CN1006339B - Process for producing thick film of high-temp. superconductive ceramic material - Google Patents
Process for producing thick film of high-temp. superconductive ceramic materialInfo
- Publication number
- CN1006339B CN1006339B CN87103947A CN87103947A CN1006339B CN 1006339 B CN1006339 B CN 1006339B CN 87103947 A CN87103947 A CN 87103947A CN 87103947 A CN87103947 A CN 87103947A CN 1006339 B CN1006339 B CN 1006339B
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- CN
- China
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- hour
- film
- temperature
- base material
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Classifications
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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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
The present invention relates to a technology for producing thick films of a high-temperature superconductive ceramic material, which has the steps that superconductive ceramic micro powder is blended with organic adhesion solvent into pasty pulp, and then the pulp is printed on a base material in the mode of circuit wire laying or patterns by a technology of silk screen process; the base material printed with the pulp is sintered under strict heat processing program and then is manufactured into a superconductive film, and the thickness of the film is in the range of 15 to 80 micro meters. The superconductive transition temperature of the film layer is more than 90K, and the resistance temperature is more than 80K.
Description
The present invention relates to the preparation technology of superconductor or film
After it is found that superconductivity the beginning of this century, the superconductor transition temperature remains on low-temperature space (5K is following) always for a long time.The 50-70 age, the niobium three tin (Nb that the A-15 structure occurs having
3Sn), niobium three germanium (Nb
3Ge) superconductor, though its critical temperature bring up to about 20K because the low-temperature superconducting operating cost is too high, the value of still not applying.In recent years, new development appears in the research of superconductor, has the oxide La of layer structure
2-xM
xCuO
4-y(M=Ca, Sr and Ba) superconductor, its transition temperature is brought up to 30-40K.Soon, find Ba-Y-Cu-O superconductor system in succession, its superconducting transition temperature has reached more than the 90K, be higher than liquid nitrogen boiling point (77K), this quantum jump evokes the strong repercussion of countries in the world scientific and technological circle, and based on this material system, replace or add the 4th method such as oxide by ion, find a series of new similar superconductor systems again successively, its suiperconducting transition zero-resistance temperature is all at liquid nitrogen temperature.In view of superconductor good electricity and magnetic property, for energy savings, development new technologies, high-tech and utilize all many-sides such as natural resources all to have special practical value.The appearance of high-temperature superconductor is brought up to liquid nitrogen temperature to the superconduction working temperature, thereby promotes the situation apply greatly.Simultaneously, along with the progress of super conductor research work, the application and development work of high-temperature superconductor is generally paid attention in countries in the world.
By above-mentioned, task of the present invention is the application of development superconductor, superconductor is made suitable form, a kind of preparation superconductor thick-film technique is provided, and this film can be directly used in the various electronic devices of preparation or as an electronic circuit part, bring into play its superconduction function under weak current.
Main points of the present invention are the silk screen process technology transplant in preparation superconductor film-forming process.It is the superconductor that will produce with special process fine (pottery) powder, be modulated into the paste shape with suitable organic bond, with screen-printing thick-film technology (Silk Screen Printing), on base material, print circuitry needed wiring or pattern, after strict heat treatment process sinters superconductor rete or components and parts into.Technical process of the present invention is divided accent oar, system film and three steps of heat treatment.At first and based on this with the Ba-Y-Cu-O of suitable chemical composition, with high temperature (Tc) the superconductor system after respective element replacement Ba or the Y, as Ba-Ln-Cu-O(Ln=Gd wherein, Ho, Er, Dy, Yb) and Ba-Y-Nb-Cu-O, the superconductivity ceramics fine powder of Ba-Y-Bi-Cu-O system reconciles into the paste shape with organic bond.The general 400-500 order of this micro mist granularity.Transferring the used organic bond of oar is terpineol solution of ethyl cellulose, and wherein the ethyl cellulose cellulose content is 2-5%.Slurry can also can be modulated in the ball grinding cylinder of inner liner polytetrafluoroethylene in agate mortar or in the agate ball mill tube.Powder is generally 3～5 to 1 with the solid-to-liquid ratio of organic bond, this ratio depend primarily on the printing or painting process to the requirement of slurry viscosity, can make powder and solvent form good pastel, simultaneously, have certain flowability again.The system film is a method of size mixing material being utilized silk screen printing, is printed as needed pattern or wiring at substrate material surface.Also instrument such as available hairbrush on base material, forms desired element or circuit to slurry coating.Said base material comprises alumina ceramic plate used in electronic device or the integrated circuit, corundum sheet, sapphire wafer, cubic zirconia (Y
2O
3Stable ZrO
2) single-chip or polycrystalline ceramics sheet, and other insulating properties oxide ceramics substrate.At last, part is made in above-mentioned printing coating, under oxygen atmosphere, carried out sintering through strict heat treatment process.At first, can under infrared lamp or vacuum, dry, remove terpineol solution 80-90 ℃ of oven dry about 30 minutes, in tube furnace, to heat up with 2-3 ℃ of/minute speed, its segmentation temperature and retention time carry out in the following order: 150 ℃/1-3 hour, 400 ℃/1-4 hour, 850 ℃/1.5-3 hour, 950-1100 ℃/2-4 hour, be cooled to 800 ℃/2-4 hour with stove then, 400 ℃/3-5 hour, at last, naturally cool to room temperature, promptly make the superconductor rete.Wherein maximum heat treatment temperature 950-1100 ℃ is to decide according to the chemical composition of material.For example for Ba
xY
1-xCuO
3System when Ba content higher (X=60-65mol%), then should be used lower temperature, when Ba content less (X=30-40mol%), should use higher sintering temperature.
Above-mentioned technology has following requirement to used superconductivity ceramics micro mist: 1) chemical composition should be within the scope that can realize superconduction, as (Ba
xY
1-x)
3Cu
3O
9, 0.3≤X≤0.75 wherein, preferable 0.6≤X≤0.67 that consists of.The method of inspection be with behind the powder compressing tablet with above-mentioned heat treatment process sintering, should be able to obtain zero-resistance temperature more than 85K.2) the superconduction powder should have the close X-ray diffraction spectrum of superconduction sintered body, promptly close phase structure.3) powder particles is little, and the primary particle size should be less than 50nm, and the reactivity height is beneficial to sintering and forms the superconduction thing mutually like this.Based on requirement to ceramic, therefore, when the preparation powder, preferably use wet chemistry method, promptly be an example as preparing powder with the fixed method of oxalates chemical coprecipitation.Made powder through fully grinding, is looked specific requirement and is sieved before use.If use above-mentioned silk-screen printing technique, can cross the 400-500 mesh sieve.
The superconductor film that above-mentioned thick-film technique is prepared is generally 15-80 μ m or thicker.This rete shows microcosmic and examines through amplifying 2000, and its superconducting thick-film section is even and careful.Measure electricity group-temperature relation with the direct current four-terminal method, its suiperconducting transition initial temperature is higher than 90K, and zero-resistance temperature surpasses 80K, and it is surplus that this material thick film is placed in the air the nearly moon, and its superconductivity does not have significant change.
Embodiment: with oxalate coprecipitation method, through the 850-870 ℃ of prepared powder of calcination, chemical composition is Ba
1.8Y
1.2Cu
2O
y, ground 500 mesh sieves through pulverizing, reconcile into paste with the terpineol solution that contains 5% ethyl cellulose, it is solid: liquid=3: 1 on potsherd and jewel wafer, makes the rete of different-thickness with silk screen method.Baking is 20 minutes under infrared lamp, heat treatment in the oxygen atmosphere then, and its temperature and retention time, order is: 150 ℃/1 hour, 400 ℃/2 hours, 850 ℃/2 hours, 1050 ℃/2 hours, 800 ℃/2 hours, 400 ℃/2 hours, naturally cool to room temperature again.
Made film layer, through resistance-temperature measuring data such as following table:
| Thicknesses of layers (μ m) | 25 | 35 | 30 | |
| Base material | Sapphire | Sapphire | The ALO potsherd | |
| Measure after 24 hours | Initial transition temperature (K) | 92 | 93 | 93 |
| Change neutral temperature (K) | 88.5 | 89.5 | 89.5 | |
| Zero-resistance temperature (K) | 80 | 84.5 | 84 | |
| Measure after 25 days | Initial transition temperature (K) | 93 | 93 | 92 |
| Change neutral temperature (K) | 87 | 89.5 | 89.5 | |
| Zero-resistance temperature (K) | 79.5 | 84.5 | 84 | |
Accompanying drawing is the resistance-temperature relationship curve that this embodiment surveyed after a couple of days, and wherein the A curve is Al
2O
3Ceramic bases, B curve are the sapphire substrate.
Claims (5)
1, a kind of preparation high temperature (Tc) superconducting ceramics thick-film technique, it is characterized in that this technology comprises sizes mixing, makes film and heat treatment, said sizing mixing is 400-500 order superconducting ceramic oxide micro mist to be added organic bond reconcile into the paste shape, its solid-liquid=3-5/1; The system film is to use silk screen process, and size mixing material is printed on the base material; Sinter the superconduction rete into through heat treatment again, this heat treatment overall process is all carried out under oxygen atmosphere, 80-90 ℃ of oven dry about 0.5 hour, heat up with 2-3 ℃ of/minute speed in tube furnace earlier, each section temperature and retention time are in proper order: 150 ℃ 1-3 hour, 400 ℃/1-4 hour, 850 ℃/1.5-3 hour, 950-1100 ℃/2-4 hour, be cooled to 800 ℃/2-4 hour with stove then, 400 ℃/3-5 hour, naturally cool to room temperature at last.
2, technology according to claim 1 is characterized in that said organic bond is the terpineol solution that contains the 2-5% ethyl cellulose.
3, technology according to claim 1 is characterized in that base material comprises alumina ceramic plate, corundum sheet, sapphire wafer, cubic zirconia single-chip or polycrystalline ceramics sheet.
4, technology according to claim 1 is characterized in that oxide superconducting powder applicatory comprises Ba-Y-Cu-O and Ba-Y-Nb-Cu-O, the Ba-Y-Bi-Cu-O system.
5, technology according to claim 1 is characterized in that the also available direct brushing method of said system film, with the slurry brushing on base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103947A CN1006339B (en) | 1987-05-22 | 1987-05-22 | Process for producing thick film of high-temp. superconductive ceramic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103947A CN1006339B (en) | 1987-05-22 | 1987-05-22 | Process for producing thick film of high-temp. superconductive ceramic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031906A CN1031906A (en) | 1989-03-22 |
| CN1006339B true CN1006339B (en) | 1990-01-03 |
Family
ID=4814653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87103947A Expired CN1006339B (en) | 1987-05-22 | 1987-05-22 | Process for producing thick film of high-temp. superconductive ceramic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006339B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101471161B (en) * | 2007-12-28 | 2010-12-08 | 北京有色金属研究总院 | Method for producing high-temperature superconducting thin film by tri-fluorate |
| CN102509765B (en) * | 2011-11-17 | 2013-08-14 | 北京鼎臣超导科技有限公司 | Method capable of preparing Bi-2212 high-temperature superconducting thick film in chemical solution manner |
| CN111359564B (en) * | 2020-03-30 | 2021-06-08 | 黄山学院 | Method for synthesizing high-quality inorganic membrane by microwave heating |
| CN115299332A (en) * | 2022-07-21 | 2022-11-08 | 广东金莱特智能科技有限公司 | Indoor planter with heating function |
-
1987
- 1987-05-22 CN CN87103947A patent/CN1006339B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031906A (en) | 1989-03-22 |
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