CN101649451A - MOD method for preparing LSCO conductive film on biaxial texture NiW alloy - Google Patents

MOD method for preparing LSCO conductive film on biaxial texture NiW alloy Download PDF

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CN101649451A
CN101649451A CN200910187309A CN200910187309A CN101649451A CN 101649451 A CN101649451 A CN 101649451A CN 200910187309 A CN200910187309 A CN 200910187309A CN 200910187309 A CN200910187309 A CN 200910187309A CN 101649451 A CN101649451 A CN 101649451A
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acetate
strontium
lanthanum
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李英楠
樊占国
李凤华
沈悦
罗清威
李成山
卢亚峰
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Northeastern University China
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Abstract

The invention relates to an MOD method for preparing an LSCO conductive film on biaxial texture NiW alloy, which belongs to the technical field of superconducting materials. The method comprises the following steps: dissolving strontium acetate, lanthanum acetate and cobaltous acetate into propionic acid step by step and adding acetylacetone to prepare precursor solution; coating the precursor solution on a biaxial texture NiW base band by a glue homogenizing machine; then carrying out pyrolysis processing and carrying out coating and pyrolysis processing again; and carrying out crystallization reaction. The prepared LSCO film has the thickness of 500-700nm, obstructs the diffusion process of a Ni element to a YBCO layer and favorably prevents the oxidation of an NiW substrate; and the electrical resistivity of the film, which is detected by a four-lead method can reach 1.1*10<-4>omega*m in a liquid nitrogen temperature zone. Compared with the traditional process, the invention reducesthe number of buffer layers, thereby reducing the preparation process and the manufacture cost of a YBCO/buffer/NiW composite material.

Description

The MOD method prepares lanthanum-strontium-cobalt-oxygen conductive film on biaxial texture NiW alloy
Technical field
The invention belongs to the superconducting material technical field, be specifically related to YBCO superconducting tape technology.
Background technology
YBa 2Cu 3O 7-x(YBCO) be a kind of very promising high temperature superconducting materia, be with a wide range of applications in fields such as electron devices.Since a lot of metal ions at high temperature can with the mutual diffusion mutually of YBCO layer, and then can the serious superconductivity that reduces YBCO, therefore need on the metal substrate earlier one or more layers cushioning layer material of deposition to stop the diffusion between metal substrate and the YBCO layer; In addition, with regard to the YBCO film, have biaxial texture and just can possess good supraconductivity, this just requires buffer layer and substrate and YBCO to have excellent lattice matching, and the biaxial texture extension of metal substrate is passed to the YBCO layer.Therefore in the process of preparation YBCO coating conductor band, the buffer layer of preparation low cost, high quality, good stability becomes a key technique.
At present, a lot of technologies all are used to prepare high-quality buffer layer, the equipment manufacturing cost of PLD, CSV and hot spray process is high, and MOD method (deposition of metal organic method) can be used for the extensive concern that numerous advantages such as big area deposition and accurate control stoichiometric ratio are subjected to the investigator because equipment is simple and with low cost.For YBCO coating superconducting band, the electric current of YBCO layer is diverted on the conductive substrates (as the NiW alloy, Ag etc.), thereby alleviate the YBCO layer local overload takes place, just can improve the superconductivity of YBCO film, therefore, preparation conductie buffer coating systems connects YBCO layer and conductive substrates, has become one of focus of superconducting tape research.At present, prepared La with the chemical solution deposition method xSr 1-xThe TiO3 conductive buffer layer has prepared La with hot spray process 0.5Sr 0.5CoO 3Conductive buffer layer, (PLD) prepared LaTiO with pulsed laser deposition 3+xConductive buffer layer has prepared BaPbO with the CSD method 3Conductive buffer layer.But also do not find at present on the NiW of biaxial texture alloy, to prepare La with the MOD method xSr 1-xCoO 3The relevant report of conductive buffer layer.
LaSrCoO has cubic perovskite structure, and lattice parameter is
Figure G2009101873095D00011
Thermal expansivity is 22.3 * 10 -6/ K, good (the a-b shaft lattice constant of YBCO is respectively with the matching of YBCO
Figure G2009101873095D00012
With
Figure G2009101873095D00013
Thermal expansivity is 11～15 * 10 -6/ K), lattice mismatch is 1.3%; On the other hand, NiW (100) alloy of Xibei Inst. of Non-Ferrous Metals superconducting material institute research and development has
Figure G2009101873095D00014
Lattice parameter, 12.8 * 10 -6The thermal expansivity of/K, the lattice mismatch of LaSrCoO/NiW (100) is 8.19%, therefore probably prepares YBCO/LaSrCoO/NiW (100) matrix material with the MOD method on NiW (100) alloy.
Summary of the invention
Problem at existing among the above-mentioned YBCO superconducting material buffer layer preparation method the invention provides a kind of MOD method and prepare lanthanum-strontium-cobalt-oxygen (La on biaxial texture NiW alloy xSr 1-xCoO 3, 0.4≤x≤0.5) and conductive film, thus being reached for the later stage prepares the YBCO composite strip and simplifies the purpose that the quantity of technology, reduction buffer layer reduces production costs.
The processing step of the inventive method is as follows.
With strontium acetate (C 4H 6SrO 4), lanthanum acetate (C 6H 9LaO 61.5H 2O) and cobaltous acetate (C 4H 6CoO 44H 2O) three kinds of salt are dissolved into propionic acid (C step by step 2H 5COOH) in, make the mixing solutions of strontium acetate, lanthanum acetate and cobaltous acetate.That is:
With strontium acetate (C 4H 6SrO 4) join propionic acid (C 2H 5COOH) in, stirring and dissolving adds lanthanum acetate (C in gained solution 6H 9LaO 61.5H 2O), stirring and dissolving adds cobaltous acetate (C again in the propionic acid solution of the strontium acetate of gained and lanthanum acetate 4H 6CoO 44H 2O), stirring and dissolving.
The mol ratio of control lanthanum acetate, strontium acetate and three kinds of salt of cobaltous acetate is a lanthanum acetate: strontium acetate: cobaltous acetate=x: (1-x): 1.0 (0.4≤x≤0.5), lanthanum ion, strontium ion and concentration of cobalt ions sum are 0.8～1.0mol/L.
In the propionic acid solution of strontium acetate, lanthanum acetate and the cobaltous acetate of gained, add methyl ethyl diketone as stablizer, per-cent meter by volume, the amount of methyl ethyl diketone be strontium acetate, lanthanum acetate and cobaltous acetate the propionic acid solution amount 10～15%, solution is the purple vitreous state, promptly makes precursor liquid.
Precursor liquid is coated on the biaxial texture NiW base band under 10～20 seconds condition of 3500～4000 rev/mins of rotations of rotating speed with sol evenning machine, the biaxial texture NiW base band thickness 0.15～0.2mm that adopts, it forms W 3～5% by mass percentage, Ni95～97%.
The NiW base band that will apply precursor liquid is then sent into tube furnace, carry out pyrolysis processing, intensification, cooling system are: be warming up to 180～200 ℃ with 150～200 ℃/hour temperature rise rates, be warming up to 240～260 ℃ with 5～10 ℃/hour temperature rise rates, be warming up to 290～310 ℃ with 40～60 ℃/hour temperature rise rates, be warming up to 390～410 ℃ with 80～120 ℃/hour temperature rise rates, reduce to room temperature with stove then.Gas in the tube furnace is pressure 0.05～0.15MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 4～6%, and a nitrogen content is 94～96%.
According to the method described above, the NiW base band that applies precursor liquid and carry out pyrolysis processing is applied and pyrolysis processing once more.
To send into tube furnace through the NiW base band of twice coating and pyrolysis processing, carry out crystallization reaction.Crystallisation process heats up, the cooling system is as follows.
Be warming up to 590～610 ℃ with 600～800 ℃/hour temperature rise rates, be warming up to 820～830 ℃, be incubated 1.5～2.5 hours, reduce to room temperature with stove then with 100～120 ℃/hour temperature rise rates.Gas in the tube furnace is pressure 0.05～0.15MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 4～6%, and a nitrogen content is 94～96%.
Advantage of the present invention is as follows.
The LSCO that the present invention grows on the NiW alloy (lanthanum-strontium-cobalt-oxygen) film, extension the cubic texture of NiW alloy, the highest 100 utmost point density are that 1774,100 φ scanning halfwidth is 0.726 °, help YBCO (yttrium barium copper oxide) layer of outer continued growth cubic texture; LSCO (lanthanum-strontium-cobalt-oxygen) film thickness of preparation is 500～700nm, has intercepted the diffusion process of Ni element to YBCO (yttrium barium copper oxide) layer, has also well stoped the oxidation of NiW substrate simultaneously; The resistivity of measuring film through four leads method can reach 1.1 * 10 at liquid nitrogen temperature -4Ω m.Compare with traditional technology, the present invention has simplified the quantity of buffer layer, thereby has reduced the preparation process and the manufacturing cost of YBCO/buffer/NiW matrix material.Wherein the meaning of Buffer is a buffer layer, comprises multiple layer under the traditional technology, and the present invention only substitutes traditional multilayered structure with LSCO one deck.
Description of drawings
Fig. 1 is the XRD figure spectrum φ-scanning of embodiment 1LaSrCoO film;
Fig. 2 is XRD figure spectrum (100) utmost point figure of embodiment 1LaSrCoO film;
Fig. 3 is the SEM photo of the LaSrCoO film of embodiment 1;
Fig. 4 is the resistivity-thetagram of embodiment 1LaSrCoO film.
Embodiment
Further specify method of the present invention by the following examples.
Embodiment 1
The MOD method prepares the processing step of lanthanum-strontium-cobalt-oxygen conductive film on biaxial texture NiW alloy as follows.
With strontium acetate (C 4H 6SrO 4), lanthanum acetate (C 6H 9LaO 61.5H 2O) and cobaltous acetate (C 4H 6CoO 44H 2O) three kinds of salt are dissolved into propionic acid (C step by step 2H 5COOH) in, make the mixing solutions of strontium acetate, lanthanum acetate and cobaltous acetate.That is:
With strontium acetate (C 4H 6SrO 4) join propionic acid (C 2H 5COOH) in, stirring and dissolving adds lanthanum acetate (C in gained solution 6H 9LaO 61.5H 2O), stirring and dissolving adds cobaltous acetate (C again in the propionic acid solution of the strontium acetate of gained and lanthanum acetate 4H 6CoO 44H 2O), stirring and dissolving.
The mol ratio of control lanthanum acetate, strontium acetate and three kinds of salt of cobaltous acetate is a lanthanum acetate: strontium acetate: cobaltous acetate=0.45: 0.55: 1.0, strontium ion, lanthanum ion and concentration of cobalt ions sum are 0.9mol/L.
In the propionic acid solution of strontium acetate, lanthanum acetate and the cobaltous acetate of gained, add methyl ethyl diketone as stablizer, per-cent meter by volume, the amount of methyl ethyl diketone be strontium acetate, lanthanum acetate and cobaltous acetate the propionic acid solution amount 12.5%, solution is the purple vitreous state, is precursor liquid.
Biaxial texture NiW base band (Xibei Inst. of Non-Ferrous Metals product) is cut into the fritter of 10cm * 10cm, precursor liquid is coated on the biaxial texture NiW base band under 15 seconds condition of 3750 rev/mins of rotations of rotating speed with sol evenning machine, the biaxial texture NiW base band thickness 0.18mm that adopts, it forms W4% by mass percentage, Ni96%.
The NiW base band that will apply precursor liquid is then sent into tube furnace, carry out pyrolysis processing, intensification, cooling system are: be warming up to 190 ℃ with 180 ℃/hour temperature rise rates, be warming up to 250 ℃ with 7.5 ℃/hour temperature rise rates, be warming up to 300 ℃ with 50 ℃/hour temperature rise rates, be warming up to 400 ℃ with 100 ℃/hour temperature rise rates, reduce to room temperature with stove then.Gas in the tube furnace is pressure 0.1MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 5%, and a nitrogen content is 95%.
According to the method described above, the NiW base band that applies precursor liquid and carry out pyrolysis processing is applied and pyrolysis processing once more.
To send into tube furnace through the NiW base band of twice coating and pyrolysis processing, carry out crystallization reaction.Crystallisation process heats up, the cooling system is as follows.
Be warming up to 600 ℃ with 700 ℃/hour temperature rise rates, be warming up to 825 ℃, be incubated 2 hours, reduce to room temperature with stove then with 110 ℃/hour temperature rise rates.Gas in the tube furnace is pressure 0.1MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 5%, and a nitrogen content is 95%.
With the microstructure of scanning electron microscopic observation LaSrCoO film, with X-ray diffractometer the LaSrCoO film is carried out preferred orientation and texture test, measure the resistivity-temperature characteristic of LaSrCoO film under no externally-applied magnetic field with four leads method.
The LSCO for preparing as can be seen from Fig. 1, Fig. 2 has in the good face and outside the face and is orientated, and evenly fine and close from the LSCO film that the SEM picture of Fig. 3 prepares as can be seen, microscopic appearance is good; From resistivity-temperature curve of Fig. 4, the LSCO film has good electrical conductivity, and still keeps this good electrical conductivity at liquid nitrogen temperature.
Embodiment 2
The MOD method prepares the processing step of lanthanum-strontium-cobalt-oxygen conductive film on biaxial texture NiW alloy as follows.
With strontium acetate (C 4H 6SrO 4), lanthanum acetate (C 6H 9LaO 61.5H 2O) and cobaltous acetate (C 4H 6CoO 44H 2O) three kinds of salt are dissolved into propionic acid (C step by step 2H 5COOH) in, make the mixing solutions of strontium acetate, lanthanum acetate and cobaltous acetate.That is:
With strontium acetate (C 4H 6SrO 4) join propionic acid (C 2H 5COOH) in, stirring and dissolving adds lanthanum acetate (C in gained solution 6H 9LaO 61.5H 2O), stirring and dissolving adds cobaltous acetate (C again in the propionic acid solution of the strontium acetate of gained and lanthanum acetate 4H 6CoO 44H 2O), stirring and dissolving.
The mol ratio of control lanthanum acetate, strontium acetate and three kinds of salt of cobaltous acetate is a lanthanum acetate: strontium acetate: cobaltous acetate=0.5: 0.5: 1.0, strontium ion, lanthanum ion and concentration of cobalt ions sum are 1.0mol/L.
In the propionic acid solution of strontium acetate, lanthanum acetate and the cobaltous acetate of gained, add methyl ethyl diketone as stablizer, per-cent meter by volume, the amount of methyl ethyl diketone be strontium acetate, lanthanum acetate and cobaltous acetate the propionic acid solution amount 15%, solution is the purple vitreous state, is precursor liquid.
Biaxial texture NiW base band (Xibei Inst. of Non-Ferrous Metals product) is cut into the fritter of 10cm * 10cm, precursor liquid is coated on the biaxial texture NiW base band under 10 seconds condition of 4000 rev/mins of rotations of rotating speed with sol evenning machine, the biaxial texture NiW base band thickness 0.2mm that adopts, it forms W 5% by mass percentage, Ni95%.
The NiW base band that will apply precursor liquid is then sent into tube furnace, carry out pyrolysis processing, intensification, cooling system are: be warming up to 200 ℃ with 200 ℃/hour temperature rise rates, be warming up to 260 ℃ with 10 ℃/hour temperature rise rates, be warming up to 310 ℃ with 60 ℃/hour temperature rise rates, be warming up to 410 ℃ with 120 ℃/hour temperature rise rates, reduce to room temperature with stove then.Gas in the tube furnace is pressure 0.15MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 6%, and a nitrogen content is 94%.
According to the method described above, the NiW base band that applies precursor liquid and carry out pyrolysis processing is applied and pyrolysis processing once more.
To send into tube furnace through the NiW base band of twice coating and pyrolysis processing, carry out crystallization reaction.Crystallisation process heats up, the cooling system is as follows.
Be warming up to 610 ℃ with 800 ℃/hour temperature rise rates, be warming up to 830 ℃, be incubated 1.5 hours, reduce to room temperature with stove then with 120 ℃/hour temperature rise rates.Gas in the tube furnace is pressure 0.15MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 6%, and a nitrogen content is 94%.
Embodiment 3
The MOD method prepares the processing step of lanthanum-strontium-cobalt-oxygen conductive film on biaxial texture NiW alloy as follows.
With strontium acetate (C 4H 6SrO 4), lanthanum acetate (C 6H 9LaO 61.5H 2O) and cobaltous acetate (C 4H 6CoO 44H 2O) three kinds of salt are dissolved into propionic acid (C step by step 2H 5COOH) in, make the mixing solutions of strontium acetate, lanthanum acetate and cobaltous acetate.That is:
With strontium acetate (C 4H 6SrO 4) join propionic acid (C 2H 5COOH) in, stirring and dissolving adds lanthanum acetate (C in gained solution 6H 9LaO 61.5H 2O), stirring and dissolving adds cobaltous acetate (C again in the propionic acid solution of the strontium acetate of gained and lanthanum acetate 4H 6CoO 44H 2O), stirring and dissolving.
The mol ratio of control lanthanum acetate, strontium acetate and three kinds of salt of cobaltous acetate is a lanthanum acetate: strontium acetate: cobaltous acetate=0.4: 0.6: 1.0, strontium ion, lanthanum ion and concentration of cobalt ions sum are 0.8mol/L.
In the propionic acid solution of strontium acetate, lanthanum acetate and the cobaltous acetate of gained, add methyl ethyl diketone as stablizer, per-cent meter by volume, the amount of methyl ethyl diketone be strontium acetate, lanthanum acetate and cobaltous acetate the propionic acid solution amount 10%, solution is the purple vitreous state, is precursor liquid.
Biaxial texture NiW base band (Xibei Inst. of Non-Ferrous Metals product) is cut into the fritter of 10cm * 10cm, precursor liquid is coated on the biaxial texture NiW base band under 20 seconds condition of 3500 rev/mins of rotations of rotating speed with sol evenning machine, the biaxial texture NiW base band thickness 0.15mm that adopts, it forms W 3% by mass percentage, Ni97%.
The NiW base band that will apply precursor liquid is then sent into tube furnace, carry out pyrolysis processing, intensification, cooling system are: be warming up to 180 ℃ with 150 ℃/hour temperature rise rates, be warming up to 240 ℃ with 5 ℃/hour temperature rise rates, be warming up to 290 ℃ with 40 ℃/hour temperature rise rates, be warming up to 390 ℃ with 80 ℃/hour temperature rise rates, reduce to room temperature with stove then.Gas in the tube furnace is pressure 0.05MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 4%, and a nitrogen content is 96%.
According to the method described above, the NiW base band that applies precursor liquid and carry out pyrolysis processing is applied and pyrolysis processing once more.
To send into tube furnace through the NiW base band of twice coating and pyrolysis processing, carry out crystallization reaction.Crystallisation process heats up, the cooling system is as follows.
Be warming up to 590 ℃ with 600 ℃/hour temperature rise rates, be warming up to 820 ℃, be incubated 1.5 hours, reduce to room temperature with stove then with 100 ℃/hour temperature rise rates.Gas in the tube furnace is pressure 0.05MPa, and furnace gas is nitrogen, hydrogen mixed gas, counts by volume, and hydrogen content is 4%, and a nitrogen content is 96%.

Claims (6)

1, a kind of MOD method prepares lanthanum-strontium-cobalt-oxygen conductive film on biaxial texture NiW alloy, it is characterized in that processing step is:
Be dissolved into strontium acetate, lanthanum acetate and three kinds of salt of cobaltous acetate in the propionic acid step by step, the mol ratio of control lanthanum acetate, strontium acetate and three kinds of salt of cobaltous acetate is a lanthanum acetate: strontium acetate: cobaltous acetate=x: (1-x): 1.0,0.4≤x≤0.5, strontium ion, lanthanum ion and concentration of cobalt ions sum are 0.8～1.0mol/L, in the propionic acid solution of lanthanum acetate, strontium acetate and the cobaltous acetate of gained, add methyl ethyl diketone as stablizer, promptly make precursor liquid;
With sol evenning machine precursor liquid is coated on the biaxial texture NiW base band;
The NiW base band that will apply precursor liquid is then sent into tube furnace, carry out pyrolysis processing, intensification, cooling system are: be warming up to 180～200 ℃ with 150～200 ℃/hour temperature rise rates, be warming up to 240～260 ℃ with 5～10 ℃/hour temperature rise rates, be warming up to 290～310 ℃ with 40～60 ℃/hour temperature rise rates, be warming up to 390～410 ℃ with 80～120 ℃/hour temperature rise rates, reduce to room temperature with stove then;
According to the method described above, the NiW base band that applies precursor liquid and carry out pyrolysis processing is applied and pyrolysis processing once more; To send into tube furnace through the NiW base band of twice coating and pyrolysis processing, carry out crystallization reaction, crystallisation process heats up, the cooling system is: be warming up to 590～610 ℃ with 600～800 ℃/hour temperature rise rates, be warming up to 820～830 ℃ with 100～120 ℃/hour temperature rise rates, be incubated 1.5～2.5 hours, reduce to room temperature with stove then.
2, prepare lanthanum-strontium-cobalt-oxygen conductive film according to the described MOD method of claim 1 on biaxial texture NiW alloy, it is characterized in that per-cent meter by volume, the amount of methyl ethyl diketone is 10～15% of a solution amount.
3, prepare lanthanum-strontium-cobalt-oxygen conductive film according to the described MOD method of claim 1 on biaxial texture NiW alloy, it is characterized in that with sol evenning machine precursor liquid being coated on the biaxial texture NiW base band, condition is 3500～4000 rev/mins of rotating speeds, rotates 10～20 seconds.
4, prepare lanthanum-strontium-cobalt-oxygen conductive film according to the described MOD method of claim 1 on biaxial texture NiW alloy, it is characterized in that biaxial texture NiW base band thickness 0.15～0.2mm of adopting, it forms W 3～5% by mass percentage, Ni95～97%.
5, on biaxial texture NiW alloy, prepare lanthanum-strontium-cobalt-oxygen conductive film according to the described MOD method of claim 1, it is characterized in that in the pyrolysis treatment step, gas in the tube furnace is pressure 0.05～0.15MPa, furnace gas is nitrogen, hydrogen mixed gas, count by volume, hydrogen content is 4～6%, and a nitrogen content is 94～96%.
6, on biaxial texture NiW alloy, prepare lanthanum-strontium-cobalt-oxygen conductive film according to the described MOD method of claim 1, it is characterized in that in the crystallization reaction step, gas in the tube furnace is pressure 0.05～0.15MPa, furnace gas is nitrogen, hydrogen mixed gas, count by volume, hydrogen content is 4～6%, and a nitrogen content is 94～96%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102061439A (en) * 2011-02-11 2011-05-18 西南交通大学 Method for preparing biaxial NiO (200) coating conductor buffer layers by medium-temperature surface oxidation epitaxy
CN104264132A (en) * 2014-09-18 2015-01-07 西北有色金属研究院 Single buffer layer of coated conductor and preparation method of single buffer layer
CN105296967A (en) * 2015-10-26 2016-02-03 西北有色金属研究院 Preparation method for pyrochlore-type Gd2Ti2O7 buffer layer thin film
CN115148411A (en) * 2022-07-18 2022-10-04 富通集团（天津）超导技术应用有限公司 YBCO superconducting ring manufacturing device and process method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102061439A (en) * 2011-02-11 2011-05-18 西南交通大学 Method for preparing biaxial NiO (200) coating conductor buffer layers by medium-temperature surface oxidation epitaxy
CN102061439B (en) * 2011-02-11 2012-10-03 西南交通大学 Method for preparing biaxial NiO (200) coating conductor buffer layers by medium-temperature surface oxidation epitaxy
CN104264132A (en) * 2014-09-18 2015-01-07 西北有色金属研究院 Single buffer layer of coated conductor and preparation method of single buffer layer
CN105296967A (en) * 2015-10-26 2016-02-03 西北有色金属研究院 Preparation method for pyrochlore-type Gd2Ti2O7 buffer layer thin film
CN105296967B (en) * 2015-10-26 2018-07-10 西北有色金属研究院 A kind of pyrochlore-type Gd2Ti2O7The preparation method of buffer layer thin film
CN115148411A (en) * 2022-07-18 2022-10-04 富通集团（天津）超导技术应用有限公司 YBCO superconducting ring manufacturing device and process method

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