CN1061866A - The manufacture method of superconducting ceramics - Google Patents
The manufacture method of superconducting ceramics Download PDFInfo
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- CN1061866A CN1061866A CN91111165A CN91111165A CN1061866A CN 1061866 A CN1061866 A CN 1061866A CN 91111165 A CN91111165 A CN 91111165A CN 91111165 A CN91111165 A CN 91111165A CN 1061866 A CN1061866 A CN 1061866A
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- China
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- superconducting ceramics
- sintering
- superconducting
- superconductor
- reduction liquid
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- 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
Superconducting ceramics preparation methods with high Tc is included in sintering and before each component of pottery is mixed with a kind of alcohol or freon.The effect of alcohol or freon is a reduction pottery when sintering, thereby can be with excessive oxygen by removing in the superconducting structure.Then superconducting ceramics is applied with organic resin film, be used to avoid the effect of air.
Description
The present invention relates to the superconductor technical field.
Known to for a long time metals such as mercury and lead; As Nb Nd, Nb
3Interphases such as Ge and Nb Ga; And as Nb
3(Al
0.8Ge
0.2But) wait ternary metal material superconduct.Yet the transition temperature of the above-mentioned habitual superconductor material of knowing can not surpass 25 ° of K.
In recent years, superconducting ceramics has caused extensive attention.Breadboard researcher has at first reported a kind of new material in Zurich in International Business Machines Corp., i.e. the high-temperature superconductor oxide body of Ba-La-Cu-O type.The La-Sr-Cu(II has then also been proposed)-the superconductor oxide of O type.The superconductor material of the other types of having found is (YBa
2) Cu
3O
6-8In view of in fact, can form the atomic unit of quasi-molecule in the crystal structure of this type superconducting ceramics, and in its structure cell one deck structure, electronics moves in one direction basically.Yet electronics is to move on three directions in the above-mentioned material of knowing, so the superconducting ceramics of this type just has higher transition temperature.
The research people of this area is devoted to improve the work of Tco, and resistance disappears under this temperature, makes it exceed the level that forefathers reach, and preferably can make its boiling point that exceeds nitrogen (77 ° of K) even higher temperature.As us described in No. 87309081.5, the european patent application, to tool stoichiometric equation (A
1-xB
x)
yCu
yO
wSuperconducting ceramics study, in this formula, A represents one or more periodic table III a family element, as rare earth element, B represents one or more periodic table II a family element, comprises beryllium and magnesium as alkali earth metal.In the research of then carrying out, we reported when this superconductor is surperficial to be contacted with air, can make it be difficult to obtain stable high Tco.
Therefore the object of the invention is to provide a kind of manufacture method of superconducting ceramics, and this superconductor has the higher transition temperature that can reach than prior art, and provides manufacturing to have the superconducting ceramics of stable transition temperature.
But former development has in the superconductor material of using value, and how people's attentiveness passes through to change the mol ratio of its composition or component element in the hope of improving Tco if concentrating on.Mainly provide a kind of improving one's methods of superconducting ceramics that prepare according to the present invention; according to this method; after forming superconductor structure; immediately superconductor is applied a kind of organic resin protective film; can avoid from ambient atmosphere, absorbing moisture like this; especially be cooled to liquid nitrogen temperature when being transformed into superconducting phase when superconductor, avoid from air, absorbing moisture.The absorption of moisture can cause the superconducting ceramics performance to reduce.
In a preferred embodiment, with forming the raw material chemical substance porphyrize of superconducting ceramics, suppress and fire shaping.To form evenly in order making, to repeat after this operation one or many, the powder of porphyrize mixes with water-free liquid, then it is pressed into the compacting thing that wherein contains liquid.To suppress thing and slowly heat, thereby can avoid anxious poly-reduction.And at 500-1400 ℃ of following sintering.After press body taken out, apply press body with organic resin film immediately in stove.The example of this organic resin is an epoxy resin, fluorine resin and polyimide resin.Known to experiment, this transition temperature can be brought up to 90-120 ° of K.
Has the triplen of the Ca-Ti ore type of distortion as shown in drawings according to superconductor material of the present invention.Main in each layer structure by a copper atom 2 and the oxygen atom 5 around copper atom 2.Oxygen room 7 plays an important role in superconductivity.For by removing excessive oxygen in the superconducting ceramics, need before sintering, water-free reduction liquid to be added in the ceramic material.The example of this reduction liquid is methyl alcohol, ethanol and freon such as Freon 113.Contained oxygen effect in reduction liquid and the ceramic material and generate steam and carbon dioxide.
Owing to, can make along the axial atomic distance of C and shorten, thereby can obtain very high transition temperature by eliminating oxygen in the effect that fully is contained in the reduction liquid in the pottery.
To characteristics of the present invention, those skilled in the art can clearly be understood by the following example.
Accompanying drawing 1 is the diagram by the distortion perovskite structure of superconducting ceramics of the present invention.
Following each embodiment will further specify the method for making of superconducting ceramics, and this superconducting ceramics meets stoichiometric equation (A
1-xB
x)
yCu
yO
w, wherein A is an one or more periodic table III a family element, as rare earth element, B is an one or more periodic table II a family element, comprises beryllium and magnesium as alkali earth metal, and x=0-1; Y=2.0-4.0; 2.5-3.5 preferably; Z=1.0-4.0,4.5-3.5 preferably, w=4.0-10.0, preferably 6.0-8.0.Example is YBa
2Cu
3O
7-x, YCa
2Cu
3O
7-x
Embodiment 1
The BaCO of scheduled volume
3, CaCO
3, CuO and Y
2O
3(High Purity Chemical Industries Co.Ltd produces, purity 99.95% or more than) is used to prepare the superconducting ceramics material by following formula, in this formula, and x=0.67, y=3, z=3 and w=6-8 promptly meet formula (YBa
2) Cu
3O
6-8Or (YBaCa) Cu
3O
6-8Wherein the w value can be controlled by adjusting sintering condition.
Behind the mixing, highly purified chemistry material is at 500 kilograms/cm in ball mill
2Compacting in container (capsule) down, and form cylindric sheet stock (10 millimeters of diameters, high 3 millimeters).Under 500-1100 ℃ (as 950 ℃), (in air) heating (sintering) and oxidation are 8 hours in oxidizing atmosphere with sheet stock, and this is referred to as presintering below step.Then with sheet stock porphyrize in ball mill, making its average grain diameter is 20-0.003 micron (as 0.5 micron or following).This step is repeated 3-5 time.Need handled to avoid in product, producing Y therein
2BaCuO
5Or cupric oxide phase.
Then, be that the powder of 20-0.0003 micron is even with methanol mixed in ball mill with average grain diameter, at 1 ton/centimetre
2In container, be pressed into the sheet material under the pressure.
With the sheet stock sintering, this is referred to as main sintering below step then.Main sintering is in oxidizing atmosphere (in air), carries out under 500-1400 ℃ 10-50 hour, for example 930 ℃ of following sintering 15 hours.When sintering carries out,, rise to predetermined temperature by room temperature with 10-1000 ℃ of speed (as per hour 100 ℃) per hour.When heating up, ceramic material partial reduction by the effect of alcohol.Under 100 ℃ of speed per hour, cool the temperature to 400 ℃ then.
So form the perovskite structure of compact texture.Dip-coating in organic siliconresin solution was then carried out hot curing 2 hours or 30 minutes again in 150 ℃ dehumidified air, thereby covered the layer of resinizing on sheet stock.When covering when being coated with epoxy resin, hot curing is to be in the air, carries out under 150 ℃ 30 minutes, or carries out under 240 ℃ 5 minutes.
The ceramic material that application makes is studied the relation between its temperature and the resistivity.When temperature was descended by 300K, resistance began to descend at about 110K, and disappears at 98K.When temperature value between room temperature and transition temperature repeatedly during lifting, this transition temperature of replication 98K.As a reference, other prepares identical superconducting ceramics material and tests, and the result represents that during the repeated temperature lifting, transition temperature is reduced to 63K.
Cover the organic resin that is applied to superconductor material and preferably be selected from soft resin.This is owing to do not wish when solidifying because the pucker ﹠ bloat of resin causes the local stress on the superconductor material.
Repeat the operation of embodiment 1, but 50% Y replaces with Yb, and with Sr replaced C a, replace methyl alcohol with freon, Y and Yb are with oxide or the adding of fluoride form.The result represents, it is 130 ° of K and the Tco value is 101 ° of K that Tc begins the temperature measuring value, and it can keep a week or longer time.
The foregoing description is only in order to illustrate the present invention, and do not comprise and be used to prepare each the element combinations situation of the super allosome ceramic material of the present invention and the applicable cases of various distinct methods, also can produce the superconductor material of improvement effectively under other combined situation.
Also can be by the used superconducting ceramics of the present invention by stoichiometric equation (A
1-xB
x)
yCu
yO
wX
vPrepare, in this formula, A is one or more periodic table III a elements, and as rare earth element, B is one or more periodic table II a elements, comprise beryllium and magnesium as alkali earth metal, X is one or more column element such as Ge down, Sn, Pb, F or Cl, x=0-1, y=2.0-4.0 preferably equals 2.5-3.5; Z=1.0-4.0 preferably equals 1.5-3.5; W=4.0-10.0 preferably equals 6.0-8.0, v=0-3, and for example this formula can be YBa
2Cu
3O
6-8In addition can also be by stoichiometric equation (A by the used superconducting ceramics of the present invention
1-xB
x)
yCu
yO
wPrepare, in this formula, A is an one or more periodic table Vb family element, and as Bi, Sb and As, B are one or more periodic table II a family element, as alkali earth metal, and x=0.3-1, y=2.0-4.0 preferably equals 2.5-3.5; Z=1.0-4.0 preferably equals 1.5-3.5, and w=4.0-10.0 preferably equals 6.0-8.0, and for example this formula can be BiCaSrCu
3O
6-8
Some preferential embodiment are described above, but what should propose is that the present invention is not limited to described embodiment, and, can suitably revise in the described scope by claims not exceeding the present invention.For example available diamond-like carbon is as protection superconducting ceramics film.The preparation method of material with carbon element can be referring to No. 88101061.8, Chinese patent application (on February 24th, 1888).In addition, applying a magnetic field is effective for the adjustment crystal axis in main sintering.In this manual, III a family element is meant that comprises the described transition elements of following data, i.e. " physics and chemical dictionary " (being published by Japanese Iwanami).In this respect, III a family element comprises as the described typical element of following data, i.e. " The Penguin Dictionary of Science " (being published by Penguin Books).
Claims (5)
1, a kind of method of making superconducting ceramics, comprising:
The chemical substance of superconducting ceramics is formed in preparation,
Described chemical substance is mixed and the porphyrize powdered by predetermined composition,
Described chemical substance is mixed with a kind of reduction liquid, and, make it have superconductivity the mixture sintering of described chemical substance and described reduction liquid.
2, by the process of claim 1 wherein that described reduction liquid is a kind of alcohol.
3, by the process of claim 1 wherein that described reduction liquid is methyl alcohol.
4, by the process of claim 1 wherein that described reduction liquid is ethanol.
5, by the process of claim 1 wherein that described reduction liquid is freon.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62214743A JPH0649626B2 (en) | 1987-08-27 | 1987-08-27 | Oxide superconducting material |
| JP214743/87 | 1987-08-27 | ||
| CN88106291.XA CN1023624C (en) | 1987-08-27 | 1988-08-25 | Method of manufacturing superconducting ceramics and products thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88106291.XA Division CN1023624C (en) | 1987-08-27 | 1988-08-25 | Method of manufacturing superconducting ceramics and products thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1061866A true CN1061866A (en) | 1992-06-10 |
Family
ID=25742482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111165A Pending CN1061866A (en) | 1987-08-27 | 1991-11-21 | The manufacture method of superconducting ceramics |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1061866A (en) |
-
1991
- 1991-11-21 CN CN91111165A patent/CN1061866A/en active Pending
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