JPH01192709A - Production of superconductin oxide ceramic powder and sintered form therefrom - Google Patents
Production of superconductin oxide ceramic powder and sintered form therefromInfo
- Publication number
- JPH01192709A JPH01192709A JP63017584A JP1758488A JPH01192709A JP H01192709 A JPH01192709 A JP H01192709A JP 63017584 A JP63017584 A JP 63017584A JP 1758488 A JP1758488 A JP 1758488A JP H01192709 A JPH01192709 A JP H01192709A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- superconducting
- superconducting oxide
- oxygen
- raw material
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims description 26
- 239000011224 oxide ceramic Substances 0.000 title claims description 24
- 239000012159 carrier gas Substances 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 26
- 238000010438 heat treatment Methods 0.000 abstract description 25
- 239000007789 gas Substances 0.000 abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical group 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 150000001342 alkaline earth metals Chemical group 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 238000000889 atomisation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052747 lanthanoid Inorganic materials 0.000 description 6
- 150000002602 lanthanoids Chemical class 0.000 description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 150000001450 anions Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005404 magnetometry Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc 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、超電導酸化物セラミクスの原料粉体、粉体お
よび焼結体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a raw material powder for superconducting oxide ceramics, a method for producing the powder, and a sintered body.
〈従来の技術〉
従来、Ｎｂ等の合金系で実用化が進め
られて来た超電導材料も、Ｌａ２−ｘＢａｘ（：ｕｏ４
゜Ｂａｏ、ａＹｏ４（：ｕ１０３等（Ｚ、ｐｈｙｓ、Ｂ
、−ＣｏｎｄｅｎｓｅｄＭａｔｔｅｒ ６４ １８９−
１９３ （１９８６））の４０に級、９０に級の材料が
発見されるにおよび特に冷媒として安価な液体窒素の利
用が可能となる９０に級酸化物セラミクス材料の実用化
を目指し、世界的な研究開発が進められている。<Conventional technology> Superconducting materials, which have been put into practical use in alloys such as Nb, are also La2-xBax (:uo4
゜Bao, aYo4 (: u103 etc. (Z, phys, B
, -CondensedMatter 64 189-
193 (1986)), 40-grade and 90-grade materials were discovered, and a worldwide effort was made to commercialize 90-grade oxide ceramic materials, which would enable the use of inexpensive liquid nitrogen as a refrigerant. Research and development is underway.
その中で酸化物セラミクス材料用原料粉体の製造方法と
しては、
■ 粉末冶金法
■ 共沈法
■ ゾルゲル法
等の検討が進められている。Among these, methods for producing raw material powder for oxide ceramic materials are being studied, such as ■ powder metallurgy method ■ co-precipitation method ■ sol-gel method.
〈発明が解決しようとする課題〉
しかし、これらの方法で得られる粉体は、純度や、組成
、結晶性、粒径等の均質性や、生産性や、粉体の焼結性
等のいずれかの点で実用上不十分である。<Problems to be solved by the invention> However, the powder obtained by these methods has poor purity, composition, crystallinity, homogeneity of particle size, etc., productivity, and sinterability of the powder. In this respect, it is insufficient in practical terms.
本発明の目的は、純度、均質性、焼結性にすぐれた粉体
を生産性よく得ることのできる超電導酸化物セラミクス
の原料粉体の製造方法と、その製造方法を用いた超電導
酸化物セラミクスの粉体および焼結体の製造方法を提供
することにある。The purpose of the present invention is to provide a method for producing raw material powder for superconducting oxide ceramics that can yield powder with excellent purity, homogeneity, and sinterability with good productivity, and a method for producing superconducting oxide ceramics using the production method. An object of the present invention is to provide a method for producing powder and sintered body.
く課題を解決するための手段〉
本発明における超電導酸化物セラミクスの原料粉体の製
造方法は、超電導酸化物を構成する元素の熱分解可能な
塩の溶液を霧化し、キャリヤガスにて熱分解装置内に導
入して酸素含有雰囲気下熱分解を行って超電導酸化物セ
ラミクスの原料粉体を得る超電導酸化物セラミクスの原
料粉体の製造方法を得るものである。Means for Solving the Problems> The method for producing raw material powder for superconducting oxide ceramics in the present invention involves atomizing a solution of a thermally decomposable salt of an element constituting a superconducting oxide, and thermally decomposing it with a carrier gas. The present invention provides a method for producing raw material powder for superconducting oxide ceramics, which is introduced into an apparatus and subjected to thermal decomposition in an oxygen-containing atmosphere to obtain raw material powder for superconducting oxide ceramics.
本発明における超電導酸化物セラミクスの粉体の製造方
法は、上記の製造方法により超電導酸化物セラミクスの
原料粉体を得、これを酸素含有雰囲気下、６００℃以下
の温度で熱処理するものである。The method for producing superconducting oxide ceramic powder in the present invention is to obtain superconducting oxide ceramic raw material powder by the above-described production method, and heat-treating the powder at a temperature of 600° C. or lower in an oxygen-containing atmosphere.
本発明における超電導酸化物セラミクスの焼結体の製造
方法は、上記の製造方法により超電導酸化物セラミクス
の原料粉体を得、これを焼結するものである。The method for producing a sintered body of superconducting oxide ceramics according to the present invention is to obtain raw material powder for superconducting oxide ceramics by the above-described production method and sintering this.
以下、本発明の具体的構成を詳細に説明する。Hereinafter, the specific configuration of the present invention will be explained in detail.
本発明の製造方法は、一般に超電導性を有する酸化物セ
ラミクスの製造に適用でき、その場合に本発明法の効果
は実現するものであるが、得られる超電導酸化物セラミ
クスの組成は、臨界温度の高さ等の点で下記のような複
合酸化物であることが好ましい。The production method of the present invention can generally be applied to the production of oxide ceramics having superconductivity, and in that case, the effects of the present invention method are achieved, but the composition of the superconducting oxide ceramics obtained is The following composite oxides are preferable in terms of height and the like.
Ｍ、Ｒ，Ｃｕｂ。M, R, Cub.
この場合、Ｍはアルカリ土類金属元素の１種または２種
以上であり、これらのうちＢａ。In this case, M is one or more alkaline earth metal elements, among which Ba.
ＳｒおよびＣａのうちから選ばれる１種または２種以上
、特にＢａおよびＳｒから選ばれる１種または２種であ
ることが好ましい。One or more types selected from Sr and Ca, particularly one or two types selected from Ba and Sr, are preferable.
なお、ＭがＢａおよび／またはＳｒとＣａとである場合
、Ｃａに対し、Ｂａおよび／またはＳｒが５０％以上で
あることが好ましい。In addition, when M is Ba and/or Sr and Ca, it is preferable that Ba and/or Sr is 50% or more with respect to Ca.
Ｒは希土類金属元素（Ｓｃ、Ｙ、ランタノイド元素およ
びアクチノイド元素）の１種または２種以上であり、こ
れらのうちＹおよびランタノイド元素（Ｌａ〜Ｌｕ）か
ら選ばれる１ ｆｉまたは２種以上、特にＹ％Ｌａ％Ｎ
ｄ％Ｅｕ。R is one or more rare earth metal elements (Sc, Y, lanthanide elements, and actinide elements), among which 1 fi or two or more selected from Y and lanthanide elements (La to Lu), especially Y %La%N
d%Eu.
Ｅｒ％Ｈｏ、ＤｙおよびＹｂから選ばれる１種または２
種以上であることが好ましいが、これらが他のランタノ
イド元素（Ｃｅ、Ｐｒ。Er% One or two selected from Ho, Dy and Yb
It is preferable that these are at least one species of other lanthanide elements (Ce, Pr, etc.).
Ｐｍ％Ｓｍ、Ｇｄ、Ｔｂ、７ｍ％Ｌｕ）のうちの１種以
上で置換されていてもよい。 これらのうちでは、Ｃｅ
、Ｐｒ、Ｓｍ％Ｔｂの１種以上が好ましい。Pm%Sm, Gd, Tb, 7m%Lu). Among these, Ce
, Pr, and one or more of Sm%Tb are preferred.
このようなランタノイド元素の１種以上が置換される場
合、置換量はＲ中の８０ ａｔ％以下、特に５０ａｔ％
以下であることが好ましい。When one or more of these lanthanide elements is substituted, the amount of substitution is 80 at% or less in R, especially 50 at%.
It is preferable that it is below.
この他、Ｃｕに対し、５０ａｔ％以下の範囲でＡｇ、Ｈ
ｇ％Ｎｉ、Ｚｎ等が置換されていてもよい。In addition, Ag, H within a range of 50 at% or less relative to Cu
g%Ni, Zn, etc. may be substituted.
ｘ＋ｙは０．７〜３．０種度であることが好ましく、ｘ
／ ｘ ＋ ｙは０．３〜０．９、より好ましくは０
．４〜Ｏ，ａである。It is preferable that x+y is 0.7 to 3.0 degree, and x
/ x + y is 0.3 to 0.9, more preferably 0
．． 4~O,a.
Ｚは、Ｒが３価（Ｃｅにおいては４価）、Ｍが２価、Ｃ
ｕが２価として計算される値の近傍の値である。In Z, R is trivalent (tetravalent in Ce), M is divalent, and C
u is a value near the value calculated as a bivalent value.
このような組成とすると、４０Ｋ、特に９０に以上の臨
界温度Ｔｃが得られる。With such a composition, a critical temperature Tc of 40K, especially 90K or more can be obtained.
なお、ＭにおけるＢａ、Ｓｒ、Ｒにおける上記土類元素
は、それぞれ単独で含有されても組み合せて含有されて
もよい。 複合添加される場合、それぞれの量比は任意
である。In addition, Ba, Sr in M, and the above-mentioned earth elements in R may be contained individually or in combination. When added in combination, the respective quantitative ratios are arbitrary.
このような複合酸化物は、ペロブスカイトないしペロプ
スカイト類似構造をもつ。Such a composite oxide has a perovskite or perovskite-like structure.
以上の組成に対し、本発明では、原料として、各構成金
属元素の熱分解可能な塩類を使用し、これを溶解し、均
一な溶液とする。In contrast to the above composition, in the present invention, thermally decomposable salts of each constituent metal element are used as raw materials and are dissolved to form a uniform solution.
塩類としては次段の熱分解温度８５０℃以上で熱分解可
能なものである必要があるが、−膜内に、塩化物、硝酸
塩、有機酸塩が適当であり、陰イオンは全構成金属元素
に対し一種であっても、二種以上であっても良い。 こ
の場合、特に硝酸塩は反応を制御しやすいので好適であ
る。Salts must be able to be thermally decomposed at a thermal decomposition temperature of 850°C or higher in the next stage; however, chlorides, nitrates, and organic acid salts are suitable for use in the membrane, and anions must contain all the constituent metal elements. It may be one type or two or more types. In this case, nitrates are particularly suitable because they allow easy control of the reaction.
塩類を溶解する溶媒は必要濃度まで塩類を溶解可能なも
のであればどのような溶媒も使用可能であるが、一般に
は水あるいは特に親水性の有機溶媒が適当である。As the solvent for dissolving the salts, any solvent can be used as long as it can dissolve the salts to the required concentration, but generally water or a particularly hydrophilic organic solvent is suitable.
なお、塩類の総濃度は、通常１ミリモル／１〜１０モル
／ｆｌ程度とする。Note that the total concentration of salts is usually about 1 mmol/1 to 10 mol/fl.
次にこの様にして得られた溶液を霧化し微細な液滴を作
るが、霧化の方法は一般にノズル法、アトマイズ法等が
適用可能である。Next, the solution obtained in this way is atomized to form fine droplets, and generally a nozzle method, an atomization method, etc. can be applied to the atomization method.
ただ液滴のサイズおよび量の制御性の面で、超音波法が
好適である。However, the ultrasonic method is preferable in terms of controllability of droplet size and amount.
特に、超音波霧化器による液滴は、サイズの揃った粒度
分布が均質で、粒径の小さい微細な液滴である。 この
ため得られる粉体は、粒径が小さく、しかも粒度分布、
結晶性、組成等の点できわめて均質で、さらにほぼ球状
をなし、形状も揃っており、中空粒子が存在せず、この
結果焼結性もきわめて高い。In particular, droplets produced by an ultrasonic atomizer are fine droplets with uniform size, homogeneous particle size distribution, and small particle size. For this reason, the obtained powder has a small particle size and a particle size distribution.
It is extremely homogeneous in terms of crystallinity, composition, etc., is almost spherical, has a uniform shape, and has no hollow particles, and as a result, has extremely high sinterability.
そして、液滴径や量の制御をきわめて正確かつ安定にで
きるので、生産性が高く、量産性も高い。In addition, since the droplet diameter and amount can be controlled extremely accurately and stably, productivity is high and mass production is also high.
さらに霧化条件をかなり自由な範囲で変更することか可
能であり粉体の平均粒径、粒度分布の制御性も高く、結
果として単にセラミクス焼結体用原料のみならず、印刷
用ペースト、各ｆｆ！溶射法等の原料粉にも適用可能な
種々のグレードの粉体が生産可能である。Furthermore, it is possible to change the atomization conditions within a fairly flexible range, and the average particle size and particle size distribution of the powder are highly controllable. ff! It is possible to produce various grades of powder that can be used as raw material powder for thermal spraying, etc.
超音波法による霧化器を用いる場合、超音波周波数、投
入パワー、振動板形状等を設定することにより、液滴の
サイズや量を制御することができる。 また、霧化時の
温度や、溶液の蒸気圧や、溶液の粘度によってもこれら
を制御することができる。When using an atomizer using an ultrasonic method, the size and amount of droplets can be controlled by setting the ultrasonic frequency, input power, diaphragm shape, etc. These can also be controlled by the temperature during atomization, the vapor pressure of the solution, and the viscosity of the solution.
一般に、用いる超音波周波数は数１０ｋＨｚ〜１０ｂＬ
Ｈｚ程度とすればよい。 また没入パワーは数１０Ｗ〜
数１００Ｗ程度とすればよいが、周波数、投入パワー共
に目的とする粒径や生産量に応じ、任意に変えることは
かまわない。Generally, the ultrasonic frequency used is several tens of kHz to 10 bL.
It may be about Hz. Also, the immersive power is several 10W~
The power may be about several hundred W, but both the frequency and the input power may be changed arbitrarily depending on the target particle size and production amount.
また、温度は一般に室温〜沸点程度とするが、比較的任
意に変更し、粒径の制御も行なえる。Further, although the temperature is generally from room temperature to about the boiling point, it can be changed relatively arbitrarily to control the particle size.
なお、液滴の粒径は溶液粘度にもよるが、必要に応じ、
界面活性剤等を溶液に添加して、その表面張力をかえて
粒径をかえることもできる。The particle size of the droplets depends on the viscosity of the solution, but if necessary,
It is also possible to change the particle size by adding a surfactant or the like to the solution to change its surface tension.
このようにして霧化器、より好ましくは超音波霧化器に
て発生する液滴は、一般に０．５〜１００μｍであるこ
とが好ましい。The droplets generated in this way by an atomizer, more preferably an ultrasonic atomizer, are generally preferably 0.5 to 100 μm in size.
なお、容器や振動子等の形状や寸法等は公知の種々のも
のであってよい。Note that the shape and dimensions of the container, the vibrator, etc. may be of various known shapes.
このようにして霧化した液滴は次段の熱分解装置に導入
されるが、本発明では液滴をキャリヤガスにて移送する
。The droplets thus atomized are introduced into the next-stage thermal decomposition apparatus, and in the present invention, the droplets are transported using a carrier gas.
キャリヤガスは特にその種類に制限はないが、熱分解装
置内にて酸化物化するために酸素含有キャリヤガスが好
ましく、通常空気あるいは酸素ガスが使用される。 こ
の他、不活性ガスをキャリヤとし、熱分解装置内もしく
は熱分解装置までの流路中にて、酸素や酸素含有ガスを
混合することも可能である。Although there is no particular restriction on the type of carrier gas, an oxygen-containing carrier gas is preferable since it is converted into an oxide in the thermal decomposition apparatus, and air or oxygen gas is usually used. In addition, it is also possible to use an inert gas as a carrier and mix oxygen or an oxygen-containing gas within the pyrolysis device or in the flow path to the pyrolysis device.
液滴をキャリヤガスにて移送するには、霧化器内にキャ
リヤガスを導入する。キャリャガスを導入するには、通
常流路出口側を排気し、この流路の人口側にキャリヤガ
スが導入されるような構造とすればよい。To transport the droplets with a carrier gas, the carrier gas is introduced into the atomizer. In order to introduce the carrier gas, the structure is such that the outlet side of the flow path is normally evacuated and the carrier gas is introduced into the population side of the flow path.
なお、キャリヤガス流速は、熱分解装置の設定温度の均
熱域を通過し、必要な程度の熱分解反応を持続するのに
必要な０．１〜数１０秒程度の滞留時間が得ら−れる程
度であることが好ましい。The flow rate of the carrier gas is such that it passes through the soaking area at the set temperature of the pyrolysis device and obtains a residence time of about 0.1 to several tens of seconds, which is necessary to sustain the necessary degree of pyrolysis reaction. It is preferable that the amount is as low as possible.
第１図には、本発明の製造方法を実施するための装置の
１例が示される。FIG. 1 shows an example of an apparatus for implementing the manufacturing method of the present invention.
第１図に示される製造装置１の超音波霧化器４には、前
記の塩類を含有する溶液２が充填されており、その容器
４１の底部には振動子４５が設けられ、振動子４５によ
る超音波によって溶液２から液滴３が発生している。The ultrasonic atomizer 4 of the manufacturing apparatus 1 shown in FIG. Droplets 3 are generated from the solution 2 by ultrasonic waves.
なお、振動子４５は容器４１の内側にあってもかまわな
い。Note that the vibrator 45 may be placed inside the container 41.
一方、容器４１の上部には流路５の入口部５１が連結さ
れており、また容器４１の側部にはキャリヤガス導入口
４３が設けられている。On the other hand, an inlet 51 of the flow path 5 is connected to the upper part of the container 41, and a carrier gas inlet 43 is provided at the side of the container 41.
そして、流路５の出口部５６には排気ポンプ８が設けら
れ、排気ポンプ８の排気により、キャリヤガスが図示矢
印方向に流入し、このキャリヤガス流により、液滴３は
流路５内を移送される。An exhaust pump 8 is provided at the outlet 56 of the flow path 5, and carrier gas flows in the direction of the arrow shown in the figure by the exhaust pump 8. Due to this carrier gas flow, the droplet 3 flows inside the flow path 5. be transported.
なお、流路５の入口部５１は、図示例では、霧化器４の
容器４１から上方に延設されているが、この他水平に延
設する等、種々の構造が可能である。 また、キャリヤ
ガス導入口４３も流路５の入口部５１の配設の仕方に応
じ種々の配置とすることができる。 さらに、流路５全
体の形状も種々のものであってよい。In the illustrated example, the inlet portion 51 of the flow path 5 extends upward from the container 41 of the atomizer 4, but various other structures are possible, such as extending horizontally. Furthermore, the carrier gas inlet 43 can also be arranged in various ways depending on how the inlet portion 51 of the flow path 5 is arranged. Furthermore, the shape of the flow path 5 as a whole may also be various.
入口部５１から流路５内をキャリヤガスによって移送さ
れる液滴３は、熱分解装置６内に到達する。The droplets 3 transported by the carrier gas through the flow path 5 from the inlet portion 51 reach the inside of the pyrolysis device 6 .
熱分解装置６への流路５中では、移送に伴い液滴３の凝
集ないし会合が生じる。 そこで、霧化装置４と熱分解
装置６との間の流路５中には、この会合粗大液滴を分離
するためのドレイン部５３を形成することが好ましい。In the flow path 5 to the pyrolysis device 6, droplets 3 aggregate or aggregate as they are transferred. Therefore, it is preferable to form a drain section 53 in the flow path 5 between the atomization device 4 and the pyrolysis device 6 to separate the aggregated coarse droplets.
このドレイン部５３は、好ましくは、流路５の一部を水
平ないし傾斜して延設された流路として、この下方面を
拡径して構成され、この下方面に設けた拡径部であるド
レイン部５３に粗大液滴が落下凝集できるようにしたも
のである。 そして、このドレイン部５３には凝集溶液
を霧化器４に還流するためのバイパス部５４が設けられ
ている。This drain part 53 is preferably formed by expanding a diameter of a lower surface of a part of the flow path 5 as a flow path extending horizontally or obliquely, and is formed by an enlarged diameter part provided on the lower surface. This allows coarse droplets to fall and coagulate in a certain drain section 53. This drain section 53 is provided with a bypass section 54 for refluxing the agglomerated solution to the atomizer 4.
このようなドレイン部５３を存する霧化器４、熱分解装
置６間の流路の温度は、通常、室温〜沸点程度とすれば
よく、温度は主に得ようとする粉体の粒径の制御に利用
できる。The temperature of the flow path between the atomizer 4 and the pyrolysis device 6, which has such a drain section 53, should normally range from room temperature to the boiling point, and the temperature mainly depends on the particle size of the powder to be obtained. Can be used for control.
加温により液滴の水分除去ないし乾燥が促進する。Heating accelerates water removal or drying of the droplets.
また、このドレイン部５３ないしその近傍の流路５中に
は、さらに超音波振動子（図示せず）を設けることが好
ましい。 この振動子のパワーは、霧化器のパワーより
小さくてよいが、これにより液滴の微小化が促進される
という利点が生じる。Further, it is preferable to further provide an ultrasonic vibrator (not shown) in the drain portion 53 or in the flow path 5 in the vicinity thereof. The power of this vibrator may be lower than the power of the atomizer, but this has the advantage of promoting miniaturization of droplets.
なお、流路５の径や寸法等は製造スケールに応じ任意で
ある。Note that the diameter, dimensions, etc. of the flow path 5 are arbitrary depending on the manufacturing scale.
このようにして、液滴３は熱分解装置６に到達する。In this way, the droplets 3 reach the pyrolysis device 6.
熱分解装置６は移送されて来た液滴や液滴が乾燥して生
成された塩類の微粉体の熱分解を行うものであり、反応
部分の温度を好ましくは８００℃以上に保つ為の熱源と
、ガスの流路５とを有する。The thermal decomposition device 6 thermally decomposes the transferred droplets and fine powder of salts produced by drying the droplets, and is a heat source to maintain the temperature of the reaction part preferably at 800°C or higher. and a gas flow path 5.
熱源と加熱方式について特に制限は無いが、反応部温度
の制御性の点で一般に電熱ヒーターや赤外ヒーター等の
外部加熱方式が適当である。 また、塩類の溶媒として
その一部または全部に有機溶媒を用いたり、可燃性のキ
ャリヤガスを用いることで熱分解装置６内での燃焼熱を
利用する内部加熱方式、さらにまたこれら外部、内部加
熱方式の併用も可能である。Although there are no particular restrictions on the heat source and heating method, external heating methods such as electric heaters and infrared heaters are generally suitable from the viewpoint of controllability of the temperature of the reaction zone. In addition, internal heating methods that use combustion heat in the pyrolysis device 6 by using organic solvents as part or all of the solvent for salts or using flammable carrier gases, and also external and internal heating methods, It is also possible to use both methods.
図示例では、流路５の加熱部５５に加熱用コイル６１を
設けた外部加熱方式の例が示される。 なお、図示例の
流路５の加熱部５５およびこれに連接する出口部５６は
、それぞれ垂直および水平に配置されるが、これらの配
置は任意である。In the illustrated example, an example of an external heating method is shown in which a heating coil 61 is provided in the heating section 55 of the flow path 5. In addition, although the heating part 55 of the flow path 5 and the outlet part 56 connected thereto in the illustrated example are arranged vertically and horizontally, these arrangements are arbitrary.
このような熱分解装置６における加熱温度は、用いる塩
の種類にもよるが、通常の塩類では８００℃以上、より
好ましくは８５０℃以上、１１００℃以下が好ましい。The heating temperature in such a thermal decomposition device 6 depends on the type of salt used, but for ordinary salts, it is preferably 800°C or higher, more preferably 850°C or higher and 1100°C or lower.
加熱時間、すなわち熱分解装置６内での滞留時間を長く
したり、短かくしたりすることによって、場合によって
はこの温度以外の温度で加熱することもできるが、８０
０℃未満では、熱分解は生じるものの、目的の酸化物格
子の生成が不十分であり、この粉体を焼結しても十分な
焼結密度かえられない。Depending on the case, it is possible to heat at a temperature other than this temperature by lengthening or shortening the heating time, that is, the residence time in the pyrolysis device 6.
At temperatures below 0°C, although thermal decomposition occurs, the desired oxide lattice formation is insufficient, and even if this powder is sintered, sufficient sintered density cannot be achieved.
また、１１００℃をこえると粒子表面が溶融し、粒子が
付着し、粗大化する。 この結果、この粉体を焼結した
とき十分な焼結密度かえられない。Moreover, when the temperature exceeds 1100° C., the particle surface melts, particles adhere to each other, and become coarse. As a result, when this powder is sintered, a sufficient sintered density cannot be obtained.
なお、熱分解装置６内における加熱時間は、一般に０．
１〜数１０秒程度とする。Note that the heating time in the pyrolysis device 6 is generally 0.
The time is approximately 1 to several tens of seconds.
熱分解装置６を出た粉体含有ガスは固気分離装置７に導
入され、ここで粉体微粒子を分離する。 固気分離装置
７については従来より実用化されている手法が使用可能
であり、例えばフィルター、電気集じん器等が使用可能
である。The powder-containing gas exiting the pyrolysis device 6 is introduced into a solid-gas separator 7, where fine powder particles are separated. As for the solid-gas separator 7, methods that have been put into practical use can be used, such as a filter, an electrostatic precipitator, etc.
このようにして分離された粉体は、はぼ球形形状である
。 また、平均粒径は一般に０．１〜５０μの程度であ
る。The powder thus separated has a nearly spherical shape. Moreover, the average particle size is generally about 0.1 to 50 microns.
特に超音波霧化を行ったときには、形状の均質性にすぐ
れ、中空粒子の存在はきわめて少ないものとなる。 ま
た、平均粒径は０．１〜５μｍ１特に０．１〜１μｍ程
度となり、焼結時に問題となる粗大な凝集粒子の存在は
きわめて少ないものとなる。 また、粒度分布も狭いも
のとなる。Particularly when ultrasonic atomization is performed, the homogeneity of shape is excellent and the presence of hollow particles is extremely small. Further, the average particle size is about 0.1 to 5 μm, particularly about 0.1 to 1 μm, and the presence of coarse agglomerated particles that pose a problem during sintering is extremely small. Furthermore, the particle size distribution is also narrow.
また、組成、結晶性も均質で、例えば９０に級のＢａｚ
Ｌ’ｎＣｔｌｓＯ７−ｘ （Ｌ ｎ ’ランタノイド元
素）では、正方晶のＢａ２ ＬｎＣｕ３酸化物のほぼ単
相の粉体を得ることができる。 また、この正方晶には
一部斜方晶を含むこともある。In addition, the composition and crystallinity are homogeneous, such as 90-grade Baz
With L'nCtlsO7-x (Ln' lanthanide element), a substantially single-phase powder of tetragonal Ba2LnCu3 oxide can be obtained. Moreover, this tetragonal crystal may include a part of orthorhombic crystal.
そして、多孔質粒子の存在もきわめて少なくなることが
特徴である。Another feature is that the presence of porous particles is extremely reduced.
このような原料粉体は、そのままでは実質的に超電導性
、すなわちマイスナー効果はほとんど示さないが、酸素
雰囲気下で熱処理することによって、超電導性を示す酸
化物セラミクス粉体とすることができる。Such raw material powder exhibits substantially superconductivity, that is, almost no Meissner effect, as it is, but by heat-treating it in an oxygen atmosphere, it can be made into an oxide ceramic powder that exhibits superconductivity.
熱処理温度は６００℃以下、特に２００〜５５０℃であ
ることが超電導性発現の上で好ましい。 また、熱処理
時間は０，５〜４０時間程度が好ましく、これら条件は
使用したランタノイド元素により比較的巾広く変化する
。The heat treatment temperature is preferably 600°C or less, particularly 200 to 550°C, from the viewpoint of developing superconductivity. Further, the heat treatment time is preferably about 0.5 to 40 hours, and these conditions vary relatively widely depending on the lanthanide element used.
用いる酸素雰囲気としては、酸素分圧０２以上とし、通
常は酸素気流中とすればよい。The oxygen atmosphere to be used may have an oxygen partial pressure of 02 or higher, usually in an oxygen stream.
なお、昇温速度、冷却速度は通常４００℃以下程度とす
る。Note that the heating rate and cooling rate are usually about 400°C or less.
このような熱処理により、粉体は超電導性を有するもの
となる。 すなわち、例えば３ａ２ＬｎＣｕ３０７−ｙ
では斜方晶の単相となり、９０に程度で超電導転移を開
始することになる。Through such heat treatment, the powder becomes superconducting. That is, for example, 3a2LnCu307-y
In this case, it becomes an orthorhombic single phase and starts superconducting transition at about 90°C.
なお、このような熱処理により、通常粉体寸法等は変わ
らない。Note that such heat treatment usually does not change the dimensions of the powder.
このような場合、このような熱処理は、前述の固気分離
装置７で分離した後、別途施せばよい。In such a case, such heat treatment may be separately performed after separation in the solid-gas separator 7 described above.
あるいは、熱分解炉６の後段の流路に例えば加熱用コイ
ル等の加熱手段を設け、上記の熱処理を行ったのち、粉
体を分離してもよい。Alternatively, a heating means such as a heating coil may be provided in the downstream flow path of the pyrolysis furnace 6, and the powder may be separated after the above heat treatment.
このような超電導酸化物セラミクスの粉体は、粉体をそ
のまま用いたり、これを各種バインダ中に分散して、磁
気シールド、電磁シールド材等としたりして用いること
ができる。Such superconducting oxide ceramic powder can be used as it is, or can be dispersed in various binders and used as magnetic shielding, electromagnetic shielding material, etc.
また、超電導酸化物セラミクスの原料粉体や超電導酸化
物セラミクスの粉体は、これを成型して焼結体としたり
、これに適当な溶剤およびバインダを加えてペースト化
して印刷したり、グリーンシート化してこれを焼結して
焼結体としたりすることができる。In addition, raw material powder for superconducting oxide ceramics and powder for superconducting oxide ceramics can be molded into a sintered body, added with an appropriate solvent and binder to form a paste, and printed on a green sheet. This can be sintered to form a sintered body.
あるいは、これらを用いて各種溶射膜を作製したり、こ
れらやその成型体ないし焼結体を用いてスパッタ膜を作
製することもできる。Alternatively, various thermal sprayed films can be produced using these, and sputtered films can also be produced using these or their molded or sintered bodies.
このような場合、焼結は、好ましくは酸素分圧０．２以
上の雰囲気下で、好ましくは８５０〜１０００℃の温度
で１〜１０時間程度行う。In such a case, sintering is preferably performed in an atmosphere with an oxygen partial pressure of 0.2 or more, preferably at a temperature of 850 to 1000°C for about 1 to 10 hours.
また、これら焼結体や膜等には、前記した６００℃以下
の熱処理を施すことが好ましい。Further, it is preferable that these sintered bodies, films, etc. be subjected to the heat treatment described above at 600° C. or lower.
〈実施例〉
以下本発明の具体的実施例を示し、本発明をさらに詳細
に説明する。<Examples> Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail.
（実施例１）
Ｂａ （ＮＯｓ） ２． Ｙ （ＮＯり ｓ 、 Ｃｕ
（ＮＯ３） ２を原料とし、Ｂａ：Ｙ：Ｃｕの比率を
２：１：３となる様に秤量後、水に溶解しメタル換算濃
度ｏ、ｏｉａｌｏｌ／ｆＬの溶液を作成した。(Example 1) Ba (NOs) 2. Y (NOri s, Cu
(NO3) 2 was used as a raw material, weighed so that the ratio of Ba:Y:Cu was 2:1:3, and then dissolved in water to create a solution with a metal equivalent concentration of o and oialol/fL.
この溶液２を、第１図に示される超音波霧化装置４ （
１，６５Ｍ Ｈｚ 、３０Ｗ）に充填し、室温にて霧化
し、空気をキャリヤガスとして４１／分の流量で熱分解
装置６に供給した。This solution 2 is transferred to an ultrasonic atomizer 4 (
1.65 MHz, 30 W), atomized at room temperature, and supplied to the pyrolysis device 6 at a flow rate of 41/min using air as a carrier gas.
熱分解装置６前方の流路５にはドレイン部５３を設けた
。 熱分解装置６としては断面積９．６ｏＩｆの炉芯管
を加熱コイル６１で加熱するものとし、炉芯管内部温度
を９５０℃に設定した。A drain section 53 was provided in the flow path 5 in front of the pyrolysis device 6. As the pyrolysis device 6, a furnace core tube with a cross-sectional area of 9.6 oIf was heated by a heating coil 61, and the internal temperature of the furnace core tube was set at 950°C.
室温での流量４ｊＱ／分は、熱分解装置６の炉芯管中の
平均線速度で９５０℃設定時約２８ａｍ／ｓｅｃとなる
。The flow rate 4jQ/min at room temperature is about 28 am/sec when the average linear velocity in the furnace core tube of the pyrolysis device 6 is set at 950°C.
炉芯管の均熱部は５ＣＩ１１であり、導入されたガスの
設定温度での滞留時間は約０．２秒である。The soaking section of the furnace core tube is 5CI11, and the residence time of the introduced gas at the set temperature is about 0.2 seconds.
熱分解装置６を通したガスは冷却後０． １μ謹のメン
ブランフィルタ−の固気分離装置７を通し、粉体を分離
した。The gas passed through the pyrolysis device 6 is cooled down to 0. The powder was separated through a solid-gas separator 7 having a 1 μm membrane filter.
得られた粉体をＳＥＭ観察した結果、平均粒径０．３８
μ１１最大粒径１．２μｍ、最小粒径０．１μｌと粒度
分布は比較的狭く、また焼結時間列となる粗大な凝集粒
子はｇめられなかった。 さらに各粒子はほぼ球形をな
し、かつ中空粒子も認められなかった。As a result of SEM observation of the obtained powder, the average particle size was 0.38.
The particle size distribution of μ11 was relatively narrow, with a maximum particle size of 1.2 μm and a minimum particle size of 0.1 μl, and no coarse agglomerated particles were observed in the sintering time sequence. Furthermore, each particle was approximately spherical, and no hollow particles were observed.
この粉体を１５ｍｍφ、１ｍｍｔのベレットに成形し、
９５０℃４時間酸素気流中で焼結し、さらに４５０℃酸
素気流中でアニールを行い焼結体サンプルとし、超電導
転移温度を四端子直流法で測定した。 その結果Ｔｃ
ｏｎｓｅｔ９６に％Ｔｃｍ１ｄ９４．５に、 Ｔｃｏｆ
ｆｓｅｔ ９４にの極めてシャープな転移を示した。This powder was formed into a pellet of 15mmφ and 1mmt,
The sample was sintered at 950°C for 4 hours in an oxygen stream, and further annealed at 450°C in an oxygen stream to obtain a sintered sample, and the superconducting transition temperature was measured using a four-probe direct current method. As a result, Tc
Onset96 to %Tcm1d94.5, Tcof
It showed an extremely sharp transition to fset 94.
熱分解装置６の設定温度を変えた以外は実施例１と同様
にして作成したサンプルの結果を表１に示す。Table 1 shows the results of a sample prepared in the same manner as in Example 1 except that the temperature setting of the pyrolysis device 6 was changed.
粒度分布については８５０〜１０５０℃でほぼ一定であ
るが、最大粒子径は８００℃と１１００℃で増大してい
る。The particle size distribution is almost constant between 850 and 1050°C, but the maximum particle size increases between 800°C and 1100°C.
Ｘ線回折の結果も併せて考慮すると、８００℃ではＢＹ
ＧＯ相（Ｂａ２Ｙ＋Ｃｕ３０７−６相、正方晶と斜方晶
を含む）の生成が少なく、ＮＯ３−イオンは熱分解して
いるものの、目的のＢＹＧＯの格子が十分束じていない
。 この結果焼結時も十分な焼結密度を得るに至ってい
ない。Considering the results of X-ray diffraction as well, at 800℃ BY
Although the formation of GO phase (Ba2Y+Cu307-6 phase, including tetragonal and orthorhombic crystals) is small, and NO3- ions are thermally decomposed, the target BYGO lattice is not sufficiently bound. As a result, sufficient sintered density cannot be obtained during sintering.
一方、超電導転移温度は主として焼結条件で決まり、お
おむね９０Ｋを示しているが、焼結密度の高い熱分解装
置設定温度８５０〜１０５０℃で高めとなった。On the other hand, the superconducting transition temperature is mainly determined by the sintering conditions, and is approximately 90K, but becomes higher at the pyrolysis device set temperature of 850 to 1050°C, which has a high sintering density.
また、同設定温度１１００℃では粒子表面の溶融が進み
、粒子間の付着が進行し、粒度分布の最大径が２．６μ
ｍと粗大化している。Furthermore, at the same set temperature of 1100°C, the melting of the particle surface progresses, adhesion between particles progresses, and the maximum diameter of the particle size distribution becomes 2.6 μm.
It is coarsening to m.
その結果焼結体密度が低めの値となったものと思われる
。 従って本発明法で作成する場合の熱分解装置の温度
設定は８５０〜１０５０℃が好適であると考えられる。It seems that as a result, the density of the sintered body became a rather low value. Therefore, it is considered that the temperature setting of the pyrolysis apparatus when producing by the method of the present invention is preferably 850 to 1050°C.
Ｘ線的には本製法で得られるＢＹＣＯ粉末は表１の範囲
では正方晶であった。 さらに、実施例１と同様にして
キャリヤガスを酸素１００％としても得られるＢＹＧＯ
は正方晶であった。 これは熱分解後粉体が直ちに低温
に冷却されるため、雰囲気中の酸素を十分に結晶構造中
にとり入れることが難しい為と考えられる。In terms of X-rays, the BYCO powder obtained by this production method was tetragonal within the range shown in Table 1. Furthermore, BYGO obtained by using 100% oxygen as the carrier gas in the same manner as in Example 1
was a tetragonal crystal. This is thought to be because the powder is immediately cooled to a low temperature after pyrolysis, making it difficult to sufficiently incorporate oxygen in the atmosphere into the crystal structure.
しかしながら、これは実施例で使用した実験装置のサイ
ズに起因するものと考えられ、量産規模の装置で粉体の
中温での滞留時間が長くなる場合は斜方晶の生成も考え
られる。However, this is considered to be due to the size of the experimental equipment used in the examples, and if the residence time of the powder at medium temperature is long in a mass-production scale equipment, formation of orthorhombic crystals is also considered.
実施例２
実施例１と同様にして粉体を作製した後、この粉体を０
２気流中４５０℃にて４時間アニールし、２００℃／
ｈ ｒで室温まで冷却した。 得られた粉体はＸ線回折
では斜方晶を示し、磁化率測定の結果９６にで超電導転
移を開始し、８６にで、一定値に達した。Example 2 After producing a powder in the same manner as in Example 1, this powder was
Annealed at 450°C for 4 hours in 2 air currents, 200°C/
Cooled to room temperature at hr. The obtained powder showed an orthorhombic structure in X-ray diffraction, and as a result of magnetic susceptibility measurement, superconducting transition started at 96 and reached a constant value at 86.
この粉体の粉体特性は実施例１と実質的に同等であった
。The powder properties of this powder were substantially the same as in Example 1.
実施例３
実施例１の粉体ｉｏｏ重量部に対し、エチルセルロース
１０ｗｔ％含有したラッカー２０重量部を加え、混練し
てペーストを作製した。Example 3 20 parts by weight of lacquer containing 10 wt % of ethyl cellulose was added to 10 parts by weight of the powder of Example 1 and kneaded to prepare a paste.
スクリーン印刷にてこのペーストを巾ｉｎｍのパターン
でアルミナ基板上に印刷後、雰囲気炉中空気を送り昇温
速度２００℃／ ｈ ｒ、９５０℃４時間焼成した。
冷却は雰囲気を酸素に切り換え、２００℃／ ｈ ｒで
冷却し、途中４５０℃で４時間温度を保った後、室温ま
で冷却した。 得られた試料を直流四端子法で測定した
結果、Ｔｃ ｏｎｓｅｔ９４ Ｋ 、 Ｔｃ ｌｌ１ｉ
ｄ９２、 ５に％Ｔｃ ｏｆｆｓｅｔ ９１． ５にと
、はぼバルク材料に匹適する値を示した。After printing this paste in a pattern with a width of inm on an alumina substrate by screen printing, air was fed into an atmospheric furnace and the paste was fired at a temperature increase rate of 200° C./hr for 4 hours at 950° C.
For cooling, the atmosphere was changed to oxygen, and cooling was carried out at 200°C/hr. During the cooling, the temperature was maintained at 450°C for 4 hours, and then cooled to room temperature. As a result of measuring the obtained sample by the DC four-terminal method, Tc onset94 K, Tc ll1i
d92, 5 to %Tc offset 91. 5, which is a value comparable to that of bulk materials.
〈発明の効果〉
以上本発明法では原料溶液の噴霧反応法により基本的に
は一段の反応工程で、直接超電導セラミック原料粉体を
作成でき、純度や粒子形状と化学組成の均質性にすぐれ
た微粉体を低コストで生産することが可能となる。<Effects of the Invention> As described above, in the method of the present invention, superconducting ceramic raw material powder can be directly produced in basically one reaction step by using a spray reaction method of raw material solution, and has excellent purity, homogeneity of particle shape and chemical composition. It becomes possible to produce fine powder at low cost.
また、微細かつ粒度分布がシャープなため、バルクの焼
結体やスクリーン印刷等の焼成厚膜用や、溶射用等の原
料粉体としても好適である。In addition, since it is fine and has a sharp particle size distribution, it is suitable as a raw material powder for bulk sintered bodies, fired thick films such as screen printing, and thermal spraying.
特に、従来からの粉末冶金プロセスにおける固相混合法
のように、仮焼後に粉砕プロセスを経る必要がなく、特
に環境からの影響を受は易い超電導酸化物セラミクス用
原料粉体の製法としては非常に優れた手法である。In particular, unlike the solid-phase mixing method in conventional powder metallurgy processes, there is no need to go through a pulverization process after calcination, making it an extremely useful method for producing raw material powder for superconducting oxide ceramics, which is particularly susceptible to environmental influences. This is an excellent method.
また、得られた原料粉体の焼結性もきわめて良好である
。 これは本発明によって得られた原料粉体の形状、粒
径、組成、結晶性等がきわめて均質で、また微細である
からであり、固相混合法による粉体と比較して、焼結性
は格段と高いものとなる。Moreover, the sinterability of the obtained raw material powder is also extremely good. This is because the raw material powder obtained by the present invention is extremely homogeneous and fine in shape, particle size, composition, crystallinity, etc., and has a higher sinterability than powder produced by solid phase mixing. will be significantly higher.
さらに、本発明によれば、上記の特徴を活かして、高い
生産性で超電導セラミクス粉体を得ることができる。
そして、得られた粉体は均質かつ微細であり、良好かつ
安定な超電導特性を示す。Furthermore, according to the present invention, superconducting ceramic powder can be obtained with high productivity by taking advantage of the above characteristics.
The obtained powder is homogeneous and fine, and exhibits good and stable superconducting properties.
また、本発明による一原料粉体ないし超電導粉体を用い
て作成した焼結体は、焼結密度が高く、良好かつ安定な
超電導特性を示す。Further, a sintered body produced using the single raw material powder or superconducting powder according to the present invention has a high sintering density and exhibits good and stable superconducting properties.
第１図は本発明の超電導酸化物セラミクスの原料粉体の
製造方法を実施するための装置を示す概略図である。
符号の説明
１・・・製造装置、
２・・・溶液、
３・・・液滴、
４・・・超音波霧化装置、
５・・・流路、
６・・・熱分解装置、
７・・・固気分離装置、
８・・・排気ボンブFIG. 1 is a schematic diagram showing an apparatus for carrying out the method for producing raw material powder for superconducting oxide ceramics of the present invention. Explanation of symbols 1... Manufacturing device, 2... Solution, 3... Droplets, 4... Ultrasonic atomization device, 5... Channel, 6... Pyrolysis device, 7.・・・Solid gas separator, 8...Exhaust bomb
Claims (3)
溶液を霧化し、キャリヤガスにて熱分解装置内に導入し
て酸素含有雰囲気下熱分解を行って超電導酸化物セラミ
クスの原料粉体を得る超電導酸化物セラミクスの原料粉
体の製造方法。(1) A solution of thermally decomposable salts of the elements constituting the superconducting oxide is atomized, introduced into a thermal decomposition device using a carrier gas, and thermally decomposed in an oxygen-containing atmosphere to produce raw material powder for superconducting oxide ceramics. A method for producing raw material powder for superconducting oxide ceramics.
ラミクスの原料粉体を得、これを酸素含有雰囲気下、６
００℃以下の温度で熱処理する超電導酸化物セラミクス
の粉体の製造方法。(2) A raw material powder for superconducting oxide ceramics is obtained by the manufacturing method according to claim 1, and this is heated in an oxygen-containing atmosphere for 60 minutes.
A method for producing superconducting oxide ceramic powder, which is heat-treated at a temperature of 00°C or lower.
ラミクスの原料粉体を得、これを焼結する超電導セラミ
クス焼結体の製造方法。(3) A method for producing a superconducting ceramic sintered body, which comprises obtaining raw material powder for superconducting oxide ceramics by the production method according to claim 1 and sintering the powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63017584A JPH01192709A (en) | 1988-01-28 | 1988-01-28 | Production of superconductin oxide ceramic powder and sintered form therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63017584A JPH01192709A (en) | 1988-01-28 | 1988-01-28 | Production of superconductin oxide ceramic powder and sintered form therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01192709A true JPH01192709A (en) | 1989-08-02 |
Family
ID=11947954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63017584A Pending JPH01192709A (en) | 1988-01-28 | 1988-01-28 | Production of superconductin oxide ceramic powder and sintered form therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01192709A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0337105A (en) * | 1989-07-03 | 1991-02-18 | Chiyoudendou Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Production of oxide superconductor |
| EP0462617A2 (en) * | 1990-06-21 | 1991-12-27 | Matsushita Electric Works, Ltd. | Silver base electrical contact material and method of making the same |
| CN1056328C (en) * | 1992-10-05 | 2000-09-13 | E·I·内穆尔杜邦公司 | Method for making palladium and palladium oxide powders by aerosol decomposition |
-
1988
- 1988-01-28 JP JP63017584A patent/JPH01192709A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0337105A (en) * | 1989-07-03 | 1991-02-18 | Chiyoudendou Hatsuden Kanren Kiki Zairyo Gijutsu Kenkyu Kumiai | Production of oxide superconductor |
| EP0462617A2 (en) * | 1990-06-21 | 1991-12-27 | Matsushita Electric Works, Ltd. | Silver base electrical contact material and method of making the same |
| US5198015A (en) * | 1990-06-21 | 1993-03-30 | Matsushita Electric Works, Ltd. | Silver base electrical contact material and method of making the same |
| CN1056328C (en) * | 1992-10-05 | 2000-09-13 | E·I·内穆尔杜邦公司 | Method for making palladium and palladium oxide powders by aerosol decomposition |
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