JPH01320257A - Production of oxide superconductor - Google Patents
Production of oxide superconductorInfo
- Publication number
- JPH01320257A JPH01320257A JP63152987A JP15298788A JPH01320257A JP H01320257 A JPH01320257 A JP H01320257A JP 63152987 A JP63152987 A JP 63152987A JP 15298788 A JP15298788 A JP 15298788A JP H01320257 A JPH01320257 A JP H01320257A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- particle size
- type
- density
- powders
- 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 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 4
- OSOKRZIXBNTTJX-UHFFFAOYSA-N [O].[Ca].[Cu].[Sr].[Bi] Chemical compound [O].[Ca].[Cu].[Sr].[Bi] OSOKRZIXBNTTJX-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000007858 starting material Substances 0.000 abstract description 5
- 229910014454 Ca-Cu Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HMTALYRPLWKYBL-UHFFFAOYSA-N [Cu]=O.[Sr].[Ca] Chemical compound [Cu]=O.[Sr].[Ca] HMTALYRPLWKYBL-UHFFFAOYSA-N 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KJYQVRBDBPBZTD-UHFFFAOYSA-N methanol;nitric acid Chemical compound OC.O[N+]([O-])=O KJYQVRBDBPBZTD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009725 powder blending Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010334 sieve classification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はビスマス（Ｂｉ）−ストロンチウム（Ｓｒ）−
カルシウム（Ｃａ）−銅（Ｃｕ）−酸化物（０）（以下
、Ｂ５ＣＣ０という）系超電導材料の線材等の酸化物超
電導体の製造方法に関し、特にその密度を高めて臨界電
流密度を向上させた酸化物超電導体の製造方法に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to bismuth (Bi)-strontium (Sr)-
Regarding a method for manufacturing oxide superconductors such as wires of calcium (Ca)-copper (Cu)-oxide (0) (hereinafter referred to as B5CC0) based superconducting materials, the critical current density is improved by particularly increasing the density. The present invention relates to a method for producing an oxide superconductor.
［従来の技術］
Ｂ５ＣＣ０系超電導材料を線材に加工するプロセスにお
いては、通常、先ずＢｉ、Ｓｒ、Ｃａ。[Prior Art] In the process of processing a B5CC0-based superconducting material into a wire rod, Bi, Sr, and Ca are usually first processed.
Ｃｕの酸化物又は炭酸塩を出発原料とし、この各原料を
所定の配合量で混合した後、この混合粉末を約９００°
Ｃの温度で仮焼きし、Ｂ５ＣＣ０系粉末粒子の焼結体を
得る。次いで、この焼結体を所定の粒度の粉末に粉砕し
、得られたＢ５ＣＣ０系粉末を所望の大きさ及び形状の
成形体に加圧成形する。Cu oxide or carbonate is used as a starting material, and after mixing each raw material in a predetermined amount, the mixed powder is heated at approximately 900°.
The mixture is calcined at a temperature of C to obtain a sintered body of B5CC0 powder particles. Next, this sintered body is pulverized into a powder having a predetermined particle size, and the obtained B5CC0-based powder is pressure-molded into a compact having a desired size and shape.
その後、上記加圧成形工程で作製した成形体を金属パイ
プ等に充填した後、パイプと共にスウェージング加工し
、又は伸線加工することにより、所望の線径の線材を得
る。Thereafter, a metal pipe or the like is filled with the molded body produced in the pressure forming step, and then swaged or wire drawn together with the pipe to obtain a wire rod of a desired wire diameter.
次いで、この線材を、所望の特性（臨界温度Ｔｃ又は臨
界電流密度Ｊｃ）が得られるように、酸化雰囲気中で約
８５０乃至９００℃に加熱して焼成処理する。Next, this wire is fired by heating to about 850 to 900° C. in an oxidizing atmosphere so as to obtain desired characteristics (critical temperature Tc or critical current density Jc).
この場合に、加圧成形される粉末は、従来、第１図に示
すような粒度分布を有している。第１図は横軸に粒子径
をとり、縦軸に積算フルイ下をとってＢ５ＣＣ０系酸化
物の粒度分布を示すグラフ図である。この第１図から明
らかなように、原料粉末は平均粒子径が４乃至５μｍで
あり、粒子径が２０μｍ以下の粒子が連続的に分布して
いる。In this case, the powder to be pressure-molded conventionally has a particle size distribution as shown in FIG. FIG. 1 is a graph showing the particle size distribution of B5CC0-based oxides, with the horizontal axis representing the particle diameter and the vertical axis representing the integrated sieve depth. As is clear from FIG. 1, the raw material powder has an average particle size of 4 to 5 μm, and particles having a particle size of 20 μm or less are continuously distributed.
［発明が解決しようとする課題］
しかしながら、このような粒度分布を有する粉末を加圧
成形した成形体は必ずしも高い密度を有するものではな
かった。また、この成形体の密度を高めるべく粉砕方法
を変更して平均粒子径を小さくし、又は大きくしても、
第１図に示す場合と同様に所定粒子径以下の粒子が連続
的に分布するという事情は変わらない、従って、同一の
加圧条件では、粉砕方法を変更しても、成形体の密度を
著しく高める迄には至らない。[Problems to be Solved by the Invention] However, a compact formed by pressure-molding a powder having such a particle size distribution does not necessarily have a high density. Furthermore, even if the pulverization method is changed to increase or decrease the average particle size in order to increase the density of the compact,
As in the case shown in Figure 1, the fact that particles with a predetermined particle size or less are continuously distributed remains the same. Therefore, under the same pressure conditions, even if the crushing method is changed, the density of the compact will significantly decrease. I can't go so far as to raise it.
このように、従来の製造方法においては、加圧成形体の
密度を高めることができないため、後工程の伸線加工及
び焼成処理により得られたＢ５ＣＣ０系超電導体は臨界
電流密度が低いという欠点を有する。In this way, in the conventional manufacturing method, it is not possible to increase the density of the pressed compact, so the B5CC0-based superconductor obtained by the post-process wire drawing and sintering treatment has the drawback of low critical current density. have
本発明はかかる問題点に鑑みてなされたものであって、
加圧成形体の密度を十分高めることができ、これにより
、臨界電流密度を著しく高くすることができる酸化物超
電導体の製造方法を提供することを目的とする。The present invention has been made in view of such problems, and includes:
It is an object of the present invention to provide a method for producing an oxide superconductor that can sufficiently increase the density of a press-molded body, thereby significantly increasing the critical current density.
［課題を解決するための手段］
本発明に係る酸化物超電導体の製造方法は、ビスマス−
ストロンチウム−カルシウム−銅−酸化物系超電導材の
原料粉末のうち、粒子径が８乃至１０μｍの第１種粉末
と、粒子径が２乃至３μｍの第２種粉末と、粒子径が０
．５μｍ以下の第３種粉末とを、（第１種粉末）：（第
２種粉末）：（第３種粉末）＝（３０乃至３４）： （
７乃至９）：１の配合重量比で混合し、この混合粉末を
加圧成形することを特徴とする。[Means for Solving the Problems] A method for producing an oxide superconductor according to the present invention includes bismuth-
Among the raw material powders of the strontium-calcium-copper-oxide superconducting material, the first type powder has a particle size of 8 to 10 μm, the second type powder has a particle size of 2 to 3 μm, and the second type powder has a particle size of 0 μm.
．． Type 3 powder of 5 μm or less and (Type 1 powder): (Type 2 powder): (Type 3 powder) = (30 to 34): (
The powder mixture is characterized by being mixed at a blending weight ratio of 7 to 9):1, and then press-molding the mixed powder.
［作用］
本願発明者等はＢ５ＣＣ０系超電導材料粉末について、
風篩分級等によって種々の粒子径の粉末粒子を採取し、
この粒子径に応じて原料粉末を数種類に分類した。そし
て、この各分類に属する粉末の配合重量を種々変更して
混合し、この混合粉末を同一加圧条件で成形してその粒
子径及び配合重量比と成形体の密度との関係を求めた。[Function] Regarding the B5CC0-based superconducting material powder, the inventors of the present application
Powder particles of various particle sizes are collected by wind sieve classification, etc.
The raw material powder was classified into several types according to the particle size. Then, the blended weights of the powders belonging to each category were varied and mixed, and the mixed powders were molded under the same pressure conditions to determine the relationship between the particle diameter and blended weight ratio and the density of the molded body.
その結果、粒子径とその配合重量比とを適切な関係に設
定することにより、成形体の密度を十分に高めることが
できることを見い出した。As a result, it was found that the density of the molded article could be sufficiently increased by setting the particle diameter and its blending weight ratio in an appropriate relationship.
本発明はこのような観点に立つそなされたものであり、
このような最適の粉末配合条件は以下のとおりである。The present invention has been made from this perspective,
Such optimal powder blending conditions are as follows.
つまり、粒子径が８乃至１０μｍのものを第１種粉末、
粒子径が２乃至３μｍのものを第２種粉末、粒子径が０
．５μｍ以下のものを第３種粉末として、原料粉末を３
種類に分類し、この粉末を第３種粉末の配合重量を１と
した場合、第１種粉末の配合重量が３０乃至３４、第２
種粉末の配合重量が７乃至９となるように混合する。In other words, those with a particle size of 8 to 10 μm are classified as type 1 powder.
Type 2 powder has a particle size of 2 to 3 μm, and the particle size is 0.
．． The raw material powder is 3.
If the blended weight of the third type powder is 1, the blended weight of the first type powder is 30 to 34, and the blended weight of the second type powder is 30 to 34.
Mix so that the weight of the seed powder is 7 to 9.
この配合重量比で均一に混合したものは、優れた充填性
を示し、高密度の成形体を得ることができる。これに対
し、この粒子径の範囲及びその配合重量比の範囲から外
れるものは、十分に高い密度を得ることができない。こ
のため、本発明は粒子径範囲及び配合重量比範囲が前述
の範囲に入る粉末を使用して加圧成形する。A product uniformly mixed at this blending weight ratio exhibits excellent filling properties and can yield a high-density molded product. On the other hand, if the particle size falls outside this range and the blending weight ratio falls within this range, a sufficiently high density cannot be obtained. Therefore, in the present invention, a powder having a particle size range and a blending weight ratio range falling within the above-mentioned range is used for pressure molding.
そして、線材に加工する場合は、通常、加圧成形後伸線
加工し、次いで焼成処理して超電導体を得る。この超電
導体は成形密度が高いので得られる臨界電流密度は著し
く上昇する。When processed into a wire rod, the superconductor is usually obtained by pressure forming, wire drawing, and then firing. Since this superconductor has a high compaction density, the obtained critical current density increases significantly.
なお、実際上、各原料粉末は鱗片状等種々の形状をなし
ているが、本発明において規定した粉末の粒子径は、こ
の粉末粒子の最長径である。Note that, in practice, each raw material powder has various shapes such as scaly shape, but the particle size of the powder specified in the present invention is the longest diameter of this powder particle.
［実施例］ 次に、本発明の実施例について具体的に説明する。[Example] Next, examples of the present invention will be specifically described.
先ず、第１図に示すような平均粒子径が５μｍのＢ ｉ
２ Ｓｒ２ Ｃａ２ Ｃｕ３０．の粉末を作製し、この
粉末を出発原料粉末として、風篩によって種々の粒子径
に分級した。その後、下記第１表に示す配合重量比の粉
末となるように混合した後、加圧成形した。なお、実施
例１乃至５は本願特許請求の範囲にて規定した範囲内の
もの、比鮫例１乃至９はこの範囲から外れるものである
。また、従来例は連続的な粒度分布を有する出発原料粉
末自体を使用して成形したものである。First, B i with an average particle diameter of 5 μm as shown in FIG.
2 Sr2 Ca2 Cu30. This powder was used as a starting material powder and was classified into various particle sizes using a wind sieve. Thereafter, the powders were mixed to obtain a powder having a blending weight ratio shown in Table 1 below, and then pressure molded. Note that Examples 1 to 5 are within the range defined in the claims of the present application, and Examples 1 to 9 are outside this range. Furthermore, in the conventional example, the starting raw material powder itself having a continuous particle size distribution was used for molding.
各試料における加圧成形体のサイズは直径が７關、長さ
が１００市であり、加圧力は２．５トンとしてラバープ
レス法により成形した。この成形体の密度は、先ず、水
銀ポロシメーターを使用して成形体の空隙率を測定し、
この空隙率から算出しな。この成形体の見かけ密度の測
定結果を前記第１表に併せて示す。The size of the pressure-molded body in each sample was 7 mm in diameter and 100 mm in length, and was molded by a rubber press method with a pressing force of 2.5 tons. The density of this molded body is determined by first measuring the porosity of the molded body using a mercury porosimeter.
Calculate from this porosity. The measurement results of the apparent density of this molded body are also shown in Table 1 above.
上記方法で作製した成形体を肉厚がＩｍｍの銀パイプに
充填封入した後、スウエージング加工によって２．０ｍ
ｍの直径まで縮径加工して線材化した。After filling and enclosing the molded body produced by the above method into a silver pipe with a wall thickness of Imm, 2.0 m by swaging processing was performed.
The wire was reduced to a diameter of m.
その後、表層の銀シースを硝酸メタノールで溶解した後
、９００℃の酸化雰囲気で１０時間熱処理した。このよ
うにして製造した各超電導材について、液体窒素中で臨
界電流密度を測定した。その結果も第１表に示す。なお
、この臨界電流密度は出発原料粉末の臨界電流密度を１
とした場合の指数表示である。Thereafter, the surface silver sheath was dissolved in methanol nitric acid, and then heat treated in an oxidizing atmosphere at 900° C. for 10 hours. The critical current density of each superconducting material produced in this way was measured in liquid nitrogen. The results are also shown in Table 1. Note that this critical current density is equal to the critical current density of the starting material powder by 1.
This is an index display when .
この第１表から明らかなように、実施例１乃至５のＢｉ
２ Ｓｒ２ Ｃａ２ Ｃｕ３０ｙ超電導体は比較例方法
又は従来方法で製造した超電導体に比較して、見かけ密
度及び臨界電流密度の双方の著しい向上が認められる。As is clear from Table 1, the Bi of Examples 1 to 5
The 2 Sr2 Ca2 Cu30y superconductor shows significant improvements in both apparent density and critical current density compared to superconductors produced by the comparative method or the conventional method.
［発明の効果］
以上説明したように本発明によれば、Ｂ５ＣＣ０系超電
導材の粉末を加圧成形する際に、粉末粒子径に基いて、
原料粉末を８乃至１０μｍ（第１種）、２乃至３μｍ（
第２種）及び０．５μｍ以下（第３種）の３種類のもの
に分類し、その配合重量比を（第１種）；（第２種）：
（第３種）＝（３０乃至３４）： （７乃至９）：１と
なるように混合、した後、加圧成形するから、高密度の
成形体を得ることができ、これにより臨界電流密度を高
くすることができる。[Effects of the Invention] As explained above, according to the present invention, when press-molding powder of B5CC0-based superconducting material, based on the powder particle diameter,
The raw material powder is 8 to 10 μm (first type), 2 to 3 μm (
Classified into three types: (Type 2) and 0.5 μm or less (Type 3), and their blending weight ratios are (Type 1); (Type 2):
(Type 3) = (30 to 34): (7 to 9): Because it is mixed so that it becomes 1 and then pressure molded, a high-density molded product can be obtained, which makes it possible to obtain a critical current density can be made higher.
第１図は粒子径分布を示すグラフ図である。 FIG. 1 is a graph showing particle size distribution.
Claims (1)
化物系超電導材の原料粉末のうち、粒子径が８乃至１０
μｍの第１種粉末と、粒子径が２乃至３μｍの第２種粉
末と、粒子径が０．５μｍ以下の第３種粉末とを、（第
１種粉末）：（第２種粉末）：（第３種粉末）＝（３０
乃至３４）：（７乃至９）：１の配合重量比で混合し、
この混合粉末を加圧成形することを特徴とする酸化物超
電導体の製造方法。(1) The particle size of the raw material powder of bismuth-strontium-calcium-copper-oxide superconducting material is 8 to 10
(1st type powder): (2nd type powder): (1st type powder): (2nd type powder): (Type 3 powder) = (30
Mixed at a blending weight ratio of 34):(7 to 9):1,
A method for producing an oxide superconductor, which comprises pressurizing this mixed powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63152987A JPH01320257A (en) | 1988-06-21 | 1988-06-21 | Production of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63152987A JPH01320257A (en) | 1988-06-21 | 1988-06-21 | Production of oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01320257A true JPH01320257A (en) | 1989-12-26 |
Family
ID=15552484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63152987A Pending JPH01320257A (en) | 1988-06-21 | 1988-06-21 | Production of oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01320257A (en) |
-
1988
- 1988-06-21 JP JP63152987A patent/JPH01320257A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0692603B2 (en) | METAL POWDER FOR PRODUCTION OF METAL SINTERED BODY AND METHOD FOR PRODUCING METAL SINTERED BODY PRODUCT USING THE SAME | |
| JPH01136094A (en) | Manufacture of ceramic nuclear fuel pellet | |
| KR960011344B1 (en) | Process for producing superconducting(bi,ti)-ca(sr,ba)cu-o ceramic | |
| JPH01320257A (en) | Production of oxide superconductor | |
| JPH01320258A (en) | Production of oxide superconductor | |
| JPH01320256A (en) | Production of oxide superconductor | |
| JPH01261263A (en) | Production of oxide superconducting material | |
| JP2587652B2 (en) | Production method of superconducting material | |
| JP2866484B2 (en) | Manufacturing method of oxide superconductor | |
| JP2969220B2 (en) | Manufacturing method of oxide superconductor | |
| JPH0784341B2 (en) | Method for producing oxide-based superconducting compact | |
| JP2969221B2 (en) | Manufacturing method of oxide superconductor | |
| JPH07300314A (en) | Preform of oxide superconductor powder and production of oxide superconducting material using said preform | |
| JPH03114112A (en) | Manufacture of bi oxide filling superconductive wire rod having high critical current density | |
| JP3314102B2 (en) | Manufacturing method of oxide superconductor | |
| JP2881423B2 (en) | Oxide superconductor and manufacturing method thereof | |
| JP2654460B2 (en) | Production method of superconducting material | |
| JP3568657B2 (en) | Manufacturing method of oxide superconductor | |
| JP3285636B2 (en) | Manufacturing method of oxide superconductor | |
| JPH06263520A (en) | Production of oxide superconductor | |
| JP3164640B2 (en) | Manufacturing method of oxide superconductor | |
| JPH0465343A (en) | Production of oxide superconducting wire | |
| JP2677830B2 (en) | Method for producing bismuth oxide superconductor | |
| JPH02145470A (en) | Production of tlbacacuo superconductor | |
| JPH01176270A (en) | Production of oxide superconducting molding |