）
（Ｌａ、Ｂａ）、Ｃｕｂ、セラミックスが３０”Ｋで超
伝導性を示すことは既に文献に報告されている。(Prior Art) It has already been reported in literature that (La, Ba), Cub, and ceramics exhibit superconductivity at 30''K.
（Ｈ，Ｔａｋａｇｉら、 Ｊａｐａｎ、 Ｊ、 Ａｐｐ
ｌ、 Ｐｈｙｓ、 ２６． （２）１９８７、 Ｌ１２
３）この文献の製造方法は原料粉体を混合し、焼結する
通常のセラミックスの製造方法で合成している。(H, Takagi et al., Japan, J. App.
l, Phys, 26. (2) 1987, L12
3) The manufacturing method described in this document is a general ceramic manufacturing method in which raw material powders are mixed and sintered.
（発明が解決しようとする問題点）
しかしこの方法では超伝導になる臨界温度が低く、広い
温度幅にわたって転移するため実用上問題があった。(Problems to be Solved by the Invention) However, this method has a practical problem because the critical temperature for superconductivity is low and the transition occurs over a wide temperature range.
本発明は上記問題点を除去するために成されたもので、
狭い温度幅にわたって転移する超伝導材料の製造方法を
提供することを目的とする。The present invention was made to eliminate the above problems, and
It is an object of the present invention to provide a method for producing a superconducting material that undergoes a transition over a narrow temperature range.
（問題点を解決するための手段）
このような問題を解決するため、セラミックの原料粉体
を細かく、均一に合成するため分子結合を直接励起して
反応させる紫外線とくにエキシマレーザ光を用いて微細
超伝導粉体を製造する。(Means for solving the problem) In order to solve this problem, in order to synthesize ceramic raw material finely and uniformly, we use ultraviolet light, especially excimer laser light, to directly excite and react the molecular bonds. Manufacture superconducting powder.
（作用）
これにより、添加する元素が均一に分散され、結晶粒径
も細かいのも、焼結反応が均一に起こり反応温度を低く
することになる。(Function) As a result, the added elements are uniformly dispersed and the crystal grain size is fine, so that the sintering reaction occurs uniformly and the reaction temperature is lowered.
（実施例１）
Ｌａ （１）Ｌａ（ＣＯ）６ガス４０ｖｏ１％、 Ｂａ
（Ｃ２Ｈａ ）ｚガス４ ｖｏ１％、Ｃｕ２（ｃｌ（
、）ｚガス１ｌｖｏ１％、およびＮｏ、ガスを４５ｖｏ
１％の割合で混合し原料ガスとする。この原料ガス１に
対しキャリヤガスとしてＡｒガスを１の割合で混合し反
応容器に導入し、 ＡｒＦ、レーザ光を照射した。(Example 1) La (1) La(CO)6 gas 40vo1%, Ba
(C2Ha)z gas 4 vol%, Cu2(cl(
,) z gas 1lvo 1%, and no, gas 45vo
They are mixed at a ratio of 1% and used as a raw material gas. This raw material gas was mixed with Ar gas as a carrier gas of 1 part in a ratio of 1 part, introduced into a reaction vessel, and irradiated with ArF and laser light.
レーザ光の窓材としては石英ガラスなどのエキシマレー
ザの波長での吸収率の低い材質を用いる。As the window material for the laser light, a material such as quartz glass that has a low absorption rate at the wavelength of the excimer laser is used.
反応容器内に反応生成物が付着しないよう反応容器の内
壁にはキャリヤガスのＡｒを吹出させておいた。生成し
た粉体はバグフィルタ（回収装置）で回収した。得られ
た粉体の平均粒径は０．１μｓであった。この粉体にバ
インダとしてＶＡＰを加え造粒し、プレス成形して、９
００℃〜１３００℃の空気雰囲気のもとて焼成し、直径
５ｍ、厚さ１■のセラミックスを得た。このセラミック
スの両面に金を蒸着し電極として電気抵抗を測定したと
ころ、３０°にで抵抗値が０の超伝導現象を示した。一
方、市販品のＬａ、Ｂａ、 Ｃｕの酸化粉体を（ＬａＯ
，９ＢａＯ，１）、ＣｕＯ４の割合になるよう混合し、
１０００〜１４００℃の温度で焼成して得たセラミック
スは１５＠にで抵抗値がＯになる。このときの抵抗値と
温度との関係を図に示し１曲線Ａは本実施例２曲線Ｂは
従来例の結果である。このようにエキシマレーザを用い
て得た粉体からセラミックスとしたとき超伝導になる温
度が従来方式で得たセラミックスの超伝導になる温度よ
り高い温度で実現する。これは添加する微量元素が均一
に分散されるためセラミックスとして製作したときに通
常のセラミックス製造方法で製作されたときと較ベセラ
ミックスの微細組織が均一で欠陥の大きさや数も通常の
セラミックスに較べ少なくなっているためである。Ar carrier gas was blown onto the inner wall of the reaction vessel to prevent reaction products from adhering to the inside of the reaction vessel. The generated powder was collected using a bag filter (collection device). The average particle size of the obtained powder was 0.1 μs. Add VAP as a binder to this powder, granulate it, press mold it, and
The ceramic was fired in an air atmosphere at a temperature of 00°C to 1300°C to obtain a ceramic having a diameter of 5 m and a thickness of 1 inch. When gold was deposited on both sides of this ceramic and the electrical resistance was measured using it as an electrode, it showed a superconducting phenomenon with a resistance value of 0 at 30°. On the other hand, commercially available oxidized powders of La, Ba, and Cu (LaO
, 9BaO, 1), and CuO4.
Ceramics obtained by firing at a temperature of 1000 to 1400°C have a resistance value of 0 at 15@. The relationship between the resistance value and the temperature at this time is shown in the figure. 1 Curve A is the result of the present example 2 Curve B is the result of the conventional example. In this way, when ceramics are made from powder obtained using an excimer laser, superconductivity is achieved at a higher temperature than the superconductivity of ceramics obtained by conventional methods. This is because the trace elements added are uniformly dispersed, so when manufactured as a ceramic, the microstructure of the ceramic is uniform compared to when manufactured using a normal ceramic manufacturing method, and the size and number of defects are also lower than that of normal ceramics. This is because the number is decreasing.
（実施例２）
Ｌａ （ＣＯ）ｓガス３８ｖｏ１％、Ｂａ（ＣＪｉ）＊
ガス２ｖｏ１％、Ｓｒ （Ｃｚ Ｈｓ ）ｚガス３ｖｏ
１％、Ｃｕ、 （ＣＨａ ）＊ガス１ｌｖｏ１％。(Example 2) La (CO)s gas 38vo1%, Ba(CJi)*
Gas 2vo 1%, Sr (Cz Hs)z gas 3vo
1%, Cu, (CHa)*gas 1lvo1%.
およびＮＯ，ガスを４５ｖｏ１％の割合で混合し原料ガ
スとする。この原料ガスを用いて実施例１と同様な方法
で粉体を得た。粉体の平均粒径は０．１１ｍであった。and NO gas are mixed at a ratio of 45 vol 1% to obtain a raw material gas. Powder was obtained in the same manner as in Example 1 using this raw material gas. The average particle size of the powder was 0.11 m.
さらにこの粉体からセラミックスを得た。Furthermore, ceramics were obtained from this powder.
このセラミックスの超伝導転移温度は３３ Ｋであった
。The superconducting transition temperature of this ceramic was 33K.
（実施例３）
Ｌａ（１）Ｌａ（ＣＯ）６ガス３６ｖｏ１％、ｙ（ｃｕ
ａ）＊ガス４ ｖｏ１％、Ｂａ （Ｃｚ Ｈｓ ）ｘガ
ス３ ｖｏ１％、５ｒ（ＣＪｓ）ｚガスＩ ９０１％、
Ｃｕｔ（Ｃｕ３）＊ガス１ｌｖｏ１％、およびＮＯ，ガ
スを４５ｖｏ１％の割合で混合し原料ガスとする。この
原料ガスを用いて実施例１と同様な方法で粉体を得た。(Example 3) La(1)La(CO)6 gas 36vo1%, y(cu
a) *Gas 4 vo1%, Ba (Cz Hs) x Gas 3 vo1%, 5r(CJs)z Gas I 901%,
Cut (Cu3)*gas 1lvo1% and NO gas are mixed at a ratio of 45vo1% to obtain a raw material gas. Powder was obtained in the same manner as in Example 1 using this raw material gas.
粉体の平均粒径は０．５−であった、さらにこの粉体が
ら、セラミックスを得た。このセラミックスの超伝導転
移温度は４５°にであった。The average particle size of the powder was 0.5-. Furthermore, ceramics were obtained from this powder. The superconducting transition temperature of this ceramic was 45°.
（実施例４）
Ｌａ（Ｃｏ）ｓガス３６ｖｏ１％、Ｙ（ＣＨ３）、ガス
４ｖｏ１％、Ｂａ （Ｃ２ｕｓ Ｌガス３ ｖｏ１％、
Ｃｕｔ （ＣＨ３）ｚガス１ｌｖｏ１％、およびＮｏ、
ガスを４０ｖｏ１％、Ｆ、ガスを５ｖｏ１％の割合で混
合し原料ガスとする。この原料ガスにＦ２エキシマレー
ザを照射して実施例１と同様な方法で粉体を得た。粉体
の平均粒径は５μｓであった。さらにこの粉体から、セ
ラミックスを得た。このセラミックスの超伝導転移温度
は４０°にであった。(Example 4) La(Co)s gas 36vol%, Y(CH3) gas 4vo1%, Ba (C2us L gas 3vo1%,
Cut (CH3)z gas 1lvo1%, and No,
Gas is mixed at a ratio of 40vol%, F, and gas at 5vol% to obtain a raw material gas. This raw material gas was irradiated with F2 excimer laser to obtain powder in the same manner as in Example 1. The average particle size of the powder was 5 μs. Furthermore, ceramics were obtained from this powder. The superconducting transition temperature of this ceramic was 40°.
このようにエキシマレーザを用いて得た粉体は、セラミ
ックスとして製作するために添加する微量元素が均一に
分散され、結晶粒径も細かい。このため焼結反応が均一
に起こり反応温度も低くすることができる。さらに得ら
れたセラミックスの微細構造は均一で欠陥も少なく、超
伝導になる臨界温度が高く、狭い温度幅にわたって転移
する優れた超伝導材料を得ることができる。In powder obtained using an excimer laser in this way, trace elements added to produce ceramics are uniformly dispersed, and the crystal grain size is fine. Therefore, the sintering reaction occurs uniformly and the reaction temperature can also be lowered. Furthermore, the microstructure of the obtained ceramic is uniform and there are few defects, and the critical temperature for becoming superconducting is high, making it possible to obtain an excellent superconducting material that undergoes transition over a narrow temperature range.
図は本発明の効果を示す比抵抗の特性図である。 代理人 弁理士 則 近 憲 佑 同 三俣弘文 The figure is a characteristic diagram of resistivity showing the effect of the present invention. Agent: Patent Attorney Noriyuki Chika Same as Hirofumi Mitsumata
Claims (4)
２ガス、Ｃｕ＿２（ＣＨ＿３）＿２ガスおよびＮＯ＿２
ガスを混合した原料ガスをキャリヤガスとしてのＡｒガ
スに混合したガスにエキシマレーザを照射し、（Ｌａ１
−ｘＢａｘ）＿２ＣｕＯ＿４の粉体からなる超伝導材料
の製造方法。(1) La(CO)_6 gas, Ba(C_2H_5)_
2 gas, Cu_2(CH_3)_2 gas and NO_2
An excimer laser is irradiated on the raw material gas mixed with Ar gas as a carrier gas, and (La1
-xBax)_2CuO_4 A method for producing a superconducting material made of powder.
生成物が０．５〜５μｍの平均粒径の粉体であることを
特徴とする超伝導材料の製造方法。(2) A method for producing a superconducting material according to claim 1, wherein the product is a powder having an average particle size of 0.5 to 5 μm.
ガスに更に、Ｓｒ（Ｃ＿２Ｈ＿５）＿２、Ｙ（ＣＨ＿３
）＿３、Ｆ＿２のうちいずれか一種類以上を加えて合成
した粉体がＳｒ、Ｙ、Ｆのうちいずれか一種類以上を含
むことを特徴とする超伝導材料の製造方法。(3) In the product described in claim 2, the raw material gas further contains Sr(C_2H_5)_2, Y(CH_3
) A method for producing a superconducting material, characterized in that the powder synthesized by adding one or more of Sr, Y, and F contains one or more of Sr, Y, and F.
するエキシマレーザがＦ＿２あるいはＡｒＦレーザであ
ることを特徴とする超伝導材料の製造方法。(4) A method for manufacturing a superconducting material according to claim 3, characterized in that the excimer laser to be irradiated is an F_2 or ArF laser.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6250587A JPS63230522A (en) | 1987-03-19 | 1987-03-19 | Production of superconductive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6250587A JPS63230522A (en) | 1987-03-19 | 1987-03-19 | Production of superconductive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63230522A true JPS63230522A (en) | 1988-09-27 |
Family
ID=13202098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6250587A Pending JPS63230522A (en) | 1987-03-19 | 1987-03-19 | Production of superconductive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63230522A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064517A (en) * | 1989-01-18 | 1991-11-12 | Idemitsu Kosan Company Limited | Method for the preparation of fine particulate-metal-containing compound |
-
1987
- 1987-03-19 JP JP6250587A patent/JPS63230522A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5064517A (en) * | 1989-01-18 | 1991-11-12 | Idemitsu Kosan Company Limited | Method for the preparation of fine particulate-metal-containing compound |
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