JPS63319244A - Mixture of oxide superconducting material - Google Patents
Mixture of oxide superconducting materialInfo
- Publication number
- JPS63319244A JPS63319244A JP62155079A JP15507987A JPS63319244A JP S63319244 A JPS63319244 A JP S63319244A JP 62155079 A JP62155079 A JP 62155079A JP 15507987 A JP15507987 A JP 15507987A JP S63319244 A JPS63319244 A JP S63319244A
- Authority
- JP
- Japan
- Prior art keywords
- superconducting material
- oxide superconducting
- mixture
- compd
- org
- 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 36
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000002887 superconductor Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000748 compression moulding Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polyvinylbutylene Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はＹ−Ｂａ−ＣｕＯあるいはＬａ−３ｒ−ＣｕＯ
系で代表される酸化物超伝導材料を成形加工するために
バインダを加えた酸化物超伝導材料混合物に関するもの
である。Detailed Description of the Invention [Industrial Application Field] The present invention is directed to Y-Ba-CuO or La-3r-CuO.
The present invention relates to an oxide superconducting material mixture to which a binder is added in order to mold and process the oxide superconducting material represented by the above-mentioned oxide superconducting material.
従来、酸化物超伝導材料を一定の形に成形する場合には
ポリビニルアルコール（ＰＶＡ）を水あるいはエチレン
グリコールに溶解した粘土が１センチポイズから数ポイ
ズの粘稠な液体を、酸化物超伝導材料の微粉末に重量比
で５〜１０％添加し、よく撹拌した後、得られた混合物
を圧縮成形（１−当たり０．１〜１ｔｏｎ程度の圧縮力
）して成形品を得ていた。この成形方法では、粉体で扱
うため押し出し成形とか、射出成形は出来ないという問
題があった。Conventionally, when molding an oxide superconducting material into a certain shape, clay made by dissolving polyvinyl alcohol (PVA) in water or ethylene glycol was used to form a viscous liquid of 1 centipoise to several poise into the oxide superconducting material. After adding 5 to 10% by weight to the fine powder and stirring well, the resulting mixture was compression molded (compression force of about 0.1 to 1 ton per unit) to obtain a molded product. This molding method has the problem that extrusion molding or injection molding cannot be performed because it is handled as a powder.
押し出し成形、射出成形を行うためには材料が粘稠でな
ければならない。ところが酸化物超伝導材料にＰＶＡ水
溶液やエチレングリコールをバインダとして多量に加え
ると水や、エチレングリコールが酸化物超伝導材料と相
互作用を起こし、これらの混合物は押し出し成形、射出
成形に適した粘稠な組成の混合物としては得られない。In order to perform extrusion molding and injection molding, the material must be viscous. However, when a large amount of PVA aqueous solution or ethylene glycol is added as a binder to an oxide superconducting material, water and ethylene glycol interact with the oxide superconducting material, resulting in a mixture with a viscosity suitable for extrusion molding and injection molding. It cannot be obtained as a mixture with a specific composition.
また、水を酸化物超伝導材料に多量に添加すると、酸化
物超伝導材料を構成しているＢａやＳｒの酸化物が水に
溶解してしまうため、成形性が付与できたとしても、超
伝導性そのものがなくなってしまう。Additionally, if a large amount of water is added to an oxide superconducting material, the Ba and Sr oxides that make up the oxide superconducting material will dissolve in the water, so even if moldability can be imparted, superconducting The conductivity itself disappears.
一方、セラミックスの成形加工技術分野ではアルミナ、
ジルコニア等の各種セラミックスを射出成形する場合に
各種の熱可塑性レジン、例えば、ポリビニルブチ）−ル
、ポリプロピレン等、レジン以外ではフタル酸ジｎ−ブ
チル、フタール酸エステルなどの可塑剤が用いられてい
る。しかしながら、酸化物超伝導材料は成形後９００℃
〜１０００℃で焼結する工程が含まれる。この焼結温度
は酸化物超伝導材料の超伝導特性を決定するために重要
であり、上記の温度範囲以外では良好な超伝導特性は得
られない。このため、′酸化物超伝導材料用バインダと
しては９００℃〜１０００℃の塩度範囲で完全に蒸発す
るか、完全に燃焼するものが好ましい。酸化物超伝導材
料のバインダとして熱可塑性レジン、フタル酸ジ−ｎブ
チル等を用いた場合、上記温度ではバインダが完全に燃
焼あるいは蒸発しなし：ため、酸化物超伝導材料組成の
中にバインダに帰因する炭素分が残留し、超伝導特性が
消失するか、あるいは超伝導特性を示す転移温度Ｔｃが
著しく低下する。On the other hand, in the field of ceramic molding technology, alumina,
When injection molding various ceramics such as zirconia, various thermoplastic resins, such as polyvinylbutylene, polypropylene, etc., and plasticizers such as di-n-butyl phthalate and phthalate esters are used in addition to resins. . However, oxide superconducting materials are heated to 900°C after molding.
A step of sintering at ~1000°C is included. This sintering temperature is important for determining the superconducting properties of the oxide superconducting material, and good superconducting properties cannot be obtained outside the above temperature range. Therefore, the binder for the oxide superconducting material is preferably one that completely evaporates or completely burns in the salinity range of 900°C to 1000°C. When a thermoplastic resin, di-n-butyl phthalate, etc. is used as a binder for an oxide superconducting material, the binder does not completely burn or evaporate at the above temperature. The resulting carbon content remains, and the superconducting properties disappear, or the transition temperature Tc exhibiting the superconducting properties decreases significantly.
本発明の目的は酸化物超伝導材料の成形混合物を提供す
ることであり、これによって酸化物超伝導材料の特性を
損なうことなく酸化物超伝導材料に容易に成形性を行与
でき、かつ各種の成形方法を可能とする混合物を提供す
ることにある。An object of the present invention is to provide a molding mixture of oxide superconducting materials, which can easily impart moldability to oxide superconducting materials without impairing the properties of the oxide superconducting materials. The object of the present invention is to provide a mixture that enables the molding method.
本発明を概説すれば酸化物超伝導材料の微粉末に成形性
を与えるバインダとして、１分子内に水酸基を３個以上
持ち、常温で液体でかつその沸点が１００℃〜５００℃
の範囲内にある有機化合物を用いる事を特徴とする。該
有機化合物としてはグリセリン、トリエタノールアミン
などが適している。To summarize the present invention, it is used as a binder that gives moldability to fine powder of oxide superconducting material, has three or more hydroxyl groups in one molecule, is liquid at room temperature, and has a boiling point of 100°C to 500°C.
It is characterized by using an organic compound within the range of . Suitable organic compounds include glycerin and triethanolamine.
従来技術に比較して、本発明によるバインダを用いるこ
とにより成形性良好な粘稠性の高い超伝導材料混合物が
得られる。この混合物を用いて、任意の成形品を作製し
た後、９００〜１０００℃で焼結することにより、残留
炭素分もなく、酸化物超伝導材料の最も重要な特性であ
るＴｃは最初に用いた原料の酸化物超伝導材料を圧縮成
形法で円板状試料を作製して９５０℃で焼結した場合と
同等か、１〜２°に低い程度である。Compared to the prior art, highly viscous superconducting material mixtures with good moldability are obtained by using the binder according to the invention. After making any molded product using this mixture, it is sintered at 900 to 1000°C, so there is no residual carbon content, and Tc, the most important property of oxide superconducting materials, is the first used. This is the same as when a disk-shaped sample is prepared by compression molding the oxide superconducting material as a raw material and sintered at 950°C, or is as low as 1 to 2°.
また、本発明に係わる混合物を用いることにより、押し
出し成形後、射出成形機を使用して酸化物超伝導材料で
構成される各種形状の成形品を作製することができる。Further, by using the mixture according to the present invention, molded articles of various shapes made of oxide superconducting material can be produced using an injection molding machine after extrusion molding.
（実施例） 以下に本発明の具体的な実施例について説明する。(Example) Specific examples of the present invention will be described below.
〔実施例１〕
ＹＢａｚＣｕ、０．−、なる組成を持つ酸化物超伝導材
料の微粉末にバインダとしてグリセリン
（ＨＯＣＨｚ−ＣＨ（ＯＨ）−ＣＨ２０Ｈ，ｂ、ｐ、
７６０ｍｍｌｔｇ、２９０℃〕を、酸化物超伝導材料に
８ｗｔ％添加した後混練し、可塑性のある混合物を得る
。この混合物を注射器に入れ、針をつけないで押し出し
、直径１゜５ｍｍの棒状成形物を得た。この成形物を厚
さ０゜０５胴の銅製のテープの上に置き、９５０℃酸素
雰囲気中で焼成した。徐冷後焼成物は酸化銅チー−４＝
プ上にあり、酸化銅テープから容易にはがれる。[Example 1] YBazCu, 0. -, glycerin (HOCHz-CH(OH)-CH20H, b, p,
760 mmltg, 290° C.] was added to the oxide superconducting material in an amount of 8 wt % and then kneaded to obtain a plastic mixture. This mixture was put into a syringe and extruded without a needle attached to obtain a rod-shaped molded product with a diameter of 1.5 mm. This molded product was placed on a copper tape having a thickness of 0.05° and fired at 950° C. in an oxygen atmosphere. After slow cooling, the fired product is on the copper oxide tape and can be easily peeled off from the copper oxide tape.
この棒状成形品のＴｃを四端子法で測定した所、第１図
に示すような結果が得られた（Ｔｃ（ミツドポイント）
＝８５Ｋ）。原料として用いた酸化物超伝導材料の微粉
末を別る方法で圧縮成形し、Ｔｃを測定した結果Ｔｃ（
オフセット）−８６にであった。When the Tc of this rod-shaped molded product was measured using the four-probe method, the results shown in Figure 1 were obtained (Tc (mid point)
=85K). The fine powder of the oxide superconducting material used as a raw material was compression molded using a different method, and the Tc was measured.
Offset) -86.
〔実施例２〕
実施例１と同じ酸化物超伝導材料微粉末に、バインダと
してトリ・エタノールアミン
（Ｎ（ＣＨｚＣＨｚＯＨ）３、ｂ、ｐ、 ７６０ｍｍ１
ｇ、 ３６０℃〕を７ｗｔ％加えて実施例１と同じ繰作
により棒状試料を作りＴｃを測定した所Ｔｃ（ミツドポ
イント）＝８６にであった。[Example 2] Tri-ethanolamine (N(CHzCHzOH)3, b, p, 760 mm1) was added as a binder to the same oxide superconducting material fine powder as in Example 1.
A rod-shaped sample was prepared by the same procedure as in Example 1 by adding 7 wt % of 360°C], and the Tc was measured, and it was found to be Tc (mid point) = 86.
〔比較例１〕
本発明の効果を比較するため、実施例１．２で用いたバ
インダと同程度の粘度を持つ流動パラフィンを酸化物超
伝導材料の微粉末に７ｗｔ％添加し可塑性のある混合物
を得た。[Comparative Example 1] In order to compare the effects of the present invention, 7 wt% of liquid paraffin having a viscosity similar to that of the binder used in Example 1.2 was added to a fine powder of an oxide superconducting material to create a plastic mixture. I got it.
さらに、実施例１と同様の棒状試料を作りＴｃ（ミツド
ポイント）を測定した結果７８にであった。このＴｃの
低下は残留炭素分の影響と思われる。また流動パラフィ
ンを用いた場合は、焼結工程で流動パラフィンが蒸発す
ることなく、成形品近傍で燃焼するため成形品は気泡が
多く、本比較例では銅テープに溶着してしまっている。Furthermore, a rod-shaped sample similar to that in Example 1 was prepared and the Tc (midpoint) was measured, and the result was 78. This decrease in Tc is thought to be due to the influence of residual carbon. In addition, when liquid paraffin is used, the liquid paraffin does not evaporate during the sintering process but burns near the molded product, so the molded product has many bubbles, which were welded to the copper tape in this comparative example.
なお、本実施例ではＹ−Ｂａ−ＣｕＯ系の酸化物超伝導
材料を用いたが、他の酸化物超伝導材料、例えばＬ ａ
−Ｓ ｒ −Ｃｕ Ｏ系でも、同様の効果が得られた
。Note that although a Y-Ba-CuO-based oxide superconducting material was used in this example, other oxide superconducting materials such as La
Similar effects were obtained with the -S r -Cu O system.
以上説明したように、本発明によるバインダと酸化物超
伝導材料を混合して用いれば、良好な可塑性と、各種成
形方法に適した特性を持つ混合物が得られる。As explained above, by mixing and using the binder according to the present invention and the oxide superconducting material, a mixture having good plasticity and properties suitable for various molding methods can be obtained.
また、成形後焼結しても原料として用いた酸化物超伝導
材料のＴｃを低下させることがないという利点がある。Further, there is an advantage that even if sintering is performed after forming, the Tc of the oxide superconducting material used as a raw material does not decrease.
第１図は、本発明によって得られた棒状成形品の温度、
抵抗特性を示す。Figure 1 shows the temperature of the rod-shaped molded product obtained by the present invention,
Indicates resistance characteristics.
Claims (1)
ち常温で液体でかつ沸点が１００〜５００℃の範囲であ
る有機化合物とが混合されていることを特徴とする酸化
物超伝導材料混合物。An oxide superconductor characterized by a mixture of a fine powder of a superconducting material and an organic compound that has three or more hydroxyl groups (OH groups), is liquid at room temperature, and has a boiling point in the range of 100 to 500°C. material mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155079A JPS63319244A (en) | 1987-06-22 | 1987-06-22 | Mixture of oxide superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155079A JPS63319244A (en) | 1987-06-22 | 1987-06-22 | Mixture of oxide superconducting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63319244A true JPS63319244A (en) | 1988-12-27 |
Family
ID=15598197
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62155079A Pending JPS63319244A (en) | 1987-06-22 | 1987-06-22 | Mixture of oxide superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63319244A (en) |
-
1987
- 1987-06-22 JP JP62155079A patent/JPS63319244A/en active Pending
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