JPH01119555A - Production of ceramic superconducting material - Google Patents
Production of ceramic superconducting materialInfo
- Publication number
- JPH01119555A JPH01119555A JP62275635A JP27563587A JPH01119555A JP H01119555 A JPH01119555 A JP H01119555A JP 62275635 A JP62275635 A JP 62275635A JP 27563587 A JP27563587 A JP 27563587A JP H01119555 A JPH01119555 A JP H01119555A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- powder
- cooled
- cooling rate
- calcined
- 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
- 239000000463 material Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000011812 mixed powder Substances 0.000 claims abstract description 5
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 claims abstract 3
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002887 superconductor Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (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〕
本発明はセラミック超伝導材料の製造方法に係り、特に
均一で緻密で高い超伝導臨界温度Ｔ、を有するセラミッ
ク超伝導材料の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a ceramic superconducting material, and particularly to a method for manufacturing a ceramic superconducting material that is uniform, dense, and has a high superconducting critical temperature T.
セラミック系超伝導材料が発見されて以来、該超伝導材
料の研究、開発が急速に発展した。昭和６２年末にはＹ
−Ｂａ−Ｃｕ−０系で超伝導臨界温度（Ｔｃ）＝９０Ｋ
を作ることができた。Since the discovery of ceramic superconducting materials, research and development of these superconducting materials have rapidly progressed. At the end of 1986, Y
-Superconducting critical temperature (Tc) = 90K in Ba-Cu-0 system
I was able to make it.
従来セラミック系超伝導材料の製造は例えばＹ−Ｂａ
−Ｃｕ −０系ならばＹ２Ｏ，、ＢａＣ０，、ＣｕＯを
出発物質として混合粉砕後、約９００〜９５０℃で１２
時間酸素雰囲気中で仮焼し、その後ボールミル粉砕、プ
レス成形を経て、約９５０〜１０００℃酸素雰囲気中で
焼成し、その後５５０℃程度に急冷し一定時間保持した
後、室温まで徐冷することによってなされる。Traditionally, ceramic superconducting materials have been manufactured using Y-Ba, for example.
-Cu -0 system uses Y2O, BaC0, and CuO as starting materials, and after mixing and pulverizing, the
By calcining in an oxygen atmosphere for an hour, then ball milling and press forming, firing in an oxygen atmosphere at approximately 950-1000℃, then rapidly cooling to approximately 550℃, holding for a certain period of time, and slowly cooling to room temperature. It will be done.
しかしながら上記焼成処理温度からの急冷するとＹ、Ｂ
ａＣｕ０ｓ及びＢａＣｕ０ｔ等の不純物第２相生成され
、超伝導臨界温度Ｔｃが低下する。また上記徐冷工程で
は超伝導粒子が巨大化し不均一な組織となり上記と同様
にＴｃが低下する。However, when rapidly cooled from the above firing temperature, Y, B
A second phase of impurities such as aCu0s and BaCu0t is generated, and the superconducting critical temperature Tc is lowered. Further, in the slow cooling step, the superconducting particles become gigantic and have a non-uniform structure, resulting in a decrease in Tc as described above.
本発明は高いＴ、を有する均一で緻密な超伝導体を製造
することを目的とする。The present invention aims to produce a uniform and dense superconductor with a high T.
上記問題点は本発明によれば
下記工程（イ）−（へ） ：
（イ） Ｙ−Ｂａ −Ｃｕ −０系セラミック粉末を混
合する工程、
（ロ）該混合粉をルツボに入れ仮焼する工程、（ハ）前
記仮焼温度から降温速度１００〜５００℃／時間で５０
０℃迄降温、冷却する工程、（ニ）該冷却セラミックを
粉砕し前記（ロ）工程１．（ハ）工程そして該（ニ）工
程を複数回繰返す工程、
（ホ）得られた仮焼粉を所定形状に成形する工程・
（へ）所定温度で焼結し降温速度１００〜５００℃／時
間で５００℃迄降温、冷却する工程、を含んでなること
を特徴とするセラミック超伝導材料の製造方法によって
解決される。According to the present invention, the above problems can be solved by the following steps (a) to (f): (a) mixing the Y-Ba-Cu-0 ceramic powder; (b) putting the mixed powder in a crucible and calcining it. Step (c) 50°C at a cooling rate of 100 to 500°C/hour from the calcination temperature.
A step of lowering the temperature to 0° C. and cooling it, (d) pulverizing the cooled ceramic and step (b) step 1. (c) Step and repeating step (d) multiple times; (e) Forming the obtained calcined powder into a predetermined shape. (f) Sintering at a predetermined temperature with a cooling rate of 100-500°C/hour The problem is solved by a method for producing a ceramic superconducting material, which is characterized by comprising a step of lowering the temperature to 500° C. and cooling it.
本発明によれば仮焼後、及び焼結後の所定温度迄の降温
速度を一定に制御しているので不純物相のない均一な超
伝導相を得ることができる。According to the present invention, since the rate of cooling down to a predetermined temperature after calcination and after sintering is controlled to be constant, a uniform superconducting phase free of impurity phases can be obtained.
以下本発明の方法の実施例を工程順に説明する。 Examples of the method of the present invention will be described below in order of steps.
（１）出発材料として”ｂｏｓ（酸化イツトリウム）、
ＢａＣ０２（炭酸バリウム） 、Ｃｕｂ（酸化銅）を元
素モル比で１：２：３となる様に秤量しボールミルによ
り２４ｈ（時間）湿式混合後乾燥した。(1) “BOS (yttrium oxide)” as a starting material,
BaC02 (barium carbonate) and Cub (copper oxide) were weighed so that the elemental molar ratio was 1:2:3, wet mixed in a ball mill for 24 hours, and then dried.
（２） Ａ ｉ ｚｏ、ルツボに上記混合粉を入れ炉
内に投入し２５０℃／ｈで８５０℃まで昇温保持後２５
０℃／ｈで降温した。(2) A i zo, put the above mixed powder in a crucible, put it into the furnace, raise the temperature to 850 ° C at 250 ° C / h and hold it for 25 minutes.
The temperature was lowered at 0°C/h.
（３）降温により５００℃まで降下した後ＡＪ！ｇｏｓ
ルツボを炉内から取出し冷却した。(3) AJ after the temperature drops to 500℃! gos
The crucible was taken out of the furnace and cooled.
（４）冷却物を乳鉢にて粉砕後、Ａ１ｚＯｓルツボに該
粉末を入れ５５０℃の炉内へ入れる。(4) After pulverizing the cooled material in a mortar, the powder is placed in an A1zOs crucible and placed in a furnace at 550°C.
（５） ２５０℃／ｈで昇温し前記（２）〜（４）工
程を３〜５回繰返す。(5) Raise the temperature at 250° C./h and repeat steps (2) to (4) 3 to 5 times.
（６）外径１５鶴高さ１鶴のベレットにプレス成形後２
５０℃／ｈの昇温速度にて９８０℃ｘ６ｈ焼結後２５０
℃／ｈにて５００℃迄降温した。(6) After press forming into a pellet with outer diameter of 15 cranes and height of 1 crane, 2
250℃ after sintering at 980℃ x 6h at a heating rate of 50℃/h
The temperature was lowered to 500°C at a rate of °C/h.
（７）降温速度をそれぞれ５０ 、１００ 、２５０
、５００、及び６００℃／ｈに変え抵抗率とＴ、の関係
を測定した。それぞれのグラフを１．２．３．４及び５
で示した。(7) Temperature decreasing rate of 50, 100, 250, respectively.
, 500, and 600° C./h to measure the relationship between resistivity and T. 1.2.3.4 and 5 for each graph
It was shown in
その結果を第１図に示す。The results are shown in FIG.
第１図によれば降温速度１００℃／ｈ、 ２５０℃／
ｈ、及び５００℃／ｈにおいて抵抗率約６０Ｘ１０−’
Ω・１以下及びＴｃ ９２Ｋ 、 ９３Ｋを得た。According to Figure 1, the temperature decreasing rate is 100℃/h, 250℃/h.
h, and resistivity approximately 60X10-' at 500°C/h.
Ω・1 or less and Tc of 92K and 93K were obtained.
また、本実施例により作成した超伝導材の粉末Ｘ線回折
による生成相と８５０℃→急冷法（６００℃／ｈ）によ
り仮焼後焼結したものの生成相とを第１表に示す。Further, Table 1 shows the phases formed by powder X-ray diffraction of the superconducting material prepared according to this example and the phases formed after calcination and sintering by the 850° C. → rapid cooling method (600° C./h).
本実施例による仮焼方法によれば不純物相は検出されず
仮焼体及び焼結体においても超伝導相Ｂａ、ＹＣｕ、Ｏ
，単相であった。According to the calcination method according to this embodiment, no impurity phase is detected, and superconducting phases Ba, YCu, O
, it was single phase.
又第１表下段に抵抗率が０になる温度Ｔｃを示す０本方
法によるＴｃは従来法より高かった。In addition, the temperature Tc at which the resistivity becomes 0 is shown in the lower part of Table 1, and the Tc obtained by the zero method was higher than that of the conventional method.
電子顕微鏡にて微細組織を観察したところ本方法により
作成した試料には、幅約２（ｏ）、長さ約５（ＤＪの結
晶相が均一にかつ緻密に存在していた。When the microstructure was observed using an electron microscope, it was found that the sample prepared by this method had a uniform and dense crystalline phase with a width of about 2 (o) and a length of about 5 (DJ).
一方従来法により作成した試料には上記サイズの結晶粒
をとりかこむ様に幅約１０（Ｄ）、長さ約５０（ｏ）の
巨大粒子が混在していた。On the other hand, in the sample prepared by the conventional method, giant particles having a width of about 10 (D) and a length of about 50 (o) were mixed in, surrounding the crystal grains of the above-mentioned size.
以下余白
第１表
〔発明の効果〕
以上説明したように本発明によれば超伝導臨界温度、Ｔ
、の高い均一で緻密な超伝導相を有するセラミック超伝
導体を得ることができる。Below is Table 1 in the margin [Effects of the invention] As explained above, according to the present invention, the superconducting critical temperature, T
A ceramic superconductor having a highly uniform and dense superconducting phase can be obtained.
ある。 be.
Claims (1)
工程、 （ロ）該混合粉末をルツボに入れ仮焼する工程、（ハ）
前記仮焼温度から降温速度１００〜５００℃／時間で５
００℃迄降温、冷却する工程、 （ニ）該冷却セラミックを粉砕し前記（ロ）工程、（ハ
）工程そして該（ニ）工程を複数回繰返す工程、 （ホ）得られた仮焼粉末を所定形状に成形する工程、 （へ）所定温度で焼結し降温速度１００〜５００℃／時
間で５００℃迄降温、冷却する工程、 を含んでなることを特徴とするセラミック超伝導材料の
製造方法。1. The following steps (a) to (e): (a) a step of mixing Y-Ba-Cu-O ceramic powder; (b) a step of calcining the mixed powder in a crucible; (c)
5 at a cooling rate of 100 to 500°C/hour from the above calcination temperature.
(d) pulverizing the cooled ceramic and repeating the steps (b), (c) and (d) several times; (e) the resulting calcined powder. A method for producing a ceramic superconducting material, comprising the following steps: (f) sintering at a predetermined temperature and lowering the temperature to 500°C at a cooling rate of 100 to 500°C/hour. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62275635A JPH01119555A (en) | 1987-11-02 | 1987-11-02 | Production of ceramic superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62275635A JPH01119555A (en) | 1987-11-02 | 1987-11-02 | Production of ceramic superconducting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01119555A true JPH01119555A (en) | 1989-05-11 |
Family
ID=17558205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62275635A Pending JPH01119555A (en) | 1987-11-02 | 1987-11-02 | Production of ceramic superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01119555A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03136950A (en) * | 1989-10-24 | 1991-06-11 | Takata Kk | Restriction/protection seat for baby |
-
1987
- 1987-11-02 JP JP62275635A patent/JPH01119555A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03136950A (en) * | 1989-10-24 | 1991-06-11 | Takata Kk | Restriction/protection seat for baby |
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