JPH02199025A - Bi-based oxide superconductor - Google Patents
Bi-based oxide superconductorInfo
- Publication number
- JPH02199025A JPH02199025A JP1018995A JP1899589A JPH02199025A JP H02199025 A JPH02199025 A JP H02199025A JP 1018995 A JP1018995 A JP 1018995A JP 1899589 A JP1899589 A JP 1899589A JP H02199025 A JPH02199025 A JP H02199025A
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- based oxide
- oxide superconductor
- superconductor
- temperature
- 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.)
- Granted
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 238000010304 firing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 150000002927 oxygen compounds Chemical class 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910001512 metal fluoride Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910014454 Ca-Cu Inorganic materials 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
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 oxides Chemical compound 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052727 yttrium 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、Ｂｉ系酸化物超電導体に関するものである
。さらに詳しくはこの発明は、より低温度での焼成を可
能とする、１１０に級の高温相を主体とするＢｉ系酸化
物超電導体に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a Bi-based oxide superconductor. More specifically, the present invention relates to a Bi-based oxide superconductor mainly consisting of a 110-grade high temperature phase, which allows firing at lower temperatures.
（従来の技術とその課題）
近年、酸化物高温超電導体の開発は、Ｌａ、Ｙ等の希土
類元素系酸化物からＢｉ系あるいはＴ、ｌ！系の酸化物
の登場によって、臨界温度（Ｔｃ）が１００に級以上の
レベルのものにその対象が移ってきている。(Conventional technology and its problems) In recent years, the development of oxide high temperature superconductors has progressed from rare earth element-based oxides such as La and Y to Bi-based or T, l! With the advent of oxides in the oxide system, the focus has shifted to those with critical temperatures (Tc) of 100 or higher.
特にＢｉ系の、Ｂ ５−３ｒ−Ｃａ−Ｃｕ −０χｉｄ
ｃの超電導体は、Ｙ系に比べて臨界温度（Ｔｃ）が高く
、しかもＴ１が毒性の強いのに比べて取扱いが安全であ
ることや、その組織構造上の特徴から全世界的に注目さ
れているものである。Especially Bi-based, B 5-3r-Ca-Cu -0χid
C superconductors have attracted worldwide attention because they have a higher critical temperature (Tc) than Y-based superconductors, are safer to handle than T1, which is more toxic, and because of their structural characteristics. It is something that
しかしながら、このＢＬ系酸化物超電導体については、
これまでに提案されている焼結方法によって製造する場
合には、８７０℃以上という高温度の焼成を必要とし、
しかも、８０にレベルに臨界温度を有する低温層と１０
０にレベルに臨界温度を有する高温相との混相状態にあ
ることが避けられなかった。However, regarding this BL-based oxide superconductor,
When manufacturing using the sintering method proposed so far, high temperature firing of 870°C or higher is required.
Moreover, a low temperature layer with a critical temperature at the level of 80 and 10
A mixed phase state with a high temperature phase having a critical temperature at the level of 0 is inevitable.
この混相状態を解消して、’ｌ’ｃ＝ＩＱＯＫ級の高温
和のＢ１−８ｒ−Ｃａ−Ｃｕ−Ｏｘｉｄｅを主なるもの
として得ようとする工夫も種々行われてきてはいる。た
とえば、このＢＳ系酸化物にＰｂ＜鉛）を添加する方法
などがすでに提案されている。Various efforts have been made to eliminate this mixed phase state and obtain B1-8r-Ca-Cu-Oxide with a high sum of 'l'c=IQOK class as the main component. For example, a method of adding Pb<lead to this BS-based oxide has already been proposed.
しかしながら、このＰｂ添加の方法は、Ｐｂの比率の制
御が難しく、しかもＴｃの改善効果も必ずしも充分でな
いという欠点があった。また、焼成の温度をより低くす
る可能性もなかった。However, this method of adding Pb has the disadvantage that it is difficult to control the Pb ratio, and the effect of improving Tc is not necessarily sufficient. There was also no possibility of lowering the firing temperature.
この発明は、以上の通りの事情に鑑みてなされたもので
あり、これまでのＢｉ系酸化物超電導体の欠点を改善し
、焼成温度をより低くする可・油性を有し、しかも１１
０に級の高温相を主体とする超電導体を再現性よく提供
することを目的としている。This invention was made in view of the above circumstances, and it improves the drawbacks of conventional Bi-based oxide superconductors, has a property of being oily and oleaginous that lowers the firing temperature, and has an 11
The purpose of this research is to provide a superconductor mainly consisting of a 0-grade high-temperature phase with good reproducibility.
（課題を解決するための手段）
この発明は、上記の課題を解決するものとして、Ｂｉ、
Ｓｒ、Ｃａおよび銅の酸素化合物に弗化物を添加して熱
処理してなることを特徴とするＢｉ系酸化物超電導体を
提供する。(Means for Solving the Problems) The present invention solves the above problems by providing Bi,
A Bi-based oxide superconductor is provided, which is formed by adding fluoride to an oxygen compound of Sr, Ca, and copper and heat-treating the mixture.
より評しくは、この発明は、Ｂｉ、Ｓｒ、Ｃａ。More specifically, this invention uses Bi, Sr, and Ca.
および銅の酸素化合物、たとえば酸化物、炭＃！ｉ塩、
硝酸塩、その他の酸素との化合物に、弗化物、たとえば
アルカリ金属弗化物、アルカリ土類金属弗化物、鉛弗化
物等を添加して、高温熱処理してなるＢ１系超電導体を
提供する。and oxygen compounds of copper, such as oxides, charcoal #! i salt,
A B1-based superconductor is provided by adding a fluoride such as an alkali metal fluoride, an alkaline earth metal fluoride, a lead fluoride, etc. to a nitrate or other compound with oxygen and heat-treating the mixture at a high temperature.
この場合の熱処理には、従来と同様の仮焼−焼成、さら
に必要に応じてのアニール処理が含まれる。この熱処理
は、その組成構成によって変動はあるが、−数的には、
８００〜８５０℃での仮焼、８３０〜８８０℃での焼成
とすることができ、いずれの場合にも、従来の焼成温度
よりは低い温度とすることができる。The heat treatment in this case includes calcination and firing as in the conventional method, and further annealing treatment as necessary. Although this heat treatment varies depending on its composition, numerically,
Calcination can be performed at 800 to 850°C and firing can be performed at 830 to 880°C, and in either case, the firing temperature can be lower than the conventional firing temperature.
酸化物の成分組成については、原料成分ベースで、Ｂｉ
：Ｓｒ：Ｃａ：Ｃｕについては、１：１：１：２を基
準として採用することができる。また弗化物の添加量は
、Ｂｉ、Ｓｒ、またはＣａの原料成分に対して、モル比
で、２０：１〜１：１程度とすることができる。Regarding the component composition of the oxide, Bi
:Sr:Ca:Cu can be adopted on the basis of 1:1:1:2. Further, the amount of fluoride added can be about 20:1 to 1:1 in molar ratio to the raw material components of Bi, Sr, or Ca.
また、熱処理は、空気または酸素の気流中で行うのが好
ましく、この場合、焼成についてはオープン系、または
クローズ系のいずれでもよい。Further, the heat treatment is preferably performed in a stream of air or oxygen, and in this case, the firing may be performed in either an open system or a closed system.
数的にはオープン系とするのが好ましい。In terms of numbers, it is preferable to use an open system.
この発明の弗化物の添加によるＢｉ系酸化物においては
、より低い焼成温度において、１１０ Ｋ級の高温相を
主体とする超電導体が得られる。弗素が、Ｂ電導体の構
造に有意な作用を及ぼしている。In the Bi-based oxide of the present invention added with fluoride, a superconductor mainly consisting of a high temperature phase of 110 K class can be obtained at a lower firing temperature. Fluorine has a significant effect on the structure of the B conductor.
以下、実施例を示してさらに詳しくこの発明について説
明する。もちろん、この発明は以下の実施例によって限
定されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples. Of course, the invention is not limited to the following examples.
実施例１
原料として、Ｂｉ＊ Ｏｓ 、５ｒＣＯｘ 、ＣｕＯお
よびＣａＦ２を３ｉ ：Ｓｒ：Ｃａ：Ｃｕ＝ｌ ：１：
１：２となるように調整しな、またＣ ａｃＯｓ ：
Ｃａ Ｆ ｉ ＝ ９ ： １としな。Example 1 As raw materials, Bi*Os, 5rCOx, CuO and CaF2 were used as 3i:Sr:Ca:Cu=l:1:
Adjust so that the ratio is 1:2, and CacOs:
CaF i = 9:1.
この原料を粉砕、混合し、仮焼しな、その後、ディスク
状（１６−φＸ ｌ ｒｍ ）に成形して焼成した。The raw materials were pulverized, mixed, and calcined, then formed into a disk shape (16-φX rm ) and fired.
この時の条件は以下の通りとしな。The conditions at this time are as follows.
仮焼温度 ８３０℃
焼成温度 ８６０℃Ｘ６０時間
雰囲気 空気オープン系
得られた焼成物について直流４端子法により抵抗率の温
度依存性を評価し、また、粉末Ｘ線回折、電子線回折に
よって構造分析を行った。Calcination temperature: 830°C Firing temperature: 860°C x 60 hours Atmosphere: Air open system The temperature dependence of resistivity of the obtained fired product was evaluated using the DC 4-probe method, and the structure was analyzed using powder X-ray diffraction and electron beam diffraction. went.
焼成物の酸化物の抵抗率は、第１図に示したように１０
８Ｋにおいて０となり、Ｔｃ＝１１０にの高温相からな
る超電導体であることが確認された。The resistivity of the oxide of the fired product is 10 as shown in Figure 1.
It became 0 at 8K, confirming that it is a superconductor consisting of a high temperature phase with Tc=110.
このもののＸ線回折の結果を示したものが第２図である
。この第２図より、（２４３）型のｇ４造が主体となっ
ていることがわかる。FIG. 2 shows the results of X-ray diffraction of this material. From this Figure 2, it can be seen that (243) type g4 construction is the main type.
比較例１
比較のために、焼成温度を、従来と同様の８７４℃の温
度とし、２０時間の焼成を行った。Comparative Example 1 For comparison, the firing temperature was set to 874° C., which is the same as the conventional method, and firing was performed for 20 hours.
この時のものは、第３図に示したようなＸ４１回折を示
し、１１０に級のＴｃは示さず、８０に級Ｔｃのものし
か得られていないことが確認された。It was confirmed that the sample at this time showed X41 diffraction as shown in FIG. 3, did not show Tc of 110, and only Tc of 80 was obtained.
この結果からも明らかなように、弗化物を添加したこの
発明の場合には、より低い焼成温度において、より高い
Ｔｃを示すものであることがわかる。As is clear from these results, it can be seen that in the case of the present invention in which fluoride is added, a higher Tc is exhibited at a lower firing temperature.
実施例２
焼成時間を２０時間としたほかは、実施例１と同様にし
て酸化物組成物を得た。Example 2 An oxide composition was obtained in the same manner as in Example 1, except that the firing time was 20 hours.
このものも、Ｔｃ＝１１０にの超電導体であることが確
認された。ただ、第４図に示したように、Ｘ線回折の結
果からは、第２図の６０時間の焼成のものに比べｒ（２
３２）型の構造の比がやや高いことがわかる。This material was also confirmed to be a superconductor with Tc=110. However, as shown in Figure 4, the results of X-ray diffraction indicate that r(2
32) It can be seen that the ratio of the type structure is somewhat high.
実施例 ３
Ｓｒ：Ｃａ：Ｃｕ＝１ ： １ ：１．８の組成と、Ｂ
ｉ ２ ０．＝０．９５
Ｐ ｂ Ｆ ２ ＝Ｏ，Ｑ５
の比率となるように実施例と同様に原料調整し、８４０
℃Ｘ１２時間の仮焼と、８４０℃×４Ｑ時間の焼成を行
った。Example 3 Composition of Sr:Ca:Cu=1:1:1.8 and B
i 2 0. The raw materials were adjusted in the same manner as in the example so that the ratio was 0.95 P b F 2 =O, Q5, and 840
Calcination at 840°C for 12 hours and firing at 840°C for 4Q hours were performed.
その結果、Ｔ ｃ （ｏｎ）＝１１４ ｋ 、 Ｔ ｃ
（ｅｎｄ） ＝８０にの酸化物超電導体を得た。As a result, T c (on)=114 k , T c
An oxide superconductor of (end) =80 was obtained.
実施例 ４
Ｂｉ ：Ｃａ：Ｃｕ＝１ ： １ ：１．８ 、および
５ｒＣＯ，＝０．９
ＫＦ ＝０．１
の組成の原料から、実施例１と同様にして、８３０℃×
１２時間の仮焼、８６Ｇ ’ＣＸ ７０ 時間ｆ） ｍ
成によって、Ｔ ｃ （Ｏｎ）＝ １１７ ｋ 、 Ｔ
ｃ （ｅｎｄ） ＝８５にの酸化物超電導体を得た。Example 4 From raw materials having the compositions Bi:Ca:Cu=1:1:1.8 and 5rCO,=0.9 KF=0.1, the same procedure as in Example 1 was carried out at 830°C×
12 hours calcination, 86G 'CX 70 hours f) m
According to the configuration, T c (On) = 117 k , T
An oxide superconductor with c (end) =85 was obtained.
この結果から、弗化物の添加によって、より低い温度で
の焼成による、より高いＴｃの実現可能性が示された。This result showed the possibility of achieving higher Tc by calcination at lower temperature with the addition of fluoride.
（発明の効果）
以上詳しく説明した通り、この発明により従来よりも低
い焼成温度による、高温相を主体とする弗素添加酸化物
Ｂ１系超電導体が提供される。(Effects of the Invention) As explained in detail above, the present invention provides a fluorine-added oxide B1-based superconductor mainly consisting of a high-temperature phase, which is fired at a lower firing temperature than conventional ones.
この発明によって、今後のＢｉ系超電導体の新しい可能
性も提示される。This invention also presents new possibilities for future Bi-based superconductors.
第１図は、この発明の一実施例の抵抗率変化を示した抵
抗率と温度の相関図である。第２図はこの実施例につい
てのＸ線回折図である。
第３図は、比較例について示したＸ線回折図である。
第４図は、この発明の別の例について示したＸ線回折図
である。
７１図
温度（Ｋ）FIG. 1 is a diagram showing the relationship between resistivity and temperature, showing changes in resistivity in an embodiment of the present invention. FIG. 2 is an X-ray diffraction diagram for this example. FIG. 3 is an X-ray diffraction diagram shown for a comparative example. FIG. 4 is an X-ray diffraction diagram showing another example of the present invention. Figure 71 Temperature (K)
Claims (7)
を添加して熱処理してなることを特徴とするＢｉ系酸化
物超電導体。(1) A Bi-based oxide superconductor, which is formed by adding fluoride to an oxygen compound of Bi, Sr, Ca, and copper and heat-treating the mixture.
ｉ系酸化物超電導体。(2) B according to claim (1), wherein the fluoride is a metal fluoride
i-based oxide superconductor.
焼成してなる請求項（１）記載のＢｉ系酸化物超電導体
。(3) The Bi-based oxide superconductor according to claim (1), which is calcined at 800-850°C and then fired at 830-880°C.
１）記載のＢｉ系酸化物超電導体。(4) A claim in which the product is annealed after calcination and firing (
1) Bi-based oxide superconductor as described.
（１）記載のＢｉ系酸化物超電導体。(5) The Bi-based oxide superconductor according to claim (1), which is heat-treated in air or in an oxygen stream.
する組成物からなるＢｉ系酸化物超電導体。(6) A Bi-based oxide superconductor consisting of a composition containing Bi, Sr, Ca, Cu, oxygen, and fluorine.
に、アルカリ金属，Ｂａ，またはＰｂを含有する組成物
からなるＢｉ系酸化物超電導体。(7) A Bi-based oxide superconductor consisting of a composition containing Bi, Sr, Ca, Cu, oxygen, and fluorine, as well as an alkali metal, Ba, or Pb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1018995A JPH07115874B2 (en) | 1989-01-28 | 1989-01-28 | Method for manufacturing Bi-based oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1018995A JPH07115874B2 (en) | 1989-01-28 | 1989-01-28 | Method for manufacturing Bi-based oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02199025A true JPH02199025A (en) | 1990-08-07 |
| JPH07115874B2 JPH07115874B2 (en) | 1995-12-13 |
Family
ID=11987145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1018995A Expired - Lifetime JPH07115874B2 (en) | 1989-01-28 | 1989-01-28 | Method for manufacturing Bi-based oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07115874B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8703651B2 (en) | 2012-07-06 | 2014-04-22 | Dale Richard Harshman | Layered ionic superconductor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02188464A (en) * | 1989-01-13 | 1990-07-24 | Matsushita Electric Ind Co Ltd | Porcelain composition |
-
1989
- 1989-01-28 JP JP1018995A patent/JPH07115874B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02188464A (en) * | 1989-01-13 | 1990-07-24 | Matsushita Electric Ind Co Ltd | Porcelain composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8703651B2 (en) | 2012-07-06 | 2014-04-22 | Dale Richard Harshman | Layered ionic superconductor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07115874B2 (en) | 1995-12-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |