JPH03183653A - Method for sintering bi-pb-sr-ca-cu-o superconductor - Google Patents
Method for sintering bi-pb-sr-ca-cu-o superconductorInfo
- Publication number
- JPH03183653A JPH03183653A JP1318855A JP31885589A JPH03183653A JP H03183653 A JPH03183653 A JP H03183653A JP 1318855 A JP1318855 A JP 1318855A JP 31885589 A JP31885589 A JP 31885589A JP H03183653 A JPH03183653 A JP H03183653A
- Authority
- JP
- Japan
- Prior art keywords
- superconductor
- heat treatment
- temperature
- sintering
- fired
- 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 31
- 238000000034 method Methods 0.000 title claims description 14
- 238000005245 sintering Methods 0.000 title claims description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 claims 1
- 229910002480 Cu-O Inorganic materials 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- 239000013590 bulk material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000001771 vacuum deposition 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)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は超伝導体の焼結方法に関し、特にＢｉ−Ｐｂ−
Ｓｒ−Ｃａ−Ｃｕ−０系超伝導体の焼結方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a method for sintering a superconductor, particularly a method for sintering a Bi-Pb-
The present invention relates to a method for sintering Sr-Ca-Cu-0 based superconductors.
Ｂｉ−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ−０系超伝導体は臨界温
度が１００Ｋを超えるという優れた材料である。The Bi-Pb-Sr-Ca-Cu-0 superconductor is an excellent material with a critical temperature exceeding 100K.
〔従来の技術Ｊ
このＢｉ−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ−０系超伝導体を合
成するには１例えばＢｉ、 Ｐｂ、 Ｓｒ、 Ｃａ及び
Ｃｕの原子比がそれぞれ０．９６．０．２４．１．０
、１．０及び１．６の割合で配合された酸化物を、ｌｌ
ｏＫ級超伝導体が生成する８５ｆｆ℃で長時間空気中で
保持した後冷却する焼成方法が採られていた。[Prior Art J] To synthesize this Bi-Pb-Sr-Ca-Cu-0 system superconductor, for example, the atomic ratios of Bi, Pb, Sr, Ca and Cu are respectively 0.96.0.24. 1.0
, 1.0 and 1.6.
The firing method used was to hold the material in air for a long time at 85ff°C, where an OK-class superconductor is produced, and then cool it.
〔発明が解決しようとする課題］
前記の方法でＢｉ−Ｐｂ−３ｒ−Ｃａ−Ｃｕ−０系超伝
導体を合成した場合、得られた焼成体は、構成する結晶
粒子はｌｌｏＫ級超伝導体になるが、それぞれの粒子間
を結合する力が弱く、超伝導体の特性の一つである臨界
電流密度が低いという問題点があった。[Problems to be Solved by the Invention] When a Bi-Pb-3r-Ca-Cu-0 based superconductor is synthesized by the above method, the resulting fired body has crystal grains that are lloK class superconductors. However, the problem was that the bonding force between each particle was weak, and the critical current density, which is one of the characteristics of superconductors, was low.
［課題を解決するための手段１
本発明者らは、Ｂｉ−Ｐｂ−Ｓｒ−にａ−Ｃｕ−０系超
伝導体の焼結方法について研究した結果、上記問題点の
ない方法を見出し本発明を完成するに到った。[Means for Solving the Problems 1] As a result of research on the sintering method of a-Cu-0 based superconductor in Bi-Pb-Sr-, the present inventors found a method that does not have the above problems and developed the present invention. I have reached the point where I have completed the .
すなわち、本発明のＢｉ−Ｐｂ−３ｒ−Ｃａ−Ｃｕ−０
系超伝導体の焼結方法の要旨は、Ｄｉ、 Ｐｂ、 Ｓｒ
、 Ｃａ及びＣｕから構成されている酸化物を、空気中
においてＢｉ−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ−０系超伝導体
を生成させるに必要な熱処理温度で加熱保持（一次熱処
理）した後、更にＢｉ−３ｒ−Ｃａ−Ｃｕ−０系超伝導
体を焼結させるに必要な熱処理温度まで徐々に昇温し、
その温度で加熱保持（二次熱処理）することにある。That is, Bi-Pb-3r-Ca-Cu-0 of the present invention
The gist of the sintering method for superconductors is as follows: Di, Pb, Sr
, After heating and holding an oxide composed of Ca and Cu at a heat treatment temperature necessary to generate a Bi-Pb-Sr-Ca-Cu-0 superconductor in air (primary heat treatment), further Gradually raise the temperature to the heat treatment temperature necessary to sinter the Bi-3r-Ca-Cu-0 based superconductor,
The purpose is to heat and hold at that temperature (secondary heat treatment).
Ｂｉ−Ｐｂ−３ｒ−Ｃａ−Ｃｕ−０系超伝導体を構成す
る配合物を焼成する際、Ｐｂは非常に揮発しやすく、特
に膜状のものを焼成する際にはこの現象が顕著である。When firing the compound constituting the Bi-Pb-3r-Ca-Cu-0 superconductor, Pb is extremely volatile, and this phenomenon is particularly noticeable when firing a film-like material. .
したがって、ＰｂはｌｌｏＫ級超伝導体の構成原子にな
る確率が低く、１１０に縁起伝導体を生成させるための
フラックスの役割をしていると考えられる。このｐｂの
存在は、ｌｌｏＫ級超伝導体が生成するための半溶融状
態を作り易くするという長所を有するが、焼成後ち粒界
相に残存し、生成した超伝導体粒子間の結合を弱くする
という欠点も有している。そのため、得られた焼成体は
超伝導特性の一つである臨界電流密度が低いという問題
を生じている。この臨界電流密度を向上させるためには
、焼成で得られた１１０に縁起伝導体の粒子を焼結する
必要がある。本発明の二次熱処理は、この焼結により超
伝導体の粒子間を結合させるものである。Therefore, Pb has a low probability of becoming a constituent atom of the lloK class superconductor, and is considered to play the role of a flux for causing 110 to form an originating conductor. The presence of PB has the advantage of making it easier to create a semi-molten state for the formation of lloK class superconductors, but it remains in the grain boundary phase after firing and weakens the bonds between the formed superconductor particles. It also has the disadvantage of Therefore, the obtained fired body has a problem in that the critical current density, which is one of the superconducting properties, is low. In order to improve this critical current density, it is necessary to sinter the particles of the fringe conductor to the 110 obtained by firing. The secondary heat treatment of the present invention bonds particles of the superconductor through this sintering.
以下、本発明の焼結方法について説明する。The sintering method of the present invention will be explained below.
一次熱処理
Ｂｉ、 Ｐｂ、 Ｓｒ、 Ｃａ及びＣｕから構成されて
いる酸化物は、従来どおりの焼成条件、すなわちＢｉ−
Ｐｂ−Ｓｒ−Ｃａ＝Ｃｕ−０系超伝導体を生成させるに
必要な熱処理温度、望ましくはその最適熱処理温度で焼
成される。例えばバルクであれば８５０℃前後で数十時
間空気中で熱処理を行ない、１１０に縁起伝導粒子を生
成させる。Primary heat treatment The oxide composed of Bi, Pb, Sr, Ca and Cu was subjected to the conventional firing conditions, namely Bi-
It is fired at a heat treatment temperature necessary to produce a Pb-Sr-Ca=Cu-0 based superconductor, preferably at its optimum heat treatment temperature. For example, in the case of a bulk product, heat treatment is performed in the air at around 850° C. for several tens of hours to generate catalytic conductive particles 110.
二次弊処理
一次熱処理によって得られた焼成体は、次に１１０に縁
起伝導体の粒子を焼結させるために、Ｂｉ−Ｓｒ−Ｃａ
−Ｃｕ−０系超伝導体を焼結させるに必要な熱処理温度
（例えばパル材であれば８６０〜８７０℃）まで昇温し
、数時間、空気中で保持し熱処理を行なう。この二次熱
処理終了後、炉内で放冷する。Secondary heat treatment The fired body obtained by the first heat treatment is then treated with Bi-Sr-Ca in order to sinter the particles of the auspicious conductor at 110.
The temperature is raised to a heat treatment temperature necessary for sintering the -Cu-0 superconductor (for example, 860 to 870°C for pal material), and the heat treatment is carried out by holding in air for several hours. After completing this secondary heat treatment, it is allowed to cool in the furnace.
ここで、−成熱処理温度から、二次熱処理温度までの昇
温は、連続的であっても、不連続的であっても良い。連
続的に温度を上げる場合には１時間当たり ０．１〜２
℃の昇温速度が好ましく、また、不連続的に温度を上げ
る場合には、２〜５℃間隔で昇温し、各温度ごとに数時
間保持するのが好ましい。Here, the temperature increase from the -forming heat treatment temperature to the secondary heat treatment temperature may be continuous or discontinuous. When increasing the temperature continuously, 0.1 to 2 per hour
A temperature increase rate of 0.degree. C. is preferable, and when the temperature is raised discontinuously, it is preferable to increase the temperature at intervals of 2 to 5.degree. C. and hold each temperature for several hours.
Ｂｉ、 Ｐｂ、 Ｓｒ、 Ｃａ及びＣｕから構成されて
いる酸化物は、特にその形状を問わない。すなわち、粉
末の成形体であっても、上記元素を含む膜状のもので６
良い。粉末を用いる場合、それぞれの金属を含む炭酸塩
、硝酸塩等の仮焼粉末であっても、それぞれの酸化物の
混合粉末でも良い。また膜の場合、製造方法としてはド
クターブレード法、スフノーン印刷方法、塗布熱分解法
、ＣＶＤ法、スパッタリング法、真空蒸着法等が挙げら
れる。The shape of the oxide composed of Bi, Pb, Sr, Ca, and Cu is not particularly limited. In other words, even if it is a powder compact, it is a film-like product containing the above elements.
good. When using powder, it may be a calcined powder of carbonate, nitrate, etc. containing each metal, or a mixed powder of each oxide. In the case of a film, manufacturing methods include a doctor blade method, a sulfone printing method, a coating pyrolysis method, a CVD method, a sputtering method, a vacuum evaporation method, and the like.
上記の酸化物の組成は、原子比で下記の範囲にすること
が好ましい６
Ｂｉ： ０．５〜１．０
Ｐｂ： ０．５ 〜１．０
Ｓｒ： ０．８〜１．２
Ｃａ： ０．８〜１．２
ｒｌｌ・ １−４〜２−ロ
上記の範囲以外の組成では、ｌｌｏＫ級超伝導体が生成
しにくい。The composition of the above oxide is preferably in the following range in terms of atomic ratio 6 Bi: 0.5 to 1.0 Pb: 0.5 to 1.0 Sr: 0.8 to 1.2 Ca: 0 .8 to 1.2 rll 1-4 to 2-b If the composition is outside the above range, it is difficult to form a lloK class superconductor.
〔実施例Ｊ
ＢｉｚＯｓ 、 ＰｂＯ、ＳｒＣＯ：＋ 、 ＣａＣ０
１及びＣｕＯの各粉末を原子比がＢｉ：Ｐｂ：Ｓｒ：Ｃ
ａ：Ｃｕ＝ ０．９６：０．２４：１．０：１．０：１
．６になるように配合した。これらの粉末をメタノール
とともにボールミルで２４時間混合した。乾燥後、８０
０℃で１０時間空気中で仮焼し、この粉末を用いて、直
径１０ｍｍ厚さ１ｍｍの円板状に２ｔｏｎの荷重を加え
て成形した。[Example J BizOs, PbO, SrCO:+, CaC0
1 and CuO powders with an atomic ratio of Bi:Pb:Sr:C
a:Cu=0.96:0.24:1.0:1.0:1
．． 6. These powders were mixed with methanol in a ball mill for 24 hours. After drying, 80
The powder was calcined in air for 10 hours at 0° C., and the powder was molded into a disk shape with a diameter of 10 mm and a thickness of 1 mm under a load of 2 tons.
この成形体を８５０’Ｃ：で５０時間焼成して、ｌｌｏ
Ｋ級の超伝導粒子を生成させ、その後、２℃ずつ昇温し
、各温度で５時間保持し、最終的に８６４℃まで焼結温
度を上げた。This molded body was fired at 850'C: for 50 hours,
K-class superconducting particles were generated, and then the temperature was raised in 2°C increments, held at each temperature for 5 hours, and finally the sintering temperature was raised to 864°C.
焼結終了後、炉の電源を切り空気中で室温まで放冷した
。得られた超伝導体の臨界温度は１０５にで、その時の
臨界電流密度は５２５ Ａ／ｃ＋ｏ”であった。After the sintering was completed, the power to the furnace was turned off and the mixture was allowed to cool to room temperature in the air. The critical temperature of the obtained superconductor was 105, and the critical current density at that time was 525 A/c+o''.
また比較例として、８５０℃で８５時間焼成した得られ
た試料の臨界温度はＩＯ２にで、臨界電流密度は１１３
Ａ／ｃｍ２であった。As a comparative example, the critical temperature of the obtained sample calcined at 850°C for 85 hours was IO2, and the critical current density was 113
It was A/cm2.
〔発明の効果１
本発明の方法によれば、二次熱処理により超伝導体粒子
間の焼結が行なわれ、従来法に比べて臨界電流密度が約
５倍増加した。[Effect of the Invention 1] According to the method of the present invention, sintering between superconductor particles was performed by secondary heat treatment, and the critical current density was increased by about 5 times compared to the conventional method.
Claims (1)
いる酸化物を、一次熱処理として空気中においてＢｉ−
Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系超伝導体を生成させるに
必要な熱処理温度で加熱保持した後、更に二次熱処理と
してＢｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系超伝導体を焼結させ
るに必要な熱処理温度まで昇温し、その温度で加熱保持
することを特徴とするＢｉ−Ｐｂ−Ｓｒ−Ｃａ−Ｃｕ−
Ｏ系超伝導体の焼結方法。(1) Oxides composed of Bi, Pb, Sr, Ca and Cu are heated in air as a primary heat treatment.
After heating and holding at a heat treatment temperature necessary to generate a Pb-Sr-Ca-Cu-O superconductor, the Bi-Sr-Ca-Cu-O superconductor is further sintered as a secondary heat treatment. Bi-Pb-Sr-Ca-Cu-, which is characterized by raising the temperature to the required heat treatment temperature and maintaining it at that temperature.
A method for sintering O-based superconductors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318855A JPH03183653A (en) | 1989-12-11 | 1989-12-11 | Method for sintering bi-pb-sr-ca-cu-o superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1318855A JPH03183653A (en) | 1989-12-11 | 1989-12-11 | Method for sintering bi-pb-sr-ca-cu-o superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03183653A true JPH03183653A (en) | 1991-08-09 |
Family
ID=18103705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1318855A Pending JPH03183653A (en) | 1989-12-11 | 1989-12-11 | Method for sintering bi-pb-sr-ca-cu-o superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03183653A (en) |
-
1989
- 1989-12-11 JP JP1318855A patent/JPH03183653A/en active Pending
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