CN101281806A - Method for preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition - Google Patents
Method for preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition Download PDFInfo
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- CN101281806A CN101281806A CNA2008100446290A CN200810044629A CN101281806A CN 101281806 A CN101281806 A CN 101281806A CN A2008100446290 A CNA2008100446290 A CN A2008100446290A CN 200810044629 A CN200810044629 A CN 200810044629A CN 101281806 A CN101281806 A CN 101281806A
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- cerium
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- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 239000004020 conductor Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008021 deposition Effects 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 title claims description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- -1 rare-earth acetate Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 60
- 238000002360 preparation method Methods 0.000 claims description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 10
- 229910052771 Terbium Inorganic materials 0.000 claims description 8
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 20
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 20
- 238000001035 drying Methods 0.000 abstract description 7
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 239000000956 alloy Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000002887 superconductor Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- 241000954177 Bangana ariza Species 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JQBILSNVGUAPMM-UHFFFAOYSA-K terbium(3+);triacetate Chemical compound [Tb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JQBILSNVGUAPMM-UHFFFAOYSA-K 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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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
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A method for producing the buffer layer of a conductor coated with high temperature superconducting coating by means of macromolecule assisted deposition, which comprises: a. preparing waterless: weigh rare-earth acetate, or rare-earth propoxide, or rare-earth acetylacetonate, or zirconium propoxide, or zirconium n-butoxide and cerium acetylacetonate at an ionic ratio of rare-earth or zirconium: cerium as x:1-x (0.01<=x<=0.5), dissolve the compound in an organic solvent to form a waterless; b. preparing colloid: add polyvinyl butyral, or polyethylene glycol, or polyvinyl pyrrolidone, or polyvinyl alcohol, or polyoxyethylene to the waterless solution to form colloid; c. coating the colloid and drying: coat the colloid on a substrate and then dry the substrate; d. sintering: load the substrate into a sintering oven, heat up to 850-1150 DEG C at 5-100DEG C/min, hold for 0.25-2h, and drop the temperature at 1-2 DEG C/min to room temperature. The method is characterized in simple process, easy operation control, low cost, and free of environment pollution; the single-layer cerium oxide buffer layer obtained can be in critical thickness of 150-200nm.
Description
Technical field
The present invention relates to a kind of preparation method of conductor of high-temperature superconductor coat, relate in particular to a kind of preparation method of buffer layers of high-temperature superconducting coating conductors.
Background technology
Second generation belt material of high temperature superconduct---RE, Ba and Cu oxide REBCO coating conductor because its good intrinsic electromagnetic property, especially its current capacity good under the highfield, is gathered around in electric power system and is had broad application prospects.
The composition of the high-temperature superconductor layer of coating conductor is REBa
2Cu
3O
x(be called for short REBCO, RE is yttrium or lanthanide series).For practical application area such as superconducting wire, superconducting magnets, the REBCO high-temperature oxide superconducting material of fragility must be coated in could reduce on the good metal substrate of mechanical performance (intensity, toughness) avoid processing or use in mechanical damage.In addition, this backing material also need have good electrical conductivity and thermal conductivity, to avoid in the use because thrashing and collapse that local quench causes.
The high-temperature superconductor layer material is because the layer structure of itself causes extremely strong anisotropy, and the load current ability on the ab face of lattice is higher than the c direction of principal axis far away.The current-carrying performance of REBCO high temperature superconducting materia is also very responsive to the lattice mismatch on a, the b direction, and big lattice mismatch angle will form weak connection, has a strong impact on its current capacity.Studies show that the current capacity of REBCO is exponential damping with the increase at lattice mismatch angle on a, the b direction.Reduce lattice mismatch angle on a, the b direction, reduce weak joint efficiency, guarantee the current capacity of REBCO, extension has been configured to indispensable technical process in its technology of preparing.Up to now, the best backing material of generally acknowledging both at home and abroad is the Ni base alloy material.Because there is certain lattice mismatch in the ab face of Ni base alloy and REBCO high temperature superconducting materia, directly epitaxial growth REBCO high temperature superconducting materia almost is impossible on the Ni base alloy baseband.Moreover, in the one-tenth phase heat treatment process of REBCO, having stronger counterdiffusion mutually and chemical reaction between Ni base alloy and the REBCO, this has just had a strong impact on the superconductivity of REBCO.Therefore, between Ni base alloy substrate and REBCO, must increase one deck cushioning layer material, should serve as from Ni base alloy to the epitaxially grown intermediate die plate of REBCO, stop the phase counterdiffusion of two kinds of materials again, mainly be Ni with REBCO in the counterdiffusion mutually of Cu, could guarantee to prepare the REBCO conductor of high-temperature superconductor coat of function admirable like this.Therefore, conductor of high-temperature superconductor coat all has substrate, resilient coating (one deck at least) and REBCO superconducting coating three-decker.
The preparation of the cushioning layer material of research coating conductor has positive meaning, and it will greatly simplify the structure and the preparation technology of coating conductor, reduces the preparation cost of superconductor, improves the cost performance of coating conductor.At present, cerium oxide CeO
2It is widely used cushioning layer material in the coating conductor.But, the cerium oxide CeO of existing preparation
2All there is the critical thickness of 50-70nm in the individual layer cushioning layer material, is difficult to intercept the diffusion of Ni, thereby is difficult to play well the effect of resilient coating.For improving the thickness of individual layer cushioning layer material, existing method is to utilize physical vaporous deposition to prepare rear-earth-doped or zirconium doping of cerium oxide CeO
2The individual layer resilient coating, its critical thickness can reach 200nm.But the physical gas-phase deposite method system complex, the cost costliness is unsuitable for large-scale industrial production.
Summary of the invention
Purpose of the present invention just provides a kind of method of preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition.This method manufacture craft is simple, and operation control is easy, and cost is low, and is free from environmental pollution; The cerium oxide CeO for preparing
2The critical thickness of individual layer resilient coating reaches 150-200nm.
The technical solution adopted for the present invention to solve the technical problems is, a kind of method of preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition, and its concrete practice is:
A, anhydrous solution preparation: the ion ratio x that presses rare earth or zirconium and cerium: 1-x 0.01≤x≤0.5 weighing rare earth acetate or rare earth propylate or rare earth acetylacetonate or propyl alcohol zirconium or tetrabutyl zirconate and acetylacetone,2,4-pentanedione cerium, be dissolved in then in organic solvent acetate or methyl alcohol or the EGME, form anhydrous solution; Rare earth is a kind of in yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), the lutetium (Lu).
B, colloid for preparing: in a anhydrous solution in step, add polyvinyl butyral resin (PVB) or polyethylene glycol (PEG) or PVP (PVP) or polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO) and be formed into colloid.
C, colloid coating are with dry: the colloid that the b step is made is coated on the substrate, and dry.
D, sinter phase into: dried substrate is put into sintering furnace sinter phase into, furnace temperature is risen to 850 ℃-1150 ℃ with the speed of 5-100 ℃/min, be incubated 0.25-2 hour, subsequently furnace temperature is reduced to room temperature with the speed of 1-2 ℃/min, promptly.
Compared with prior art, the beneficial effect of technical solution of the present invention is:
With acetylacetone,2,4-pentanedione cerium and alloy-rare earth acetate or rare earth propylate or rare earth acetylacetonate or propyl alcohol zirconium or tetrabutyl zirconate, be dissolved in the corresponding organic solvent and form anhydrous solution, in anhydrous solution, add macromolecular material again and form organic substance colloidal dispersion.Acetylacetone,2,4-pentanedione cerium and alloy are evenly distributed in this colloidal dispersion as deposit, promptly are evenly distributed on the substrate after the coating, become phase by high temperature sintering then, prepare rare earth or zirconium doping of cerium oxide resilient coating.The macromolecule polymer material of choosing is in the forming process of resilient coating, play following effect: improve the viscosity that contains sedimental whole organic system, make it be suitable for coating, acetylacetone,2,4-pentanedione cerium and alloy evenly distribute, it is effective to mix, and the thickness of resilient coating is improved; And set up extremely strong link between macromolecule polymer material that in organic-compound system, adopts and the acetylacetone,2,4-pentanedione cerium deposit, the 3 D stereo network that formation has good stability, thus the stress of film can discharge by the relaxation of three-dimensional structure in sintering process; Can avoid so also promptly forming in the process of resilient coating in the sintering film forming, owing to thin-film memory Stress Release cause the generation of micro-crack, thereby further improved the critical thickness of resilient coating.In preparation process, the additional proportion of control cerium salt and rare earth organic salt or organic zirconates can make things convenient for the Doped Rare Earth in the cerium oxide individual layer resilient coating of controlled doping or the cation proportioning of zirconium ion and cerium, thereby controls the thickness of resilient coating.
In a word, by the assistant depositing effect of the macromolecule polymer material selected for use and the doping effect of corresponding rare earth organic salt or organic zirconates, it is good to adopt the inventive method to make doping of cerium oxide individual layer resilient coating texture, the surfacing densification, critical thickness reaches 150-200nm, as its function admirable of individual layer resilient coating of coating conductor.And the preparation technology of the inventive method is simple, and operation control easily; In whole process of preparation, do not use the harmful substance of contaminated environment yet, free from environmental pollution.
In the phase front that sinters into of carrying out the above-mentioned d step, also carry out the preceding thermal decomposition process of sintering, its concrete practice is: the substrate that will be coated with colloid places sintering furnace, makes furnace temperature rise to 200 ℃-230 ℃ from room temperature, speed with 0.1-1 ℃/min rises to 280 ℃-400 ℃ again, is incubated 15-20 minute.Handle through the predecomposition before such sintering, the resilient coating that can make sintering form is more smooth finer and close.
The colloid coating with the concrete practice of drying was during above-mentioned c went on foot: on substrate, with the sol evenning machine rotation, colloid evenly is coated on the substrate colloid drops, baking temperature is 100 ℃-200 ℃.Under this temperature conditions, can so that the organic solvent in the colloid can be more, vapor away quickly.
Below in conjunction with the drawings and specific embodiments the present invention is done a step explanation.
Description of drawings
Fig. 1 is the terbium Tb doping of cerium oxide Tb of the embodiment of the invention one
0.4Ce
0.6O
1.8The X ray diffracting spectrum of the individual layer resilient coating of coating conductor.
Fig. 2 is the terbium Tb doping of cerium oxide Tb of the embodiment of the invention one
0.4Ce
0.6O
1.810000 times of scanning electron microscopy (SEM) photo of the individual layer resilient coating of coating conductor.
Fig. 3 is the terbium Tb doping of cerium oxide Tb of the embodiment of the invention one
0.4Ce
0.6O
1.8The thickness measuring result of the individual layer resilient coating of coating conductor.
Fig. 4 is the zirconium Zr doping of cerium oxide Zr of the embodiment of the invention four
0.5Ce
0.5O
2The X ray diffracting spectrum of the individual layer resilient coating of coating conductor.
Fig. 5 is the zirconium Zr doping of cerium oxide Zr of the embodiment of the invention four
0.5Ce
0.5O
210000 times of scanning electron microscopy (SEM) photo of the individual layer resilient coating of coating conductor.
Fig. 6 is the zirconium Zr doping of cerium oxide Zr of the embodiment of the invention four
0.5Ce
0.5O
2The thickness measuring result of the individual layer resilient coating of coating conductor.
Among Fig. 1, Fig. 4, ordinate is diffracted intensity (Intensity), arbitrary unit (a.u.); Abscissa is the angle of diffraction 2 θ, and unit is degree (deg).。Among Fig. 3, Fig. 6, abscissa is the horizontal displacement of the probe of step tester, and ordinate is the vertical deviation of measuring, the unit nanometer.
Embodiment
Embodiment one
A kind of embodiment of the present invention is:
The preparation of a, anhydrous solution: is terbium (Tb) with acetate terbium and acetylacetone,2,4-pentanedione cerium in cation ratio: the ratio of cerium (Ce)=0.01: 0.99, be dissolved in the acetate, and form anhydrous solution.
B, colloid for preparing: in a anhydrous solution in step, add polyvinyl butyral resin (PVB), form the colloid of good film-forming property.
C, colloid coating are with dry: the colloid that the b step is made is coated on the Ni alloy substrates, places 200 ℃ to carry out drying again.
Thermal decomposition process before the sintering: the substrate that will be coated with colloid places sintering furnace, makes furnace temperature slowly rise to 210 ℃ from room temperature, and rises to 290 ℃ with the speed of 0.15 ℃/min, is incubated 20 minutes.
D, sinter phase into: place sintering furnace to put into sintering furnace the substrate after the thermal decomposition, with furnace temperature fast with rise to 1150 ℃ of 100 ℃/min, be incubated 2 hours, furnace temperature is reduced to room temperature with the speed of 1 ℃/min subsequently, promptly makes terbium doped cerium oxide high-temperature superconducting coating conductor buffer layer.The molecular formula of the padded coaming that this is routine is specially Tb
0.01Ce
0.99O
1.995
Embodiment two
This routine preparation method is made of following steps successively:
The preparation of a, anhydrous solution: with propyl alcohol praseodymium and acetylacetone,2,4-pentanedione cerium by cation ratio Pr: Ce=0.1: 0.9 ratio is dissolved in the methyl alcohol formation anhydrous solution.
B, colloid for preparing: in a anhydrous solution in step, add polyethylene glycol (PEG), form the colloid of good film-forming property.
C, colloid coating are with dry: the colloid that the b step is made is coated on the Ni alloy substrates, places 100 ℃ to carry out drying again.
Carry out the preceding thermal decomposition process of sintering: the substrate that will be coated with colloid places sintering furnace, makes furnace temperature slowly rise to 200 ℃ from room temperature, and rises at 280 ℃ with the speed of 0.1 ℃/min, is incubated 15 minutes.
D, sinter phase into: place sintering furnace to put into sintering furnace the substrate after the thermal decomposition, furnace temperature fast with rise to 850 ℃ of 5 ℃/min, is incubated 0.5 hour, furnace temperature is reduced to room temperature with the speed of 2 ℃/min subsequently, and promptly making molecular formula is Pr
0.1Ce
0.9O
1.95The doped cerium oxide buffer layers of high-temperature superconducting coating conductors that constitutes
Embodiment three
This routine preparation method is made of following steps successively:
The preparation of a, anhydrous solution: with acetylacetone,2,4-pentanedione dysprosium and acetylacetone,2,4-pentanedione cerium by cation ratio Dy: Ce=0.3: 0.7 ratio is dissolved in the EGME formation anhydrous solution.
B, colloid for preparing: in a anhydrous solution in step, add PVP (PVP), form the colloid of good film-forming property.
C, colloid coating are with dry: the colloid that the b step is made is coated on the Ni alloy substrates, places 150 ℃ to carry out drying again.
Carry out the preceding thermal decomposition process of sintering: the substrate that will be coated with colloid places sintering furnace, makes furnace temperature slowly rise to 215 ℃ from room temperature, and rises at 350 ℃ with the speed of 0.5 ℃/min, is incubated 18 minutes.
D, sinter phase into: place sintering furnace to put into sintering furnace the substrate after the thermal decomposition, with furnace temperature fast with rise to 1000 ℃ of 25 ℃/min, be incubated 1 hour, furnace temperature is reduced to room temperature with the speed of 1.5 ℃/min subsequently, promptly make by dysprosium doping of cerium oxide buffer layers of high-temperature superconducting coating conductors, the molecular formula of the cushioning layer material that this is routine is Dy
0.3Ce
0.7O
1.85
Embodiment four
This routine preparation method is made of following steps successively:
The preparation of a, anhydrous solution: with propyl alcohol zirconium and acetylacetone,2,4-pentanedione cerium by cation ratio Zr: Ce=0.01: 0.99 ratio is dissolved in the methyl alcohol formation anhydrous solution.
B, colloid for preparing: in a anhydrous solution in step, add polyethylene glycol oxide (PEO), form the colloid of good film-forming property.
C, colloid coating are with dry: the colloid that the b step is made is coated on the Ni alloy substrates, places 200 ℃ to carry out drying again.
Carry out the preceding thermal decomposition process of sintering: the substrate that will be coated with colloid places sintering furnace, makes furnace temperature slowly rise to 230 ℃ from room temperature, and rises at 400 ℃ with the speed of 1 ℃/min, is incubated 15 minutes.
D, sinter phase into: place sintering furnace to put into sintering furnace the substrate after the thermal decomposition, with furnace temperature fast with rise to 1150 ℃ of 100 ℃/min, be incubated 2 hours, furnace temperature is reduced to room temperature with the speed of 1 ℃/min subsequently, promptly make by zirconium doping of cerium oxide buffer layers of high-temperature superconducting coating conductors, the molecular formula of the resilient coating that this is routine is Zr
0.01Ce
0.99O
2
Embodiment five
This routine preparation method is made of following steps successively:
The preparation of a, anhydrous solution: with tetrabutyl zirconate and acetylacetone,2,4-pentanedione cerium by cation ratio Zr: Ce=0.5: 0.5 ratio is dissolved in the EGME formation anhydrous solution.
B, colloid for preparing: in a anhydrous solution in step, add polyvinyl alcohol (PVA), form the colloid of good film-forming property.
C, colloid coating are with dry: the colloid that the b step is made is coated on the Ni alloy substrates, places 100 ℃ to carry out drying again.
D, sinter phase into: place sintering furnace to put into sintering furnace dried substrate, with furnace temperature fast with rise to 850 ℃ of 5 ℃/min, be incubated 0.25 hour subsequently furnace temperature reduce to room temperature with the speed of 2 ℃/min, promptly make by zirconium doping of cerium oxide buffer layers of high-temperature superconducting coating conductors, the molecular formula of the resilient coating that this is routine is Zr
0.5Ce
0.7O
2
Fig. 1,4 is respectively the X ray diffracting spectrum of the resilient coating that embodiment one, four makes, and as seen from the figure, the resilient coating that the ownership gets has good c-axis texture for being cubic structure; 10000 times of scanning electron microscopy (SEM) photo of Fig. 2,5 resilient coatings that make for embodiment one, four, as seen from the figure, all smooth densification of all buffer-layer surfaces does not have tangible crackle and hole; The resilient coating that Fig. 3,6 makes for embodiment one, four adopts the step instrument to test the result of its thickness, and as seen from the figure, the thickness of all individual layer resilient coatings is all greater than 150nm.
Because yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) that the present invention uses, these elements all belong to rare earth element, they are at chemical property such as ionic valence condition, extremely close on the ionic radius, replace each other easily and intersolubility fine, the oxide of its formation all belongs to cubic system, and lattice parameter all mates with REBCO or Ni alloy phase.In addition, the oxide of element zirconium (Zr) and elemental cerium (Ce) can dissolve each other with bigger solid solubility.Therefore, be not limited to the element among the above embodiment, and adopt any one element in rare earth element and the zr element or the mixing of more than one elements, all can prepare the cerium oxide individual layer resilient coating of the rare earth doped or zirconium of function admirable.
The present invention is dissolved in organic solvent when forming anhydrous solution at alloy and acetylacetone,2,4-pentanedione cerium, and the amount of organic solvent gets final product with alloy and the acetylacetone,2,4-pentanedione cerium that it can fully dissolve adding.The part by weight 1 of common alloy and acetylacetone,2,4-pentanedione cerium and organic solvent: 3-8.The addition of polyvinyl butyral resin (PVB) or polyethylene glycol (PEG) or PVP (PVP) or polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO) is not strict with yet in b goes on foot, as long as can make anhydrous solution be formed into the good colloid of film properties.
Claims (3)
1, a kind of method of preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition, its concrete practice is:
A, anhydrous solution preparation: the ion ratio x that presses rare earth or zirconium and cerium: 1-x 0.01≤x≤0.5 weighing rare earth acetate or rare earth propylate or rare earth acetylacetonate or propyl alcohol zirconium or tetrabutyl zirconate and acetylacetone,2,4-pentanedione cerium, be dissolved in then in organic solvent acetate or methyl alcohol or the EGME, form anhydrous solution; Rare earth is a kind of in yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), the lutetium (Lu);
B, colloid for preparing: in a anhydrous solution in step, add polyvinyl butyral resin (PVB) or polyethylene glycol (PEG) or PVP (PVP) or polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO) and be formed into colloid;
C, colloid coating are with dry: the colloid that the b step is made is coated on the substrate, and dry;
D, sinter phase into: dried substrate is put into sintering furnace sinter phase into, furnace temperature is risen to 850 ℃-1150 ℃ with the speed of 5-100 ℃/min, be incubated 0.25-2 hour, subsequently furnace temperature is reduced to room temperature with the speed of 1-2 ℃/min, promptly.
2, the method for a kind of preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition as claimed in claim 1, it is characterized in that: carrying out before sintering into of described d step handle mutually, also carry out thermal decomposition process, its concrete practice is: the substrate that will be coated with colloid places sintering furnace, make furnace temperature rise to 200 ℃-230 ℃ from room temperature, speed with 0.1-1 ℃/min rises to 280 ℃-400 ℃ again, is incubated 15-20 minute.
3, the method for a kind of preparing high temperature superconduction coating conductor buffer layer using polymer auxiliary deposition as claimed in claim 1, it is characterized in that: described c in the step colloid coating with the dry concrete practice be: with colloid drops on substrate, rotate with sol evenning machine, colloid evenly is coated on the substrate, and baking temperature is 100 ℃-200 ℃.
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