JPH01278466A - Production of superconductor - Google Patents

Production of superconductor

Info

Publication number
JPH01278466A
JPH01278466A JP63106695A JP10669588A JPH01278466A JP H01278466 A JPH01278466 A JP H01278466A JP 63106695 A JP63106695 A JP 63106695A JP 10669588 A JP10669588 A JP 10669588A JP H01278466 A JPH01278466 A JP H01278466A
Authority
JP
Japan
Prior art keywords
powder
temperature
mixed powder
superconductor
mixing
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
Application number
JP63106695A
Other languages
Japanese (ja)
Inventor
Nobuyuki Yoshioka
信行 吉岡
Yoshiyuki Kashiwagi
佳行 柏木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Meidensha Corp
Meidensha Electric Manufacturing Co Ltd
Original Assignee
Meidensha Corp
Meidensha Electric Manufacturing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Meidensha Corp, Meidensha Electric Manufacturing Co Ltd filed Critical Meidensha Corp
Priority to JP63106695A priority Critical patent/JPH01278466A/en
Publication of JPH01278466A publication Critical patent/JPH01278466A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E40/00Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

Landscapes

  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

PURPOSE:To obtain a superconductor, capable of exhibiting superconductivity at liquid nitrogen temperature or above and having stabilized characteristics from inexpensive materials by mixing powders of compounds respectively containing Sr, Ca, Bi and Cu at a specific ratio, calcining and sintering the resultant mixed powder by a specified method. CONSTITUTION:The objective superconductor is produced by the following steps (a)-(c); (a) mixing bismuth oxide powder with calcium compound powder and copper oxide powder to provide mixed powder, calcining the resultant mixed powder at a lower temperature than the sintering temperature and pulverizing the calcined mixture to afford processed powder; (b) mixing the processed powder with bismuth oxide powder to provide mixed powder, pressurizing the mixed powder to afford a compact and (c) sintering the compact at 830-880 deg.C temperature in an oxidizing atmosphere to provide a sintered compact. The sintered compact consists of Bi, Sr, Ca, Cu and O and the atomic ratios of the metallic components are Sr:Ca=1:0.3-3, Bi:Cu=1:1.8-4 and (Sr+ Ca):(Bi+Cu)=1:1-2.

Description

【発明の詳細な説明】 A、産業上の利用分野 本発明は、一定の温度で電気抵抗がゼロになるいわゆる
超電導体に係り、特に液体窒素温度以上で超電導特性を
示す超電導体の製造方法に関する。
DETAILED DESCRIPTION OF THE INVENTION A. Industrial Application Field The present invention relates to a so-called superconductor whose electrical resistance becomes zero at a certain temperature, and particularly relates to a method for producing a superconductor that exhibits superconducting properties at temperatures above liquid nitrogen temperature. .

B9発明の概要 本発明は、ビスマス酸化物の粉末、カルシウム化合物の
粉末、銅酸化物の粉末を混合して仮焼成すると共にこれ
を粉砕して加工粉末を得、これにストロンチウム化合物
の粉末を加えて混合し、これを加圧成形した後に酸化性
雰囲気中で本焼成して得た、 ビスマス(Bi)、ストロンチウム(Sr)、カルシウ
ム(Ca)、銅(Cu)、及び酸素(O)の成分からな
る焼結体で、液体窒素温度以上(絶対温度77℃)以上
で超電導を示す超電導体の製造方法にある。
B9 Summary of the Invention The present invention involves mixing bismuth oxide powder, calcium compound powder, and copper oxide powder, calcining the mixture, and pulverizing the mixture to obtain a processed powder, to which powder of a strontium compound is added. Components of bismuth (Bi), strontium (Sr), calcium (Ca), copper (Cu), and oxygen (O) obtained by mixing the mixture under pressure, molding it under pressure, and then firing it in an oxidizing atmosphere. A method for producing a superconductor which exhibits superconductivity at a temperature higher than liquid nitrogen temperature (absolute temperature 77°C) and higher.

C1従来の技術 1911年にカメリング・オンネスにより超電導現象が
発見されて以来、実用化に向けてさまざまな研究開発が
進められている。実用化には、臨界温度(Tc)が高け
れば高い程、冷却コストが安くて済むため、より高温で
の超電導の可能性をめぐってその超電導材料の激しい開
発競争が展開されている。
C1 Conventional Technology Since the discovery of superconductivity by Kamerling Onnes in 1911, various research and development efforts have been made toward practical application. For practical application, the higher the critical temperature (Tc), the lower the cooling cost, so there is intense competition to develop superconducting materials with the potential for superconducting at higher temperatures.

最近、液体窒素の温度77に以上の温度にて超電導現象
を生じるものとして、ストロンチウム・イッテルビウム
・銅酸化物・イツトリウム系銅酸化物といった超電導材
料が発見されたと発表されるに至っている。
Recently, it has been announced that superconducting materials such as strontium, ytterbium, copper oxide, and yttrium-based copper oxide have been discovered as materials that exhibit superconducting phenomena at temperatures above the temperature of liquid nitrogen of 77°C.

D3発明が解決しようとする課題 液体窒素の温度以上の温度で超電導現象を生じることか
ら、この超電導を利用した具体的な適用範囲が拡大して
きた。
D3 Problems to be Solved by the Invention Since superconductivity occurs at temperatures higher than the temperature of liquid nitrogen, the range of specific applications utilizing this superconductivity has expanded.

しかし、上述のようなイツトリウムは希少材料であるこ
とから、高価であり、超電導の適用範囲の拡大にはおの
ずと限界があり、安価な超電導材料の開発が望まれてい
るが、その開発は、まだ緒についたばかりであるのが現
状である。
However, since yttrium is a rare material as mentioned above, it is expensive, and there is a natural limit to the expansion of the application range of superconductivity.Therefore, there is a desire to develop inexpensive superconducting materials, but the development has not yet been completed. The current situation is that it has just started.

これらの点に鑑み、本発明は、安価な材料にて77にで
超電導状態となる超電導体の製造方法を提供しようとす
るしのである。
In view of these points, the present invention seeks to provide a method for manufacturing a superconductor that becomes superconducting at 77 using inexpensive materials.

E0課題を解決するための手段と作用 発明台らは、種々の材料の配合、焼成温度等の実験を重
ねた結果、ビスマス(Bi)、ストロンチウム(Sr)
、カルシウム(Ca)、銅(Cu)、及び酸素(O)の
成分からなる焼結体で、ビスマス酸化物、カルシウム化
合物、銅酸化物の粉末を混合し、この混合粉末を本焼成
の温度より低い温度にて仮焼成すると共にこれを粉砕し
て加工粉末を得、これにストロンチウム化合物の粉末を
加えて混合し、これを加圧成形した後に酸化性雰囲気中
で且つ830〜880℃の範囲の温度で本焼成して焼結
体とすることにより、Bi−Sr−Ca−Cu−0の成
分からなり、且つ旧、Sr、Ca。
Means and effects for solving the E0 problem As a result of repeated experiments on the composition of various materials, firing temperatures, etc., the inventors discovered bismuth (Bi), strontium (Sr), etc.
, calcium (Ca), copper (Cu), and oxygen (O), in which powders of bismuth oxide, calcium compound, and copper oxide are mixed, and this mixed powder is heated at a temperature higher than the main firing temperature. Temporarily calcined at a low temperature and pulverized to obtain a processed powder, strontium compound powder is added and mixed, this is pressure molded, and then heated in an oxidizing atmosphere at a temperature of 830 to 880°C. By performing main firing at this temperature to form a sintered body, it consists of the components Bi-Sr-Ca-Cu-0, and contains old, Sr, and Ca.

Cuの成分の原子比が、 S r : Ca= 1 + 0.3〜3I3 i :
 Cu= I : 1.8〜4(Sr+Ca): (B
i+Cu)=1 : I〜2の範囲であれば、液体窒素
温度の冷却で抵抗ゼロのち密でしかも特性の安定した超
電導体が得られることを見いだした。
The atomic ratio of the Cu components is Sr:Ca=1+0.3~3I3i:
Cu=I: 1.8~4(Sr+Ca): (B
i+Cu)=1: It has been found that in the range of I to 2, a dense superconductor with zero resistance and stable characteristics can be obtained by cooling to liquid nitrogen temperature.

なお、ストロンチウム化合物としては、ストロンチウム
炭酸化物(SrCC++)、ストロンチウム酸化物(S
rO)、 ストロンチウム水酸化物(S r (OH) z)、の
何れか一種以上を用いる。
Note that strontium compounds include strontium carbonate (SrCC++), strontium oxide (SrCC++), and strontium oxide (SrCC++).
rO) and strontium hydroxide (S r (OH) z).

また、カルシウム化合物としては、 カルシウム炭酸化物(Ca COa )、カルシウム酸
化物(Cab)、 カルシウム水酸化物(Ca(O1−1)y)、の何れが
一種以上を用いる。
Further, as the calcium compound, one or more of calcium carbonate (CaCOa), calcium oxide (Cab), and calcium hydroxide (Ca(O1-1)y) is used.

なお、各成分の原子比及び温度が、前記の範囲外の場合
には、液体窒素で超電導が生じる焼結体を得ることがで
きなかった。
Note that when the atomic ratio and temperature of each component were outside the above ranges, it was not possible to obtain a sintered body in which superconductivity occurred in liquid nitrogen.

F、実施例 以下、本発明を実施例に基づいて説明する。F. Example Hereinafter, the present invention will be explained based on examples.

先ず、出発原料として粒径108m以下のビスマス酸化
物(BixO3)の粉末、ストロンチウム炭酸化物(S
rCOa)の粉末、カルシウム炭酸化物(Ca CO3
)の粉末、銅酸化物(Cub)の粉末を各々I1.1m
o1%、22.2mo1%。
First, as starting materials, bismuth oxide (BixO3) powder with a particle size of 108 m or less, strontium carbonate (S
rCOa) powder, calcium carbonate (Ca CO3
) powder and copper oxide (Cub) powder at I1.1m each.
o1%, 22.2mo1%.

22.2mo1%、44.4mo1%となるように秤量
する。
Weigh out 22.2 mo1% and 44.4 mo1%.

次に、I’3itO*、Ca COs、CuOの粉末を
ボールミルで、アルコール(又は原料粉末と反応しない
溶媒)と玉石を入れ数時間充分に混合し、得られたスラ
リーを約100℃の温度で乾燥する。
Next, the powders of I'3itO*, Ca COs, and CuO were thoroughly mixed in a ball mill with alcohol (or a solvent that does not react with the raw material powder) and cobblestones for several hours, and the resulting slurry was heated at a temperature of about 100°C. dry.

次に乾燥して得た混合粉末をアルミナ容器に入れ、酸化
性雰囲気中にて後工程の本焼成の温度より低い温度(約
840℃)で約4時間加熱処理(いわゆる仮焼成)する
Next, the mixed powder obtained by drying is placed in an alumina container and heat-treated (so-called preliminary firing) for about 4 hours in an oxidizing atmosphere at a temperature (about 840° C.) lower than the temperature of the main firing in the subsequent step.

次に得られた焼成粉を充分に粉砕し微細化した加工粉を
得る。
Next, the obtained fired powder is sufficiently ground to obtain a fine processed powder.

次に、この加工粉末と、SrCO,sの粉末とをボール
ミルで、アルコール(又は原料粉末と反応しない溶媒)
と玉石をいれ数時間充分に混合し、得られたスラリーを
約100℃の温度で乾燥する。
Next, this processed powder and SrCO,s powder were mixed in a ball mill using alcohol (or a solvent that does not react with the raw material powder).
and cobblestones and thoroughly mixed for several hours, and the resulting slurry is dried at a temperature of about 100°C.

そして、バインダーとしてポリビニルアルコールを、原
料粉末に対して1重量%となるようにポリビニルアルコ
ール溶液の形で添加する。
Then, polyvinyl alcohol is added as a binder in the form of a polyvinyl alcohol solution to 1% by weight based on the raw material powder.

そしてアルコールを更に加え充分に混練した後、乾燥し
、ふるいにて150メツシユ以下の顆粒状の造粒粉を得
る。
After further adding alcohol and thoroughly kneading, the mixture is dried and sieved to obtain granulated powder having a size of 150 mesh or less.

次に、この造粒粉を金型に充填した後、1〜2T o 
n / c m ”程度の圧力で圧縮成形して、外径4
0mm、厚み約6mmの成形体を作る。
Next, after filling this granulated powder into a mold, 1~2T o
Compression molded at a pressure of about n/cm" to an outer diameter of 4
A molded body with a diameter of 0 mm and a thickness of approximately 6 mm is made.

次に、この成形体を焼成容器内に設置し、酸化性雰囲気
で、前工程の熱処理温度の約840℃より高い温度で且
つ約880℃より低い温度(840〜880℃)で数時
間加熱して焼結体(セラミックス)を得る。
Next, this molded body is placed in a firing container and heated in an oxidizing atmosphere at a temperature higher than the heat treatment temperature of the previous step of about 840°C and lower than about 880°C (840 to 880°C) for several hours. to obtain a sintered body (ceramics).

上記の製造方法により得られた焼結体を、幅4mm、厚
さ4mm、長さ40mmの形状に切り出して第1図に示
すように電極を設けて4端子法により、焼結体の抵抗を
測定した。
The sintered body obtained by the above manufacturing method was cut into a shape with a width of 4 mm, a thickness of 4 mm, and a length of 40 mm. Electrodes were provided as shown in Figure 1, and the resistance of the sintered body was determined by the four-terminal method. It was measured.

即ち第1図は抵抗値を測定するための説明図で、焼結体
Sの長方向の両端側に電流を流すための端子a、a′を
設け、その内側に抵抗値を測定するための電圧端子す、
b’を設け、これを液体窒素の低温槽に入れ、端子a、
a′に1アンペアの安定化電流を流して端子b’、b’
間の電圧を電圧計(V)で測定して端子す、b′間の電
圧降下によって抵抗値を測定する。なお、Aは電流計を
示す。
That is, Fig. 1 is an explanatory diagram for measuring the resistance value. Terminals a and a' for flowing current are provided on both ends of the sintered body S in the longitudinal direction. Voltage terminal
b', put it in a liquid nitrogen cryostat, and connect terminals a,
A stabilized current of 1 ampere is applied to terminals b' and b'.
The voltage between terminals A and B' is measured with a voltmeter (V), and the resistance value is determined by the voltage drop between terminals A and B'. Note that A indicates an ammeter.

第2図は、その測定結果を示すもので、絶対温度約11
0にで超電導現象か始まり約85Kに至って電気抵抗が
ゼロになることが確認された。
Figure 2 shows the measurement results, with an absolute temperature of approximately 11
It was confirmed that the superconducting phenomenon begins at 0, and the electrical resistance becomes zero when the temperature reaches about 85K.

他の組成比についても同様な実験を行ったので、面性の
例も含めて記載する。
Similar experiments were conducted for other composition ratios, so examples of surface properties will also be described.

(以下余白) (混合時の吊を原子比に換算したt、の)但し、表の実
施例2が上述したものを示す。
(Hereinafter, blank space) (t, which is obtained by converting the suspension at the time of mixing into an atomic ratio) However, Example 2 in the table shows the above.

なお、上記の表の結果からr3iSSrSCasCuの
成分原子比の関係が、 同じアルカリ土類であるSr、Caの関係は、S r 
: Ca= l : 0.3〜3他のBi、Cuの関係
は、 13 i : Cu= l : 1.8〜4そしてこれ
ら両前の関係は、 (Sr+Ca): (Bi+Cu)=1 : 1〜2の
範囲の場合には、液体窒素で超電導現象(抵抗ゼロ又は
微小値)か生じる焼結体を得ることができた。
Furthermore, from the results in the table above, the relationship between the component atomic ratios of r3iSSrSCasCu is as follows: The relationship between Sr and Ca, which are the same alkaline earths, is S r
: Ca= l : 0.3~3 The other relationship between Bi and Cu is 13 i : Cu= l : 1.8~4 and the relationship between these two is (Sr+Ca): (Bi+Cu)=1:1 In the range of ~2, it was possible to obtain a sintered body in which a superconducting phenomenon (resistance of zero or minute value) occurred in liquid nitrogen.

しかし、温度が830℃未満、880℃超過では所望の
超電導現象が生じる焼結体を得ろことができなかった。
However, if the temperature is lower than 830°C or higher than 880°C, it was not possible to obtain a sintered body in which the desired superconducting phenomenon occurred.

G1発明の効果 以上のように本発明による超電導体は、液体窒素温度(
77K)において完全に超電導状態となる。
G1 Effects of the Invention As described above, the superconductor according to the present invention has a temperature of liquid nitrogen (
It becomes completely superconducting at 77K).

しかも、従来のイツトリウムを用いたものは、Tcが9
0に程度であったが、本発明のものにあっては、約10
5にであり、より高温度で超電導現象を生じることから
安定した超電導状態を維持できるものである。
Moreover, the conventional one using yttrium has a Tc of 9
However, in the case of the present invention, it was about 10
5, and since the superconducting phenomenon occurs at higher temperatures, a stable superconducting state can be maintained.

その上、原料粉末を予め本焼成温度以下の温度で加熱す
ることにより本焼成時の反応がゆるやかになり、品質の
安定した超電導体を得ることができる。
Moreover, by heating the raw material powder in advance at a temperature below the main firing temperature, the reaction during the main firing becomes gradual, and a superconductor with stable quality can be obtained.

しかも安価な原材料にて超電導体を形成でき、その上液
体窒素温度での冷却でよいことから、−層実用化に近す
き、特に電ツバ運輸等に関連した電気抵抗、及び精密計
器素子、その他エネルギー交換などの分野にflI用可
能となる等極めて優れた効果を発揮する。
In addition, since superconductors can be formed using inexpensive raw materials and only need to be cooled at liquid nitrogen temperatures, they are close to practical application, especially for electrical resistance related to electric rail transportation, precision instrument elements, etc. It exhibits extremely excellent effects, such as making it possible to use flI in fields such as energy exchange.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は本発明の焼結体の抵抗値測定の方法を説明する
ための説明図、第2図は本発明の焼結体の絶対温度(K
)に対する抵抗値(m0cm)の特性曲線図を示す。 1、a′・・・電流供給用端子、b、b’ ・・・電圧
測定端子、S・・・焼結体。 第1図 抵抗値の測定方法 第2図 絶対温度(K)□
Figure 1 is an explanatory diagram for explaining the method of measuring the resistance value of the sintered body of the present invention, and Figure 2 is the absolute temperature (K) of the sintered body of the present invention.
) is a characteristic curve diagram of the resistance value (m0cm). 1, a'... Current supply terminal, b, b'... Voltage measurement terminal, S... Sintered body. Figure 1 How to measure resistance Figure 2 Absolute temperature (K) □

Claims (1)

【特許請求の範囲】[Claims] (1)ビスマス酸化物の粉末と、カルシウム化合物の粉
末と、銅酸化物の粉末とを混合して混合粉末を得、該混
合粉末を本焼成の温度より低い温度にて仮焼成し、該仮
焼成物を粉砕して加工粉末を得る工程と、 該加工粉末と、ストロンチウム化合物の粉末とを混合し
て混合粉末を得、該混合粉を加圧して成形体を得る工程
と、 該成形体を酸化性雰囲気中で且つ830〜880℃の範
囲の温度で本焼成して焼結体を得る工程とからなり、 焼結体がビスマス(Bi)、ストロンチウム(Sr)、
カルシウム(Ca)、銅(Cu)、及び酸素(O)の成
分からなり、且つBi−Sr−Ca−Cuにおける成分
の原子比が、 Sr:Ca=1:0.3〜3 Bi:Cu:1:1.8〜4 (Sr+Ca):(Bi+Cu)=1:1〜2であるこ
とを特徴とした超電導体の製造方法。
(1) Bismuth oxide powder, calcium compound powder, and copper oxide powder are mixed to obtain a mixed powder, and the mixed powder is pre-calcined at a temperature lower than the main firing temperature. A step of pulverizing the fired product to obtain a processed powder; A step of mixing the processed powder and a strontium compound powder to obtain a mixed powder; and a step of pressurizing the mixed powder to obtain a molded body; The process consists of a step of main firing in an oxidizing atmosphere at a temperature in the range of 830 to 880°C to obtain a sintered body, and the sintered body contains bismuth (Bi), strontium (Sr),
It consists of calcium (Ca), copper (Cu), and oxygen (O), and the atomic ratio of the components in Bi-Sr-Ca-Cu is Sr:Ca=1:0.3-3 Bi:Cu: 1:1.8-4 (Sr+Ca):(Bi+Cu)=1:1-2 A method for producing a superconductor.
JP63106695A 1988-04-28 1988-04-28 Production of superconductor Pending JPH01278466A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63106695A JPH01278466A (en) 1988-04-28 1988-04-28 Production of superconductor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63106695A JPH01278466A (en) 1988-04-28 1988-04-28 Production of superconductor

Publications (1)

Publication Number Publication Date
JPH01278466A true JPH01278466A (en) 1989-11-08

Family

ID=14440167

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63106695A Pending JPH01278466A (en) 1988-04-28 1988-04-28 Production of superconductor

Country Status (1)

Country Link
JP (1) JPH01278466A (en)

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