JPH02145423A - Production of oxide-based superconductor - Google Patents
Production of oxide-based superconductorInfo
- Publication number
- JPH02145423A JPH02145423A JP30023488A JP30023488A JPH02145423A JP H02145423 A JPH02145423 A JP H02145423A JP 30023488 A JP30023488 A JP 30023488A JP 30023488 A JP30023488 A JP 30023488A JP H02145423 A JPH02145423 A JP H02145423A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- superconductor
- crystallized
- oxide
- melting
- 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
- 239000002887 superconductor Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000001962 electrophoresis Methods 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000004017 vitrification Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000012768 molten material Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、超伝導体組成の粉末を電気泳動法で電着させ
て超伝導体を作製する方法において、粉末の調製時間短
縮化、組成均質化および微細化を図った作製方法に関す
る。Detailed Description of the Invention (Industrial Application Field) The present invention provides a method for producing a superconductor by electrodepositing a powder having a superconducting composition by electrophoresis, reducing the preparation time of the powder, and improving the composition of the superconductor. This invention relates to a manufacturing method that achieves homogenization and miniaturization.
（従来技術）
酸化物系超伝導体は、加工性が劣るので、作製の時に目
的の形状に作製する必要がある。このような超伝導体の
作製方法として、超伝導体粉末材料を目的の形状に加工
した電極に電気泳動法で電着させる方法がある。(Prior Art) Oxide-based superconductors have poor workability, so it is necessary to manufacture them into a desired shape. As a method for producing such a superconductor, there is a method in which a superconductor powder material is electrodeposited onto an electrode processed into a desired shape by electrophoresis.
この方法は、原料を組成が超伝導体の配合比になるよう
に混合して仮焼成した後、粉砕して超伝導体材料とし、
この材料を溶媒中に懸濁させ、電気泳動法により目的の
形状に加工した電極上に析出させるか、または、電着後
に焼成する方法であるが、超伝導体材料の粉砕は、焼成
したものを単に機械的に粉砕する方法で行っていた。This method involves mixing the raw materials so that the composition matches that of the superconductor, pre-calcining them, and then pulverizing them to produce a superconductor material.
This material is suspended in a solvent and deposited on an electrode processed into the desired shape using electrophoresis, or the superconductor material is pulverized by firing after electrodeposition. This was done by simply mechanically crushing.
（発明が解決しようとする問題点）
しかしながら、この方法でＢｉ −Ｓｒ −ｅａ −Ｃ
ｕ −０系の超伝導体を作製する場合、電着後焼成して
も、焼成時の反応が同相反応であるため、粒界と粒内の
組成が異なり、全体を均質な組成にできず、また、金属
元素と酸素との相互拡散も遅く、焼成を数百時間行わな
いと安定した超伝導体が得られないという問題があった
。さらに、焼成時に温度管理を厳格に行わないと、超伝
導相の比率が低下し、超伝導性が悪化するという問題も
あった。(Problem to be solved by the invention) However, in this method, Bi -Sr -ea -C
When producing a u-0-based superconductor, even if it is fired after electrodeposition, the reaction during firing is an in-phase reaction, so the composition at grain boundaries and inside the grains is different, making it impossible to make the entire composition homogeneous. In addition, interdiffusion between metal elements and oxygen is slow, and a stable superconductor cannot be obtained unless sintering is performed for several hundred hours. Furthermore, if the temperature is not strictly controlled during firing, the ratio of the superconducting phase decreases, leading to a problem in that the superconductivity deteriorates.
本発明は、かかる点に鑑み、全体の組成が均質になり、
電着後の焼成省略により作製時間を短縮できる電気泳動
法による超伝導体作製方法を提供するものである。In view of this, the present invention has a homogeneous overall composition,
The present invention provides a method for producing a superconductor by electrophoresis, which can shorten the production time by omitting baking after electrodeposition.
（問題点を解決するための手段）
本発明は、電気泳動法に使用する超伝導体材料の調製方
法を改善して、均質化された超伝導体微細粉末にするこ
とにより電着するだけで目的の形状の超伝導体になるよ
うにし、電着後の焼成を不要にして作製時間を短縮化す
るようにした。具体的には、原料を融解することにより
超伝導体材料調製反応の短時間化、組成の均質化を図り
、さらに、融解物を急速冷却して歪の大きいガラス化す
ることにより、粉砕した場合、原料を単に機械的に粉砕
した場合より粒子を微細化させるとともに、その粒子微
細化により超伝導体にするために加熱結晶化を容易にし
た。(Means for Solving the Problems) The present invention improves the method for preparing superconductor materials used in electrophoresis, and makes homogenized superconductor fine powders that can be simply electrodeposited. The goal was to create a superconductor with the desired shape, and eliminate the need for firing after electrodeposition, thereby shortening the manufacturing time. Specifically, by melting the raw materials, we aim to shorten the superconductor material preparation reaction time and homogenize the composition, and further, by rapidly cooling the melt and turning it into highly strained vitrification, when pulverized. In addition to making the particles finer than when the raw material was simply mechanically pulverized, the finer particles made it easier to heat and crystallize the material to make it a superconductor.
すなわち、本発明は、融解後急速冷却によりガラス化す
るように配合した［ｌｉ、 Ｓｒ、 ＣａおよびＣｕの
塩または酸化物を適当なる組成比に混合し、７５０〜８
６０℃で仮焼成、粉砕した後、加圧成形して７５０〜８
６０℃で焼結し、その後、その焼結体を回転冷却ロール
の上部に配置して下部より融解しながら、その液滴をロ
ール間に滴下して急速冷却することによりガラス化し、
しかる後に、微粉砕して７５０℃〜８６０℃で加熱して
結晶化し、この結晶化粉末を溶媒中に懸濁して電気泳動
法により電極に電着させることによりＢｉ系酸化物超伝
導体を作製するようにした。That is, in the present invention, salts or oxides of [li, Sr, Ca, and Cu are mixed in an appropriate composition ratio to vitrify by rapid cooling after melting, and
After pre-calcining and crushing at 60℃, it is press-molded to 750~8
Sintered at 60°C, then placed the sintered body on the top of a rotating cooling roll and while melting from the bottom, droplets of the sintered body are dropped between the rolls for rapid cooling to vitrify it,
Thereafter, it is finely pulverized and crystallized by heating at 750°C to 860°C, and this crystallized powder is suspended in a solvent and electrodeposited by electrophoresis to produce a Bi-based oxide superconductor. I decided to do so.
（作用）
Ｂ１、Ｓｒ％ＣａおよびＣｕの塩または酸化物を混合し
て７５０〜８６０℃で仮焼成すると、均質な複合酸化物
が得られる。仮焼成温度が７５０℃未満であると、反応
がほとんど進行せず、原料の混合物しか得られない。ま
た、８６０℃を越えると、融解が起り、容器との反応や
不純物の混入などの問題が生じる。(Function) B1, Sr% When salts or oxides of Ca and Cu are mixed and calcined at 750 to 860°C, a homogeneous composite oxide is obtained. If the pre-calcination temperature is less than 750°C, the reaction will hardly proceed and only a mixture of raw materials will be obtained. Furthermore, if the temperature exceeds 860°C, melting will occur, causing problems such as reaction with the container and contamination of impurities.
仮焼成物を粉砕、加圧成形して７５０〜８６０℃で焼結
し、それを融解すると、反応が液相反応のため、固相反
応より反応速度が速くなり、組成も一層均質になる。焼
結温度が７５０℃未満であると、焼結がほとんど起らず
、保持して下部から順次融解させる融解用原料としての
充分な機械的強度が得られない。また、８６０℃を越え
ると、融解が起り、融解用原料としての形状を維持でき
ない。When the calcined product is crushed, pressure-molded, sintered at 750 to 860°C, and then melted, the reaction is a liquid phase reaction, so the reaction rate is faster than a solid phase reaction, and the composition becomes more homogeneous. If the sintering temperature is less than 750°C, sintering will hardly occur, and sufficient mechanical strength will not be obtained as a melting raw material that is held and sequentially melted from the bottom. Further, if the temperature exceeds 860°C, melting occurs and the shape as a raw material for melting cannot be maintained.
焼結体の融解は、焼結体を回転冷却ロールの上部に配置
して、その下部より融解させると、融解物が回転冷却ロ
ールの間に滴下し、急速冷却され、ガラス化する。この
ガラスは、急速冷却したままであるので、大きな歪を有
し、粉砕した場合、極めて微細化し易い。このため、粉
末は、焼成したものを単に機械的に粉砕した場合より着
しく細かくなる。この粉末を７５０〜８６０℃に加熱す
ると、結晶化し、超伝導性を示すようになる。この結晶
化は、粉末が微細化されているので、加熱は短時間で済
むとともに、均質に結晶化される。結晶化温度は、７５
０℃未満であると、結晶化が不十分で、８６０℃を越え
ると、粒子間の融着が起る。The sintered body is melted by placing the sintered body on top of a rotating cooling roll and melting the sintered body from the bottom. The melt drips between the rotating cooling rolls and is rapidly cooled and vitrified. Since this glass remains rapidly cooled, it has a large strain, and when crushed, it tends to become extremely fine. Therefore, the powder becomes finer than when the fired product is simply mechanically pulverized. When this powder is heated to 750 to 860°C, it crystallizes and exhibits superconductivity. This crystallization requires only a short heating time because the powder is finely divided, and the crystallization is uniform. The crystallization temperature is 75
If the temperature is less than 0°C, crystallization will be insufficient, and if it exceeds 860°C, fusion between particles will occur.
この結晶化粉末は、電気泳動法により電着させると、微
粉末であるので、ち密になり、電着後の仮焼成や焼結を
施さなくても良好な超伝導性を示し、仮焼成や焼結が不
要になる。When this crystallized powder is electrodeposited by electrophoresis, it becomes dense because it is a fine powder, and exhibits good superconductivity even without calcination or sintering after electrodeposition. Sintering becomes unnecessary.
（発明の具体的開示）
［１ｉｖ Ｓｒ、 ＣａおよびＣｕの塩または酸化物の
配合は、Ｂ１２Ｏ３、ＳｒＯ＋ Ｃａｂ（等モル％）、
ＣｕＯのモル％が第１図の点線に囲まれた範囲になるよ
うにすると、融解、急速冷却によりガラス化できる。(Specific Disclosure of the Invention) [1iv The formulation of salts or oxides of Sr, Ca and Cu is B12O3, SrO+Cab (equal mol%),
When the mol% of CuO is within the range surrounded by the dotted line in FIG. 1, it can be vitrified by melting and rapid cooling.
７５０〜８６０℃での仮焼成は、２〜２０時間実施する
のが好ましい。この仮焼成前に４５０〜５５０℃に加熱
して分解温度の低いものを予め熱分解して仮焼成時間を
短くしてもよい。It is preferable to carry out the temporary calcination at 750 to 860°C for 2 to 20 hours. Before this pre-calcination, the material having a low decomposition temperature may be thermally decomposed by heating to 450 to 550° C. to shorten the pre-calcination time.
仮焼成したものを加圧成形する形状は、任意の形状でよ
く、例えば、棒状、板状、球状でもよいが、棒状もしく
は板状にすると、連続融解が可能になる。The shape in which the pre-fired material is pressure-molded may be any shape, such as a rod, a plate, or a sphere, but continuous melting becomes possible when it is shaped into a rod or a plate.
加圧成形したものの焼結時間は、２〜４時間にするのが
好ましく、成形物の下部よりの融解は、ハロゲンランプ
を熱源とする赤外線集光加熱炉などによればよい。The sintering time of the pressure-molded product is preferably 2 to 4 hours, and melting from the bottom of the molded product may be performed using an infrared condensing heating furnace using a halogen lamp as a heat source.
融解物の急速冷却は、金属製の回転双ロールに融解物の
液滴を滴下して厚さを１０〜５０μ論にすればよい。１
０μ輸未渦にするには、ロールの回転数を速くしなけれ
ばならないので、遠心力で融解物が飛散する割合が多く
なり、５０μ卸より厚くすると、試料全体のガラス化が
困難になる。Rapid cooling of the molten material can be achieved by dropping droplets of the molten material on two rotating metal rolls to a thickness of 10 to 50 microns. 1
In order to create a vortex of 0μ, the number of revolutions of the rolls must be increased, which increases the rate at which the molten material is scattered due to centrifugal force, and if it is thicker than 50μ, it becomes difficult to vitrify the entire sample.
ガラス化粉末の結晶化は、７５０〜８６０℃で４〜２０
時間実施するのが好ましい。７５０℃で２０時間加熱し
ても十分結晶化せず、８６０℃で４時間加熱すると、結
晶性の良好な超伝導体粉末が得られる。The crystallization of vitrified powder is 4-20℃ at 750-860℃.
Preferably, it is carried out for an hour. Even when heated at 750°C for 20 hours, sufficient crystallization did not occur, and when heated at 860°C for 4 hours, a superconductor powder with good crystallinity was obtained.
（実施例）
Ｂｉ（ＮＯｓ）ｓ ・５ＬＯ１Ｃａ（ＮＯ−）２・４ｆ
１２０．５ｒ（ＮＯ＋）２、Ｃｕ（ＮＯ３）２・３１１
２０を［１ｉＬ７２（ＳｒＯ・Ｃａ０）１７２ＣｕＯの
擬三成分系（ＳｒＯ／ＣａＯのモル比１）において、Ｂ
ｉｏ、７２／（ＳｒＯ−ＣａＯ）＋７２／ＣｕＯのモル
％が２２／４０／３４となるように配合して、５００℃
で熱分解した後、粉砕し、さらに８６０℃で２０時間仮
焼成して粉砕した。この仮焼成材料の粒径は２〜５μ艶
であった。(Example) Bi(NOs)s ・5LO1Ca(NO-)2・4f
120.5r(NO+)2, Cu(NO3)2・311
B
io, 72/(SrO-CaO)+72/CuO was blended so that the mol% was 22/40/34, and heated at 500°C.
The mixture was thermally decomposed, pulverized, and further calcined at 860° C. for 20 hours and pulverized. The particle size of this pre-fired material was 2 to 5 μm glossy.
その後、仮焼成材料を３ｍｍ角、長さ４５ＩＩｌＩ１１
の棒状に加圧成形して、８６０℃で焼結し、ハロゲンラ
ンプを熱源とする赤外線集光加熱炉の中につり下げた。After that, the pre-fired material is made into a 3 mm square with a length of 45IIlI11.
It was press-molded into a rod shape, sintered at 860°C, and suspended in an infrared condensing heating furnace using a halogen lamp as a heat source.
この状態でハロゲンランプを点灯し、その集光を先端部
に当てて先端部より順次融解させ、液滴を３０００ｒｐ
輸で回転する鋼製双ロールの間に滴下し、急速冷却させ
て薄膜ガラス化させた。In this state, a halogen lamp is turned on, and the focused light is applied to the tip to melt the droplet sequentially from the tip, and the droplet is heated at 3000 rpm.
It was dropped between two rotating steel rolls and rapidly cooled to form a thin film of vitrification.
この薄ｓｌｆラスの厚みは約３０μ鎮で、Ｘ線回折で若
干ＣａＯの結晶が認められただけで、はとんどガラス化
されていた［第２図の（１）１。The thickness of this thin SLF lath was approximately 30 μm, and although only a few CaO crystals were observed by X-ray diffraction, most of it was vitrified [(1) 1 in Figure 2.
次に、薄膜ガラスを粉砕して、８６０℃で４時間加熱し
て結晶化し、超伝導体材料とした。この材料の粒径は０
．１−０．５μｍで、χ線回折で結晶化が認められた［
第２図の（２）］。Next, the thin film glass was crushed and crystallized by heating at 860° C. for 4 hours to obtain a superconductor material. The particle size of this material is 0
．． Crystallization was observed by chi-ray diffraction at 1-0.5 μm [
(2) in Figure 2].
以上のようにして調製した超伝導体材料１０９をヨウ素
４０艶８添加アセトン中に超音波照射下に懸濁させてへ
ｇ板を作用極、ｐｔ板を対極にして２００■で１０分間
電解し、電着させた。The superconductor material 109 prepared as described above was suspended in acetone containing 40% iodine and 8% iodine under ultrasonic irradiation, and electrolyzed at 200 μm for 10 minutes using the Heg plate as the working electrode and the PT plate as the counter electrode. , electrodeposited.
電着物をΔＳ板より剥離して１０ｍＡの電流を流して電
気抵抗を測定したところ、第３図に示すように、８６に
で電気抵抗はゼロになった。When the electrodeposited material was peeled off from the ΔS plate and the electrical resistance was measured by passing a current of 10 mA, the electrical resistance became zero at 86, as shown in FIG.
（比較例）
実施例での仮焼成材料を融解、ガラス化せずに同一条件
で電気泳動法により電着させ、電気抵抗を測定したとこ
ろ、８６にでは絶縁状態であった。(Comparative Example) When the pre-fired material in Example was electrodeposited by electrophoresis under the same conditions without being melted or vitrified, and the electrical resistance was measured, it was found that No. 86 was in an insulating state.
（発明の効果）
以上のように、本発明は、超伝導体原料を一旦融解して
、急冷によりガラス化し、そのガラス化物を粉砕、結晶
化して超伝導体材料を調製するのであるから、粉末材料
のｓｌＩ！ｌｉ！時間は短くなり、組成も均質になる。(Effects of the Invention) As described above, in the present invention, a superconductor material is prepared by melting a superconductor raw material, vitrifying it by rapid cooling, and crushing and crystallizing the vitrified material. Material slI! li! The time will be shorter and the composition will be more homogeneous.
また、ガラス化させたものを粉砕したものは、粒径が微
細であるので、短時間に結晶化でき、均質に結晶化され
、電着物もち密になる。このため、電着後の焼成や焼結
を省略しても、超伝導性を示す。Further, since the vitrified material is crushed and has a fine particle size, it can be crystallized in a short period of time, and is uniformly crystallized, so that the electrodeposited material becomes dense. Therefore, it exhibits superconductivity even if baking and sintering after electrodeposition are omitted.
第１図は、ＢｉＯｓｌｚ （ＳｒＯ ・ＣａＯ）＋７
２ＣｕＯの擬三成分系（ＳｒＯ／ＣａＯのモル比１）に
おいて、急速冷却によりガラス化する組成の範囲を示す
図である，、第２図は、実施例におけるガラス化したも
のとそのガラス化物を結晶化させたもののＸ線回折図で
ある。
第３図は、
実施例で結晶化させたものの電気
抵抗と温度との関係を示すグラフである。Figure 1 shows BiOslz (SrO ・CaO)+7
Figure 2 shows the range of compositions that can be vitrified by rapid cooling in a quasi-ternary system of 2CuO (SrO/CaO molar ratio 1). It is an X-ray diffraction diagram of a crystallized product. FIG. 3 is a graph showing the relationship between electrical resistance and temperature of the crystallized material in the example.
Claims (5)
たＢｉ、Ｓｒ、ＣａおよびＣｕの塩または酸化物を適当
な組成比に混合し、７５０〜８６０℃で仮焼成、粉砕し
た後、加圧成形して７５０〜８６０℃で焼結し、その後
、その焼結体を回転冷却ロールの上部に配置して下部よ
り融解しながら、その液滴をロール間に滴下して急速冷
却することにより薄膜ガラス化し、しかる後に、微粉砕
して７５０〜８６０℃で加熱して結晶化し、この結晶化
粉末を溶媒中に懸濁して電気泳動法により電極に電着さ
せることを特徴とする酸化物系超伝導体の作製方法。(1) Salts or oxides of Bi, Sr, Ca, and Cu that are blended to vitrify by rapid cooling after melting are mixed in an appropriate composition ratio, calcined at 750 to 860°C, pulverized, and then pressurized. The sintered body is formed and sintered at 750 to 860°C, and then the sintered body is placed on the top of a rotating cooling roll, and while melting from the bottom, the droplets are dropped between the rolls for rapid cooling to form a thin film. The oxide-based superorganism is vitrified, then finely pulverized and crystallized by heating at 750 to 860°C, and the crystallized powder is suspended in a solvent and electrodeposited on an electrode by electrophoresis. Method for making conductors.
請求の範囲第１項に記載の酸化物系超伝導体の作製方法
。(2) The method for producing an oxide-based superconductor according to claim 1, wherein the pre-calcination is performed for 2 to 20 hours.
ｒ、ＣａおよびＣｕの塩の粉末を熱分解することを特徴
とする特許請求の範囲第１項に記載の酸化物系超伝導体
の作製方法。(3) Bi, S is heated to 450-550℃ before temporary sintering.
2. The method for producing an oxide superconductor according to claim 1, which comprises thermally decomposing powders of salts of r, Ca, and Cu.
の範囲第１項に記載の酸化物系超伝導体の作製方法。(4) The method for producing an oxide-based superconductor according to claim 1, characterized in that sintering is performed for 2 to 4 hours.
を特徴とする特許請求の範囲第１項に記載の酸化物系超
伝導体の作製方法。(5) The method for producing an oxide superconductor according to claim 1, characterized in that the thickness of the thin film vitrification is 10 to 50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30023488A JPH02145423A (en) | 1988-11-28 | 1988-11-28 | Production of oxide-based superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30023488A JPH02145423A (en) | 1988-11-28 | 1988-11-28 | Production of oxide-based superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02145423A true JPH02145423A (en) | 1990-06-04 |
Family
ID=17882327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30023488A Pending JPH02145423A (en) | 1988-11-28 | 1988-11-28 | Production of oxide-based superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02145423A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6002583A (en) * | 1997-01-31 | 1999-12-14 | Citizen Watch Co., Ltd. | Portable computer provided with removable battery pack |
| US6078496A (en) * | 1994-09-06 | 2000-06-20 | Citizen Watch Co., Ltd | Portable computer with hinged detachable battery pack |
| US7448747B2 (en) | 2001-01-17 | 2008-11-11 | Silverbrook Research Pty Ltd | Personal digital assistant terminal with internal printer and a receptacle for receiving a cartridge containing at least one ink |
-
1988
- 1988-11-28 JP JP30023488A patent/JPH02145423A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6535378B1 (en) | 1994-06-09 | 2003-03-18 | Citizen Watch Co., Ltd. | Portable computer with detachable battery pack |
| US6078496A (en) * | 1994-09-06 | 2000-06-20 | Citizen Watch Co., Ltd | Portable computer with hinged detachable battery pack |
| US6002583A (en) * | 1997-01-31 | 1999-12-14 | Citizen Watch Co., Ltd. | Portable computer provided with removable battery pack |
| US7572003B2 (en) | 2001-01-17 | 2009-08-11 | Silverbrook Research Pty Ltd | Personal digital assistant incorporating a print roll cartridge storing ink and print media |
| US7591553B2 (en) | 2001-01-17 | 2009-09-22 | Silverbrook Research Pty Ltd | Personal digital assistant with internal printer having capping mechanism |
| US7458678B2 (en) | 2001-01-17 | 2008-12-02 | Silverbrook Research Pty Ltd | Personal digital assistant (PDA) body defining a print roll cartridge bay |
| US7465109B2 (en) | 2001-01-17 | 2008-12-16 | Silverbrook Research Pty Ltd | Compact personal digital assistant having in-built printer |
| US7556370B2 (en) | 2001-01-17 | 2009-07-07 | Silverbrook Research Pty Ltd | Personal digital assistant with print cartridge dock |
| US7448747B2 (en) | 2001-01-17 | 2008-11-11 | Silverbrook Research Pty Ltd | Personal digital assistant terminal with internal printer and a receptacle for receiving a cartridge containing at least one ink |
| US7572004B2 (en) | 2001-01-17 | 2009-08-11 | Silverbrook Research Pty Ltd | Print engine with chassis ink channels between printhead and cartridge |
| US7448746B2 (en) | 2001-01-17 | 2008-11-11 | Silverbrook Research Pty Ltd | Personal digital assistant with internal printer and a body section connected through a hinge joint |
| US7708399B2 (en) | 2001-01-17 | 2010-05-04 | Silverbrook Research Pty Ltd | Print engine assembly with dual motor assemblies |
| US7722186B2 (en) | 2001-01-17 | 2010-05-25 | Silverbrook Research Pty Ltd | Personal digital assistant incorporating a printer |
| US7887180B2 (en) | 2001-01-17 | 2011-02-15 | Silverbrook Research Pty Ltd | Hinged personal digital assistant (PDA) with internal printer |
| US7901069B2 (en) | 2001-01-17 | 2011-03-08 | Kia Silverbrook | Print engine assembly with dual motor assemblies |
| US7934829B2 (en) | 2001-01-17 | 2011-05-03 | Silverbrook Research Pty Ltd | Mobile computing device incorporating printer and print media roll |
| US7954940B2 (en) | 2001-01-17 | 2011-06-07 | Silverbrook Research Pty Ltd | Personal digital assistant having printhead |
| US7984986B2 (en) | 2001-01-17 | 2011-07-26 | Silverbrook Research Pty Ltd | Hand held personal digital assistant having an internal printer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH02145423A (en) | Production of oxide-based superconductor | |
| WO1989010800A1 (en) | Process for preparing a barium titanate film | |
| JP2540639B2 (en) | Method for manufacturing bismuth-based superconductor | |
| JP2685951B2 (en) | Method for manufacturing bismuth-based superconductor | |
| JPH01219014A (en) | Production of dielectric material powder | |
| Gorokhovskii et al. | Synthesis of glass-ceramic materials in the BaO–PbO–B2O3–Al2O3–TiO2 system | |
| JP2555706B2 (en) | Manufacturing method of Bi-based superconducting oxide powder containing lead and sintered body thereof | |
| JPH0354103A (en) | Production of oxide superconductor | |
| US4906608A (en) | Method for preparing superconductors ceramic composition | |
| JPS63315572A (en) | Production of superconductor | |
| DE3803530A1 (en) | Superconductor and process for the production thereof | |
| JPH03115159A (en) | Production of bi-based superconductor | |
| JP3157184B2 (en) | Manufacturing method of high-density oxide superconductor | |
| JPH0524863B2 (en) | ||
| JP2545443B2 (en) | Method for manufacturing oxide superconductor | |
| JPH0443860B2 (en) | ||
| JPH0624975B2 (en) | Method for producing titanate powder | |
| JPH02120234A (en) | Production of oxide superconductor | |
| JP3444930B2 (en) | Manufacturing method of oxide superconductor | |
| JPS63265812A (en) | Manufacture of ba2ycu3o7-x compound | |
| JPH0859342A (en) | Production of high temperature superconductor | |
| JPH01239054A (en) | Production of oxide superconductor | |
| JP2004269309A (en) | Oxide superconductor and its manufacturing method | |
| JPH01278449A (en) | Production of oxide superconductor | |
| JPH0575713B2 (en) |