JPH0556304B2 - - Google Patents
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- Publication number
- JPH0556304B2 JPH0556304B2 JP62187986A JP18798687A JPH0556304B2 JP H0556304 B2 JPH0556304 B2 JP H0556304B2 JP 62187986 A JP62187986 A JP 62187986A JP 18798687 A JP18798687 A JP 18798687A JP H0556304 B2 JPH0556304 B2 JP H0556304B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- baf
- saturated solution
- temperature
- superconducting
- 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.)
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Links
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 29
- 239000012047 saturated solution Substances 0.000 claims description 27
- 239000000919 ceramic Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020012 Nb—Ti Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000009466 transformation Effects 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
Landscapes
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】
利用産業分野
この発明は、マイスナー効果を呈する耐水性の
すぐれた超電導セラミツクスの製造方法に係り、
得られた焼結体全体が、超電導性を有する低温安
定相からなる耐水性のすぐれたBaO−Y2O3−
CuO系あるいはBaO−La2O3−CuO系超電導セラ
ミツクスの製造方法に関する。[Detailed description of the invention] Industrial field of application The present invention relates to a method for producing superconducting ceramics exhibiting the Meissner effect and having excellent water resistance.
The entire obtained sintered body is BaO−Y 2 O 3 − with excellent water resistance, consisting of a low-temperature stable phase with superconductivity.
This invention relates to a method for manufacturing CuO-based or BaO-La 2 O 3 -CuO-based superconducting ceramics.
背景技術
従来、超電導材料としてはNb−Ti、Nb−Sn、
Nb3Sn等の合金系、あるいは金属間化合物材料が
知られている。Background technology Conventionally, superconducting materials include Nb-Ti, Nb-Sn,
Alloy materials such as Nb 3 Sn or intermetallic compound materials are known.
前記超電導材料は、電気抵抗が零になる臨界温
度（Tc）がせいぜい30kでマイスナー効果を示す
ものであつた。 The superconducting material exhibits the Meissner effect when the critical temperature (Tc) at which the electrical resistance becomes zero is at most 30k.
しかし、最近、臨界温度（Tc）が90k付近でマ
イスナー効果を示す、高温超電導材料として、
BaO−Y2O3−CuO系あるいはBaO−La2O3−
CuO系超電導セラミツクスが提案され、多くの研
究調査が行われるようになつた。 However, recently, high-temperature superconducting materials that exhibit the Meissner effect at a critical temperature (Tc) of around 90k have been developed.
BaO−Y 2 O 3 −CuO system or BaO−La 2 O 3 −
CuO-based superconducting ceramics have been proposed, and many research studies have begun.
前記BaO−Y2O3−CuO系超電導セラミツクス、
例えば、YBa2Cu3O7-xセラミツクス（ｘ＝０〜
0.25）は550℃〜600℃付近で相転移が行われ、こ
の場合、高温相の正方晶組織では超電導相を示さ
ず、低温安定相の斜方晶組織が超電導相を示すこ
とが知られている。 The BaO-Y 2 O 3 -CuO-based superconducting ceramics,
For example, YBa 2 Cu 3 O 7-x ceramics (x=0~
0.25) undergoes a phase transition around 550°C to 600°C, and in this case, it is known that the tetragonal structure of the high temperature phase does not show a superconducting phase, but the orthorhombic structure of the low temperature stable phase shows a superconducting phase. There is.
一方、かかる超電導セラミツクスの焼成に関
し、従来の粉末冶金法による焼結法では、950℃
付近で焼結し、その後冷却する方法が取られてい
た。 On the other hand, regarding the firing of such superconducting ceramics, the conventional sintering method using powder metallurgy has a temperature of 950°C.
The method used was to sinter the material nearby and then cool it.
この焼結に際し、正方晶組織の高温相から斜方
晶組織の低温安定相への変態の際に酸素の吸収が
行われる。 During this sintering, oxygen is absorbed during transformation from a high-temperature phase with a tetragonal structure to a low-temperature stable phase with an orthorhombic structure.
ところが、変態時の供給酸素が不足した場合、
低温においても、正方晶組織が準安定相として存
在し、特に、緻密な焼結体においては内部まで酸
素を供給することができず、得られた焼結体の全
体を超電導相の斜方晶組織に変態させることは困
難であつた。 However, if the oxygen supply during metamorphosis is insufficient,
Even at low temperatures, the tetragonal structure exists as a metastable phase, and in particular, in dense sintered bodies, oxygen cannot be supplied to the inside, and the entire sintered body is transformed into a superconducting orthorhombic phase. It was difficult to transform the organization.
そこで、粒度3μm以下のYBa2Cu3O7-x組成で、
かつ低温安定相からなる原料粉末をO220％以上
含有の雰囲気中で特定圧力、温度条件にて加圧焼
結することにより、焼結体全体が斜方晶組織から
なる超電導セラミツクスが得られることを知見し
た。 Therefore, with a YBa 2 Cu 3 O 7-x composition with a particle size of 3 μm or less,
By pressurizing and sintering the raw material powder consisting of a low-temperature stable phase under specific pressure and temperature conditions in an atmosphere containing 20% or more O 2 , a superconducting ceramic whose entire sintered body has an orthorhombic structure can be obtained. I found out that.
しかし、前記超電導セラミツクスは空気中に放
置すると、空気中の水分と前記セラミツクス組成
中のBaOが反応して溶出し、前記セラミツクス
の特性劣下と共に崩壊する問題があつた。 However, when the superconducting ceramic is left in the air, the moisture in the air and BaO in the ceramic composition react with each other and are eluted, causing the ceramic to deteriorate and disintegrate.
発明の目的
この発明は、BaO−Y2O3−CuO系あるいは
BaO−La2O3−CuO系超電導セラミツクスの耐水
性を大幅に向上させることを目的とし、焼結体の
全体が超電導相の斜方晶組織からなり耐水性のす
ぐれた超電導セラミツクスの製造方法を目的とし
ている。Purpose of the invention This invention is based on BaO−Y 2 O 3 −CuO or
With the aim of significantly improving the water resistance of BaO-La 2 O 3 -CuO-based superconducting ceramics, we developed a method for manufacturing superconducting ceramics with excellent water resistance, in which the entire sintered body has an orthorhombic structure of the superconducting phase. The purpose is
発明の概要
発明者は前記従来の問題点を解決するために
種々検討した結果、斜方晶の低温安定相からなる
超電導セラミツクス焼結体をBaF2飽和溶液中に
浸漬すると、前記焼結体表面中のBaOは飽和溶
液中のＦと反応して、表面のBaOが溶出して
BaF2に変化して、前記焼結体の耐水性は改善さ
れることを知見した。Summary of the Invention As a result of various studies to solve the above-mentioned conventional problems, the inventor found that when a superconducting ceramic sintered body consisting of an orthorhombic low-temperature stable phase is immersed in a BaF 2 saturated solution, the surface of the sintered body changes. BaO inside reacts with F in the saturated solution, and BaO on the surface is eluted.
It was found that the water resistance of the sintered body was improved by changing to BaF 2 .
さらに、前記焼結体が浸漬されたBaF2飽和溶
液中に、前記飽和溶液のBa量に対して特定量の
Ba塩を追加することにより、BaF2飽和溶液に浸
漬して生成された焼結体表面のBaF2は、更に追
加Ba塩のBaと飽和溶液中のＦとの反応により、
焼結体表面のBaF2層厚が増大されて、焼結体の
耐水性は一段と改善されて向上することを知見し
た。 Furthermore, a specific amount of Ba is added to the BaF 2 saturated solution in which the sintered body is immersed, relative to the amount of Ba in the saturated solution.
By adding Ba salt, BaF 2 on the surface of the sintered body generated by immersion in a BaF 2 saturated solution is further reduced by a reaction between Ba in the additional Ba salt and F in the saturated solution.
It was found that the water resistance of the sintered body was further improved by increasing the thickness of the BaF 2 layer on the surface of the sintered body.
すなわち、この発明は、
斜方晶組織からなるMBa2Cu3O7-x組成（但し、
Ｍ＝Ｙ，La）の焼結体をBaF2飽和溶液中に浸漬
後、前記焼結体を非還元性雰囲気中で200℃〜600
℃に加熱して、拡散熱処理することを特徴とする
耐水性のすぐれた超電導セラミツクスの製造方法
であり、
また、耐水性を一段と向上させるために、前記
焼結体をBaF2飽和溶液中に浸漬し、
さらに、前記飽和溶液中に前記飽和溶液のBa
量の２倍〜10倍のBa塩を添加して浸漬し、
その後、前記溶液より取り出した焼結体に、非
還元性雰囲気中で200℃〜600℃の熱処理を施し
て、拡散熱処理することを特徴とする耐水性のす
ぐれた超電導セラミツクスの製造方法である。 In other words, the present invention provides an MBa 2 Cu 3 O 7-x composition consisting of an orthorhombic structure (however,
After immersing the sintered body of M=Y, La) in a BaF 2 saturated solution, the sintered body was heated at 200°C to 600°C in a non-reducing atmosphere.
This is a method for producing superconducting ceramics with excellent water resistance, characterized by heating to ℃ and diffusion heat treatment.In addition, in order to further improve water resistance, the sintered body is immersed in a BaF 2 saturated solution. and further, Ba of the saturated solution is added to the saturated solution.
2 to 10 times the amount of Ba salt is added and immersed, and then the sintered body taken out from the solution is heat treated at 200°C to 600°C in a non-reducing atmosphere to undergo diffusion heat treatment. This is a method for producing superconducting ceramics with excellent water resistance.
発明の構成
この発明においては、下記の各種製造方法で得
られた焼結体を用いる。Structure of the Invention In this invention, sintered bodies obtained by various manufacturing methods described below are used.
斜方晶の低温安定相からなるMBa2Cu3O7-x組
成（但し、Ｍ＝Ｙ，La、ｘ＝０〜0.25）の原料粉
末をO220vol％以上含有の雰囲気中で、550℃〜
600℃で圧力200Kg／cm2〜2000Kg／cm2の条件にて加
圧焼結して得られた焼結体、
あるいは斜方晶の低温安定相と正方晶の高温不
安定相との混合組織からなるMBa2Cu3O7-x組成
（但し、Ｍ＝Ｙ，La、ｘ＝０〜0.25）の原料粉末
を特定気圧のO2100vol％雰囲気中で加熱して、
原料粉末をすべて正方晶の高温不安定組織に変化
させた後、100vol％O2雰囲気中で斜方晶の安定
生成領域温度の550℃〜600℃にて加圧焼結して得
られた焼結体、
または前記組織からなる同一組成の原料粉末
を、特定気圧のO220vol％以上の雰囲気中で600
℃〜1050℃で加圧焼結後、炉冷して得られた焼結
体、
前記の各種製造方法で得られた焼結体を、温度
20℃〜50℃のBaF2飽和溶液中に５分〜60分間浸
漬すると、焼結体表面のBaOは耐水性のすぐれ
たBaF2に変化する。 A raw material powder with an MBa 2 Cu 3 O 7-x composition (M = Y, La, x = 0 to 0.25) consisting of an orthorhombic low-temperature stable phase was heated at 550°C in an atmosphere containing 20 vol% or more of O 2 . ~
A sintered body obtained by pressure sintering at 600℃ and a pressure of 200Kg/cm 2 to 2000Kg/cm 2 , or a mixed structure of an orthorhombic low-temperature stable phase and a tetragonal high-temperature unstable phase. A raw material powder with a composition of MBa 2 Cu 3 O 7-x (where M = Y, La, x = 0 to 0.25) is heated in an O 2 100 vol% atmosphere at a specific pressure,
After converting all the raw material powder into a tetragonal unstable high-temperature structure, the sintered material was pressure sintered in a 100 vol% O 2 atmosphere at a temperature in the stable orthorhombic formation region of 550°C to 600°C. A raw material powder of the same composition consisting of aggregates or the above-mentioned structure is heated for 600 minutes in an atmosphere containing 20 vol% or more of O 2 at a specific atmospheric pressure.
A sintered body obtained by pressure sintering at ℃ to 1050℃ and then furnace cooling, a sintered body obtained by the various manufacturing methods described above,
When immersed in a BaF 2 saturated solution at 20° C. to 50° C. for 5 minutes to 60 minutes, BaO on the surface of the sintered body changes to BaF 2 which has excellent water resistance.
前記処理を施した焼結体を前記飽和溶液より取
出して、大気中または不活性ガス等非還元性雰囲
気中で、200℃〜600℃に１時間〜10時間の加熱保
持することにより、焼結体表面のBaF2は、焼結
体内部に拡散すると共に密着性は向上し、耐水性
が改善される。 The sintered body subjected to the above treatment is removed from the saturated solution and sintered by heating and holding at 200°C to 600°C for 1 to 10 hours in the air or a non-reducing atmosphere such as an inert gas. BaF 2 on the body surface diffuses into the interior of the sintered body, improving adhesion and improving water resistance.
また、この発明は、耐水性をさらに改善向上さ
せるために、前述の如く焼結体を20℃〜50℃の
BaF2飽和溶液中に浸漬して、焼結体表面のBaO
を耐水性のすぐれたBaF2に変化させた後、前記
飽和溶液中に、さらに特定量のBa量を有するBa
塩を添加して、焼結体を更に10分以下の浸漬を継
続することにより、添加されたBa塩のBaと前記
飽和溶液中のＦとの反応により、生成された
BaF2が焼結体表面に付着し、BaF2層は増大す
る。 In addition, in order to further improve water resistance, this invention allows the sintered body to be heated at 20°C to 50°C as described above.
BaO on the surface of the sintered body was immersed in BaF2 saturated solution.
After converting BaF 2 into BaF 2 with excellent water resistance, a specific amount of Ba is added to the saturated solution.
By adding salt and continuing to immerse the sintered body for 10 minutes or less, Ba salt was generated by the reaction of Ba in the added Ba salt with F in the saturated solution.
BaF 2 adheres to the surface of the sintered body, and the BaF 2 layer increases.
その後、焼結体表面のBaF2の焼結体への拡散、
密着性改善のため、大気中または不活性ガス中で
200℃〜600℃に１時間〜10時間の加熱保持する拡
散熱処理を施す。 After that, the BaF 2 on the surface of the sintered body diffuses into the sintered body,
In air or inert gas to improve adhesion.
Diffusion heat treatment is performed by heating and holding at 200°C to 600°C for 1 to 10 hours.
なお、この発明において、焼結体の加圧焼結法
は熱間静水圧プレス法、あるいはホツトプレス法
のいずれでもよい。 In this invention, the pressure sintering method for the sintered body may be either a hot isostatic pressing method or a hot pressing method.
限定理由
この発明において、焼結体を浸漬するBaF2飽
和溶液の温度は20℃〜50℃が好ましく、20℃未満
ではBaOの水への溶出が十分でなく、50℃を超
えると効果の増大が望めず好ましくない。Reason for limitation In this invention, the temperature of the BaF 2 saturated solution in which the sintered body is immersed is preferably 20°C to 50°C. Below 20°C, the elution of BaO into water is insufficient, and when it exceeds 50°C, the effect increases. is undesirable and undesirable.
また、浸漬時間は５分未満ではBaF2の生成が
十分でなく、60分を超えると効果の増大が望めな
いので好ましくない。 Further, if the immersion time is less than 5 minutes, BaF 2 will not be sufficiently generated, and if it exceeds 60 minutes, no increase in the effect can be expected, which is not preferable.
さらに、焼結体表面に生成するBaF2量を増大
させるため、BaF2飽和溶液に添加するBa塩とし
ては、Ba（NO3）2、BaCl2等が好ましい。 Furthermore, in order to increase the amount of BaF 2 generated on the surface of the sintered body, Ba(NO 3 ) 2 , BaCl 2 or the like is preferable as the Ba salt added to the BaF 2 saturated solution.
その添加量は、BaF2飽和溶液中のBa量の２倍
未満では、BaF2層生成量が少なく、10倍を超え
ると効果の増大が少なくなるので、Ba塩の添加
量はBaF2飽和溶液中のBa量の２倍〜10倍が好ま
しい。 If the amount of Ba salt added is less than twice the amount of Ba in the BaF 2 saturated solution, the amount of BaF 2 layer formation will be small, and if it exceeds 10 times the amount of Ba salt, the increase in effect will be small . The amount of Ba is preferably 2 times to 10 times the amount of Ba inside.
また、BaF2飽和溶液中に、特定量のBa塩を添
加し浸漬して、焼結体表面のBaF2層厚を増大さ
せるための浸漬時間は、10分を超えると反応が完
了し、新たなBaF2の生成が起こらないため、浸
漬時間は10分以下で十分である。 In addition, the immersion time for increasing the BaF 2 layer thickness on the surface of the sintered body by adding a specific amount of Ba salt into a BaF 2 saturated solution is longer than 10 minutes, and the reaction is completed and a new layer is formed. A soaking time of 10 minutes or less is sufficient because no significant BaF 2 is generated.
焼結体表面に生成したBaF2層の拡散、密着性
改善のための熱処理条件は、温度200℃未満では
拡散が起こり難く、また600℃を超えると正方晶
（非超電導相）生成を招来するので好ましくない。 The heat treatment conditions for improving the diffusion and adhesion of the two BaF layers formed on the surface of the sintered body are such that diffusion is difficult to occur at temperatures below 200°C, and temperatures above 600°C result in the formation of tetragonal crystals (non-superconducting phase). So I don't like it.
また、熱処理時間としては、１時間未満では、
拡散が十分でないため密着性が悪く、10時間を超
えると効果が飽和するため、１時間〜10時間とす
る。 In addition, if the heat treatment time is less than 1 hour,
Adhesion is poor due to insufficient diffusion, and the effect is saturated if it exceeds 10 hours, so the time is set to 1 to 10 hours.
実施例
純度99.9％以上の粒度2μm以下のBaCO3、
Y2O3、CuO粉末を、組成比２：１：３のモル比
に配合して、アルコールを収容したボールミル中
で、６時間混合した後、乾燥させた。Example: BaCO 3 with a purity of 99.9% or more and a particle size of 2 μm or less,
Y 2 O 3 and CuO powder were mixed in a molar ratio of 2:1:3, mixed for 6 hours in a ball mill containing alcohol, and then dried.
さらに、径100mm×長さ4m、傾斜角25゜の傾斜
型回転炉を用い、炉の上方より下方へ、前記配合
原料粉末を落下させつつ、100vol％O2雰囲気中
で、前記回転炉を回転させながら、930℃、20時
間の仮焼を行なつた。 Furthermore, using a tilted rotary furnace with a diameter of 100 mm x length of 4 m and an inclination angle of 25 degrees, the rotary furnace was rotated in a 100 vol% O 2 atmosphere while dropping the blended raw material powder from the top of the furnace to the bottom. Calcining was carried out at 930°C for 20 hours.
その後、600℃まで冷却速度100℃／Hrにて冷
却し、さらに、580℃に10時間保持した後、室温
まで炉冷して、仮焼粉を得た。 Thereafter, it was cooled to 600° C. at a cooling rate of 100° C./Hr, further held at 580° C. for 10 hours, and then cooled in a furnace to room temperature to obtain a calcined powder.
前記仮焼粉をＸ線回析法にて結晶構造を調査し
た結果、斜方晶からなる低温安定相組織であつ
た。 The crystal structure of the calcined powder was investigated by X-ray diffraction, and it was found to have a low-temperature stable phase structure consisting of orthorhombic crystals.
前記仮焼粉を乾式にて、平均粒度1.5μmに微粉
砕した。 The calcined powder was dry-pulverized to an average particle size of 1.5 μm.
微粉砕粉を、寸法径15mmφ、高さ10mm寸法、材
質SiCからなるダイスに装入し、100vol％O2雰囲
気中で、590℃まで100℃／Hrの条件にて加熱後、
590℃で圧力500Kg／cm2にて10時間保持して、加圧
焼結を行つた。 The finely pulverized powder was charged into a die made of SiC with a diameter of 15 mmφ and a height of 10 mm, and heated at 100°C/Hr to 590°C in a 100vol% O 2 atmosphere.
Pressure sintering was carried out by holding at 590° C. and a pressure of 500 Kg/cm 2 for 10 hours.
その後、炉冷して、寸法径15mmφ、高さ６mmの
焼結体を得た。 Thereafter, it was cooled in a furnace to obtain a sintered body with a diameter of 15 mm and a height of 6 mm.
得られた焼結体を25℃のBaF2飽和溶液500ml中
に10分浸漬すると、表面は少し白色に変色した。 When the obtained sintered body was immersed in 500 ml of BaF 2 saturated solution at 25° C. for 10 minutes, the surface turned slightly white.
その後、前記飽和溶液中に、飽和溶液中のBa
量の４倍に相当する５％Ba（NO3）2溶液を80ml添
加して、撹拌溶液中に焼結体を更に10分間浸漬し
た。 Then, add Ba in the saturated solution to the saturated solution.
80 ml of 5% Ba(NO 3 ) 2 solution corresponding to four times the amount was added, and the sintered body was immersed in the stirred solution for an additional 10 minutes.
つぎに、大気中で300℃で５時間の熱処理を施
した後、60℃の水中に10時間放置の耐候テストを
行つたが、この発明の処理焼結体は水による何ら
の溶出も起こらず、臨界温度（Tc）90kでのTc
のシヤープな（温度幅＜１℃）、高い超電導性を
初期特性通り有するセラミツクスが得られた。 Next, a weathering test was conducted in which the treated sintered body of this invention was heat-treated at 300°C for 5 hours in the air and then left in water at 60°C for 10 hours, but the treated sintered body of this invention did not elute with water. , critical temperature (Tc) at 90k
Ceramics with a sharp (temperature range <1°C) and high superconductivity as expected from the initial characteristics were obtained.
比較のため、BaF2飽和溶液中での浸漬処理を
施さず、実施例と同一条件にて得られた焼結体を
前記と同一の耐候テストを行つた結果、比較焼結
体はBaが約２％溶出し、その時の臨界温度
（Tc）は90〓であるが、Tcがシヤープでなく
（温度幅２〜5k）、部分的に超電導を示さない部
分があつた。 For comparison, a sintered body obtained under the same conditions as the example without immersion treatment in a BaF 2 saturated solution was subjected to the same weathering test as above. As a result, the comparative sintered body had a Ba content of about 2% elution occurred, and the critical temperature (Tc) at that time was 90ⓓ, but Tc was not sharp (temperature range 2 to 5k), and there were some parts that did not exhibit superconductivity.
Claims (1)
し、Ｍ＝Ｙ，La）の焼結体をBaF2飽和溶液中に
浸漬後、前記焼結体を非還元性雰囲気中で200℃
〜600℃の熱処理を施すことを特徴とする耐水性
のすぐれた超電導セラミツクスの製造方法。 ２ 斜方晶組織からなるMBa2Cu3O7-x組成（但
し、Ｍ＝Ｙ，La）の焼結体をBaF2飽和溶液中に
浸漬し、さらに、前記飽和溶液中に前記飽和溶液
のBa量の２倍〜10倍のBa塩を添加して浸漬した
後、 前記溶液より取り出した焼結体に、非還元性雰
囲気中で200℃〜600℃の熱処理を施すことを特徴
とする耐水性のすぐれた超電導セラミツクスの製
造方法。[Claims] 1. After immersing a sintered body having an orthorhombic structure and a composition of MBa 2 Cu 3 O 7-x (where M=Y, La) in a BaF 2 saturated solution, the sintered body is 200℃ in non-reducing atmosphere
A method for producing superconducting ceramics with excellent water resistance, characterized by heat treatment at ~600°C. 2. A sintered body of MBa 2 Cu 3 O 7-x composition (where M = Y, La) consisting of an orthorhombic structure is immersed in a BaF 2 saturated solution, and further, the saturated solution is added to the saturated solution. Water resistant, characterized by adding Ba salt in an amount of 2 times to 10 times the amount of Ba and immersing it, and then subjecting the sintered body taken out from the solution to heat treatment at 200°C to 600°C in a non-reducing atmosphere. A method for producing superconducting ceramics with excellent properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62187986A JPS6433086A (en) | 1987-07-28 | 1987-07-28 | Production of superconducting ceramics having superior water resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62187986A JPS6433086A (en) | 1987-07-28 | 1987-07-28 | Production of superconducting ceramics having superior water resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6433086A JPS6433086A (en) | 1989-02-02 |
| JPH0556304B2 true JPH0556304B2 (en) | 1993-08-19 |
Family
ID=16215616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62187986A Granted JPS6433086A (en) | 1987-07-28 | 1987-07-28 | Production of superconducting ceramics having superior water resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6433086A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2629450B1 (en) * | 1988-04-01 | 1992-04-30 | Rhone Poulenc Chimie | STABILIZED SUPERCONDUCTING MATERIALS AND PROCESS FOR OBTAINING SAME |
-
1987
- 1987-07-28 JP JP62187986A patent/JPS6433086A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6433086A (en) | 1989-02-02 |
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