JPH01188419A - Production of powdery starting material for high temperature superconducting ceramic - Google Patents
Production of powdery starting material for high temperature superconducting ceramicInfo
- Publication number
- JPH01188419A JPH01188419A JP63010579A JP1057988A JPH01188419A JP H01188419 A JPH01188419 A JP H01188419A JP 63010579 A JP63010579 A JP 63010579A JP 1057988 A JP1057988 A JP 1057988A JP H01188419 A JPH01188419 A JP H01188419A
- Authority
- JP
- Japan
- Prior art keywords
- earth element
- salt
- amt
- alkaline earth
- rare earth
- 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 description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000007858 starting material Substances 0.000 title abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 150000003335 secondary amines Chemical class 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- 150000003141 primary amines Chemical class 0.000 abstract description 2
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- 150000002823 nitrates Chemical class 0.000 abstract 1
- 239000002887 superconductor Substances 0.000 abstract 1
- 150000003512 tertiary amines Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 238000005245 sintering Methods 0.000 description 9
- 150000002910 rare earth metals Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910020012 Nb—Ti Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001281 superconducting alloy Inorganic materials 0.000 description 2
- -1 tertiary amine compounds Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 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、易焼結性稀土類元素−アルカリ土類元素−銅
酸化物系高温超電導セラミックスの原料粉末の製法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing raw material powder for easily sinterable rare earth element-alkaline earth element-copper oxide based high temperature superconducting ceramics.
（従来技術及びその問題点）
稀土類元素−アルカリ土類元素−銅酸化物系セラミック
スのうち、酸素欠陥型層状ペロプスカイト構造を有する
ものは、９０に以上の高い臨界温度を持つ超電導物質で
あることが知られるようになり、多方面への応用が期待
されている。(Prior art and its problems) Among rare earth element-alkaline earth element-copper oxide ceramics, those having an oxygen-deficient layered perovskite structure are superconducting materials with a high critical temperature of 90 or higher. This has become well known and is expected to be applied in many fields.
これらの稀土類元素−アルカリ土類元素−銅酸化物系高
温超電導セラミックスは、液体窒素のような安価な冷媒
で冷却することによっても超電導状態になるため、液体
ヘリウム中でしか超電導状態を示さないＮｂ−Ｔｉ系超
電導合金などの代わりに、超電導マグネットなどに使え
れば、経済的に大きなメリットがある。These rare earth element-alkaline earth element-copper oxide-based high-temperature superconducting ceramics become superconducting even when cooled with an inexpensive coolant such as liquid nitrogen, so they only exhibit superconducting state in liquid helium. If it can be used in superconducting magnets instead of Nb-Ti superconducting alloys, there will be great economic advantages.
しかし、これまで作られてきた超電導セラミックスは臨
界電流密度が数十Ａ ／ ｃｉと低く、従来−数的に使
われてきたＮｂ−Ｔｉ系超電導合金の１／２００〜１／
４００に過ぎないという欠点があった。However, the critical current density of the superconducting ceramics that have been produced so far is as low as several tens of A/ci, which is 1/200 to 1/2 of the conventionally used Nb-Ti superconducting alloys.
The drawback was that it was only 400.
また、常電導〜超電導の転移の温度幅が広く急峻さに欠
けているという点も問題であった。Another problem was that the temperature range of the transition from normal conductivity to superconductivity was wide and lacked steepness.
これらの問題点の一つの原因として、超電導セラミック
スが多孔質で密度が低いことが指摘されている。It has been pointed out that one of the causes of these problems is that superconducting ceramics are porous and have a low density.
これまで稀土類元素−アルカリ土類元素−銅酸化物系高
温超電導セラミックスは乾式あるいは湿式で混合するこ
とによって調製した原料粉末を、加圧・焼結して作られ
てきた。Hitherto, rare earth element-alkaline earth element-copper oxide-based high-temperature superconducting ceramics have been made by pressurizing and sintering raw material powders prepared by dry or wet mixing.
乾式混合法は、超電導セラミックスの構成成分の酸化物
あるいは炭酸塩の粉末、例えばＹ２Ｏ１、ＢａＣ０ｚ、
ＣｕＯの粉末を出発原料として、ボールミル、播潰機あ
るいは乳棒・乳鉢などで粉砕、混合した後に焼結して、
超電導セラミックスの原料粉末を調製する方法である。In the dry mixing method, powders of oxides or carbonates of the constituent components of superconducting ceramics, such as Y2O1, BaC0z,
Using CuO powder as a starting material, it is ground and mixed using a ball mill, crusher, pestle, mortar, etc., and then sintered.
This is a method for preparing raw material powder for superconducting ceramics.
一方、湿式混合法は、乾式混合法と同様の出発原料に、
出発原料と反応せずかつこれを実質的に溶解しない溶媒
を加えて、機械的に混合する方法である。On the other hand, the wet mixing method uses the same starting materials as the dry mixing method.
This is a method in which a solvent that does not react with the starting materials and does not substantially dissolve them is added and mixed mechanically.
上記両温合法は技術的に容易で安全性の高い方法である
が、得られた原料粉末は、粒径が１〜５μｍ以上と大き
く、粒径分布も均一ではなく、さらに成分のばらつきも
大きい。Both of the above heating methods are technically easy and highly safe methods, but the obtained raw material powder has a large particle size of 1 to 5 μm or more, the particle size distribution is not uniform, and there is also a large variation in components. .
従って、この原料粉末を焼結して作られた高温超電導セ
ラミックスは密度が小さく、臨界電流密度も低いという
問題がある。Therefore, high-temperature superconducting ceramics made by sintering this raw material powder have a problem of low density and low critical current density.
また多段湿式法においては、超電導セラミックスの各構
成成分の溶液から多段で成分を沈澱させるが、繁雑な工
程を要する等の欠点がある。Furthermore, in the multi-stage wet method, components are precipitated from a solution of each component of superconducting ceramics in multiple stages, but there are drawbacks such as requiring complicated steps.
（問題点解決のための技術的手段）
本発明は、従来の混合法及び湿式法の欠点を解決した、
易焼結性の超電導セラミックス原料粉末の製法である。(Technical means for solving the problems) The present invention solves the drawbacks of the conventional mixing method and wet method.
This is a method for producing easily sinterable superconducting ceramic raw material powder.
本発明は、稀土類元素塩、アルカリ土類元素塩及び銅塩
の混合溶液と、アンモニウム塩及びアミンの混合溶液を
接触させて形成した沈澱物を、水洗または水洗せずにろ
過分離、乾燥し、次いで仮焼成することを特徴とする稀
土類元素−アルカリ土類元素−銅酸化物系超電導セラミ
ックスの原料粉末の製法である。In the present invention, a precipitate formed by contacting a mixed solution of a rare earth element salt, an alkaline earth element salt, and a copper salt with a mixed solution of an ammonium salt and an amine is filtered, separated, and dried with or without washing with water. This is a method for producing a raw material powder for rare earth element-alkaline earth element-copper oxide based superconducting ceramics, which is characterized in that it is then calcined.
本発明において稀土類元素−アルカリ土類元素−銅酸化
物系超電導セラミックスは、次の一般式ＡＸＢＹＣｕ、
０ｔ−ｚで表される。式中ＡはＳｃ。In the present invention, the rare earth element-alkaline earth element-copper oxide based superconducting ceramic has the following general formula AXBYCu,
It is represented by 0tz. In the formula, A is Sc.
Ｙ及び周期律表のランタン系列元素から選択される少な
くとも一種類の稀土類元素を示し、ランタン系列元素の
具体例としてはＬａ５Ｎｄ、、Ｓｍ。It represents at least one kind of rare earth element selected from Y and the lanthanum series elements of the periodic table, and specific examples of the lanthanum series elements include La5Nd, Sm.
Ｅｕ、Ｇｄ及びＥｒが挙げられる。式中Ｂは周期律表の
ＩＩＡ族から選択される少なくとも一種類のアルカリ土
類元素を示し、その具体例としてはＣａ、Ｂａ及びＳｒ
が挙げられる０式中Ｘは０．８より大きく、１．２より
小さく、Ｙは１．６より大きく、２．４より小さく、Ｚ
は０より大きく、０．５より小さい数値である。また、
本発明における高温超電導セラミックスは、銅の一部を
最大５０モル％まで他の金属、例えばＶＳＺｒ。Examples include Eu, Gd and Er. In the formula, B represents at least one alkaline earth element selected from Group IIA of the periodic table, and specific examples include Ca, Ba, and Sr.
In the formula 0, X is larger than 0.8 and smaller than 1.2, Y is larger than 1.6 and smaller than 2.4, and Z
is a numerical value greater than 0 and smaller than 0.5. Also,
The high temperature superconducting ceramic in the present invention contains a portion of copper and up to 50 mol% of other metals, such as VSZr.
Ｎｂ、、Ｍｏ、Ｈｆ、Ｔａ、Ｗ、ＰｂあるいはＢｉで置
換されたものも含んでいる。It also includes those substituted with Nb, Mo, Hf, Ta, W, Pb, or Bi.
本発明の稀土類元素塩、アルカリ土類元素塩及び銅塩と
しては、塩酸塩、硝酸塩等を用いることができる。As the rare earth element salt, alkaline earth element salt, and copper salt of the present invention, hydrochloride, nitrate, etc. can be used.
アンモニウム塩としては、炭酸塩、重炭酸塩等を用いる
ことができる。その使用量は、上記アルカリ土類元素塩
と当モル以上であれば良い。As the ammonium salt, carbonate, bicarbonate, etc. can be used. The amount used may be at least the equivalent molar amount of the alkaline earth element salt.
アミン類としては、第１、第２あるいは第３級アミン化
合物を用いることができるが、特に第２級アミン化合物
（Ｒ，ＮＨ； Ｒは炭素数１〜４のアルキル基）が好ま
しい。その使用量は、上記銅塩に対して１．５モル倍以
上であれば良い。As the amines, primary, secondary or tertiary amine compounds can be used, but secondary amine compounds (R, NH; R is an alkyl group having 1 to 4 carbon atoms) are particularly preferred. The amount used should be at least 1.5 times the amount of the above copper salt by mole.
上記冬場の溶媒としては、それらを溶かすものであれば
特に制限はないが、例えば水、水−アルコール、アルコ
ール等を使用できる。The winter solvent is not particularly limited as long as it dissolves them, and for example, water, water-alcohol, alcohol, etc. can be used.
本発明において沈澱物は、例えば稀土類元素塩、アルカ
リ土類元素塩及び銅塩の混合溶液を攪拌しながら、それ
にアンモニウム塩及びアミンの混合溶液を添加すること
によって形成できる。上記の条件下で沈澱物を形成後、
さらにアミン類を稀土類元素塩、アルカリ土類元素塩及
び銅塩の全モル数に対して当モル以上加えると銅化合物
の沈澱物の形成率が向上する。In the present invention, the precipitate can be formed, for example, by adding a mixed solution of an ammonium salt and an amine to a mixed solution of a rare earth element salt, an alkaline earth element salt, and a copper salt while stirring the mixed solution. After forming a precipitate under the above conditions,
Furthermore, when amines are added in an amount equivalent to or more than the total number of moles of the rare earth element salt, alkaline earth element salt, and copper salt, the rate of formation of a copper compound precipitate is improved.
形成した沈澱物をそのまま濾過分離、乾燥できるが、沈
澱物を水洗した後に濾過分離、乾燥しても良い。The formed precipitate can be directly separated by filtration and dried, but the precipitate may be washed with water, then separated by filtration and dried.
乾燥後に粉末を仮焼結する。仮焼結の温度は４００〜９
３０℃が好ましい。仮焼結温度が４００°Ｃよりも低い
時は、混合粉末の脱水及び熱分解が充分に進行しないた
め好ましくない。又、仮焼結温度が９３０°Ｃよりも高
い時は、混合粉末の粒子が粗大化するため好ましくない
。After drying, the powder is pre-sintered. Temperature of pre-sintering is 400~9
30°C is preferred. When the pre-sintering temperature is lower than 400°C, dehydration and thermal decomposition of the mixed powder do not proceed sufficiently, which is not preferable. Moreover, when the preliminary sintering temperature is higher than 930°C, the particles of the mixed powder become coarse, which is not preferable.
本発明の方法で得られた超電導セラミックスの原料粉末
を高圧で成形し７００〜９５０°Ｃで焼結することによ
り、超電導セラミックスとすることができる。Superconducting ceramics can be obtained by molding the raw material powder of superconducting ceramics obtained by the method of the present invention under high pressure and sintering at 700 to 950°C.
（本発明の効果）
本発明の方法により得られた、稀土類元素−アルカリ土
類元素−銅酸化物系超電導セラミックスの原料粉末は、
各構成元素化合物が共沈法するため組成が均一で、かつ
粒子径がサブミクロン級の微粒子であり、良好な焼結性
を持っている。この粉末を焼結して得られた超電導セラ
ミックスは、密度 ５．３ｇ／ｃｍ以上の緻密なセラミ
ックスであり、電流密度も従来のものに比べて大きくな
っている。(Effects of the present invention) The raw material powder for rare earth element-alkaline earth element-copper oxide based superconducting ceramics obtained by the method of the present invention is as follows:
Since each constituent element compound is co-precipitated, the composition is uniform, the particle size is submicron-level fine particles, and it has good sinterability. The superconducting ceramic obtained by sintering this powder is a dense ceramic with a density of 5.3 g/cm or more, and the current density is also higher than that of conventional ceramics.
（実施例） 以下に本発明の実施例を示す。(Example) Examples of the present invention are shown below.
実施例１
炭酸アンモニウム０．０４モルの水溶液２５０戚に、ジ
エチルアミン０．０４モルの水溶液３０Ｏｄを混合し、
炭酸アンモニウム・ジエチルアミン水溶液を調製した。Example 1 30 Od of an aqueous solution of 0.04 mol of diethylamine was mixed with 250 Od of an aqueous solution of 0.04 mol of ammonium carbonate,
An aqueous ammonium carbonate/diethylamine solution was prepared.
次に上記炭酸アンモニウム・ジエチルアミン水溶液を攪
拌しながら、硝酸イツトリウム０．０２モル、硝酸バリ
ウム０．０４モル、硝酸銅０．０６モルを均一に溶解し
た水溶液４５０ｍを添加し、共沈澱物を得た。Next, while stirring the ammonium carbonate/diethylamine aqueous solution, 450 ml of an aqueous solution in which 0.02 mol of yttrium nitrate, 0.04 mol of barium nitrate, and 0.06 mol of copper nitrate were uniformly dissolved was added to obtain a coprecipitate. .
さらに共沈澱物の水溶液を攪拌しながら、ジエチルアミ
ン０．３４モルの水溶液３００ ｍｌを添加し、約１時
間攪拌後、−晩装置し沈澱反応を完結させた。Further, while stirring the aqueous solution of the coprecipitate, 300 ml of an aqueous solution of 0.34 mol of diethylamine was added, and after stirring for about 1 hour, the mixture was left in the apparatus overnight to complete the precipitation reaction.
共沈澱物を濾、過分離、乾燥後、粉砕し７５０°Ｃで２
時間仮焼結し、ｉｔ／ｄプレス成形後、９００°Ｃで５
時間焼結し、超電導セラミックス焼結体を得た。The coprecipitate was filtered, filtered, dried, ground, and heated at 750°C for 2 hours.
After pre-sintering and IT/D press molding, 5 hours at 900°C.
A superconducting ceramic sintered body was obtained by sintering for a period of time.
この超電導セラミックスの密度は５．５４ ｇ／ｄであ
り、臨界温度°（Ｔ ｃ ）は９５に、臨界電流密度は
３５０ Ａ／ｄであった。The density of this superconducting ceramic was 5.54 g/d, the critical temperature ° (T c ) was 95, and the critical current density was 350 A/d.
実施例２
共沈澱物の濾過分離、乾燥において、二〇共沈澱物を蒸
留水で水洗し、濾過分離、乾燥をした以外は、実施例１
と同様に行った。Example 2 Example 1 except that in the filtration separation and drying of the coprecipitate, the coprecipitate was washed with distilled water, filtered, separated, and dried.
I did the same thing.
この超電導セラミックスの密度は５．６３ ｇ／ｄであ
り、臨界温度（Ｔ ｃ ）は９６に、臨界電流密度は３
７０Ａ／ｃＪであった。The density of this superconducting ceramic is 5.63 g/d, the critical temperature (T c ) is 96, and the critical current density is 3.
It was 70A/cJ.
実施例３
硝酸イツトリウムの代わりに、硝酸エルビウムを使用し
た以外は実施例２と同様に行った。Example 3 The same procedure as Example 2 was carried out except that erbium nitrate was used instead of yttrium nitrate.
この超電導セラミックスの密度は５．５２ｇ／ｃｄであ
り、臨界温度（Ｔ ｃ ）は９８に、臨界電流密度は３
７２ Ａ／ｄであった。The density of this superconducting ceramic is 5.52 g/cd, the critical temperature (T c ) is 98, and the critical current density is 3.
It was 72 A/d.
実施例４
硝酸イツトリウムの代わりに、硝酸サマリウムを使用し
た以外は実施例２と同様に行った。Example 4 The same procedure as Example 2 was carried out except that samarium nitrate was used instead of yttrium nitrate.
この超電導セラミックスの密度は５．６０ ｇ／ｃｔＡ
であり、臨界温度（Ｔ ｃ ）は９７に、臨界電流密度
は３６５ Ａ／ｄであった。The density of this superconducting ceramic is 5.60 g/ctA
The critical temperature (T c ) was 97, and the critical current density was 365 A/d.
比較例１
酸化イツトリウム０．５モル、炭酸バリウム２．０モル
、酸化銅３モルの粉末を、播潰機を用いて乾式混合した
。この粉末を空気中で８２０°Ｃ１２時間焼成した。こ
の粉末をＩｔ／ｄプレス成形後、９００°Ｃで６時間焼
結し、セラミックス焼結体を得た。Comparative Example 1 Powders containing 0.5 mol of yttrium oxide, 2.0 mol of barium carbonate, and 3 mol of copper oxide were dry mixed using a crusher. This powder was calcined in air at 820°C for 12 hours. This powder was subjected to It/d press molding and sintered at 900°C for 6 hours to obtain a ceramic sintered body.
このセラミックスの密度は５．２５ｇ／ＣＴＡであり、
臨界温度（Ｔｃ）は９１に、臨界電流密度は２７０Ａ／
ｃｄであった。The density of this ceramic is 5.25g/CTA,
Critical temperature (Tc) is 91, critical current density is 270A/
It was a CD.
Claims (1)
と、アンモニウム塩及びアミンの混合溶液を接触させて
形成した沈澱物を、水洗または水洗せずにろ過分離、乾
燥し、次いで仮焼成することを特徴とする稀土類元素−
アルカリ土類元素−銅酸化物系超電導セラミックスの原
料粉末の製法。A precipitate formed by contacting a mixed solution of a rare earth element salt, an alkaline earth element salt, and a copper salt with a mixed solution of an ammonium salt and an amine is separated by filtration with or without water washing, dried, and then calcined. A rare earth element characterized by
A method for producing raw material powder for alkaline earth element-copper oxide superconducting ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63010579A JPH01188419A (en) | 1988-01-22 | 1988-01-22 | Production of powdery starting material for high temperature superconducting ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63010579A JPH01188419A (en) | 1988-01-22 | 1988-01-22 | Production of powdery starting material for high temperature superconducting ceramic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01188419A true JPH01188419A (en) | 1989-07-27 |
Family
ID=11754155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63010579A Pending JPH01188419A (en) | 1988-01-22 | 1988-01-22 | Production of powdery starting material for high temperature superconducting ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01188419A (en) |
-
1988
- 1988-01-22 JP JP63010579A patent/JPH01188419A/en active Pending
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