CN113593765A - Preparation method of bismuth-based high-temperature superconducting wire/strip - Google Patents

Preparation method of bismuth-based high-temperature superconducting wire/strip Download PDF

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CN113593765A
CN113593765A CN202110761866.4A CN202110761866A CN113593765A CN 113593765 A CN113593765 A CN 113593765A CN 202110761866 A CN202110761866 A CN 202110761866A CN 113593765 A CN113593765 A CN 113593765A
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heat treatment
phase
silver
powder
strip
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CN113593765B (en
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崔利军
王明江
孙霞光
刘建伟
闫果
刘向宏
冯勇
张平祥
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Western Superconducting Technologies Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
    • H01B12/04—Single wire
    • 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

The invention discloses a preparation method of a bismuth-series high-temperature superconducting wire/strip, which comprises the following steps: 1) mixing raw materials, and carrying out pre-phase reaction to obtain a phase composition; 2) filling the obtained phase component powder into a silver tube, and carrying out phase forming heat treatment reaction to obtain precursor powder; 3) after the phase-forming heat treatment reaction, heating the silver tube filled with the precursor powder and vacuumizing the silver tube to obtain a Bi-2223 or Bi-2212 single core rod; 4) preparing Bi-2223 multi-core strip or Bi-2212 multi-core wire. The Bi-2223 superconducting tape and the Bi-2212 superconducting wire obtained by the preparation method can avoid the phenomena of tape bubbling and wire diameter thickening after final phase forming heat treatment of the wire tape due to gas adsorbed by the powder and residual gas between the powder, so that the critical current of the wire tape is reduced, and the performance of the bismuth-system high-temperature superconducting wire/tape is remarkably improved.

Description

Preparation method of bismuth-based high-temperature superconducting wire/strip
Technical Field
The invention belongs to the technical field of high-temperature superconducting wire preparation, and particularly relates to a preparation method of a bismuth-based high-temperature superconducting wire/strip.
Background
Among bismuth-based high-temperature superconducting materials, Bi-2223((Bi, Pb)2Sr2Ca2Cu3Ox) Superconducting transition temperature T ofcAbout 110K, has critical current of more than 100A in a liquid nitrogen temperature zone (77K), can meet the application requirements of superconducting devices such as a superconducting cable, a superconducting motor, a superconducting current limiter, a superconducting current lead and the like on superconducting materials in the liquid nitrogen temperature zone, and Bi-2212
(Bi2Sr2CaCu2Ox) Superconducting transition temperature T ofcThe material is about 90K, has an irreversible field (4.2K) of more than 100T, can still bear the engineering current density with practical application significance under the condition of a high magnetic field of 45T, and is a superconducting material which is very important in the fields of high-field magnet manufacture and high-magnetic field scientific research.
At present, the powder tube filling method (PIT) is the mainstream technology for preparing high-performance Bi-2223 and Bi-2212 high-temperature superconducting wires/strips. The Bi-2223 and Bi-2212 superconducting materials are processed into a linear strip by the technology and then prepared into a magnet, a current lead or a cable for application. The specific processing procedure of the two materials comprises the steps of filling the precursor powder into a silver or silver metal tube (matrix material), and then obtaining the multi-core wire strip through drawing, assembling, redrawing and rolling processing. After the Bi-2223 superconducting material is drawn and processed to obtain the multi-core wire, the multi-core wire needs to be further rolled into a strip form, so that the textured arrangement of crystal grains inside the strip is realized, and the current carrying capacity of the strip is further improved; the Bi-2212 superconducting material is processed into a multi-core wire rod form, and the texture of crystal grains is realized by a slow cooling process in the heat treatment process.
The precursor powder of the Bi-2223 superconducting material before tube loading is a phase component comprising (Bi, P)b)2Sr2CaCu2OxTrace amount of Bi2Sr2CuOx、(Sr,Ca)xCuyOzAnd CuO; the precursor powder of the Bi-2212 superconducting material before tube installation is a Bi-2212 phase with the purity of more than 99 percent. The average particle size of precursor powder of Bi-2223 and Bi-2212 superconducting materials is only 1-3 mu m, and the precursor powder is in a sheet shape and has a large specific surface area, so that the surfaces of the two powders are easy to adsorb water, nitrogen and oxide gas of carbon and nitrogen to form adsorbed gas. In addition, the tube packing density of the two precursor powders is only 30% -50% of the theoretical density of the superconducting material, and a large amount of space is still present inside the silver tube or the silver alloy tube after the powder is packed, and the space is filled with air and is called gap gas. In the final high-temperature phase-forming heat treatment process of the Bi-2223 superconducting tape, the gas pressure of adsorbed gas and interstitial gas in the tape is increased at high temperature, so that the tape bubbles, the connectivity of core wires in the tape is damaged, and the critical current is greatly reduced. In the final texture forming high-temperature heat treatment process of the Bi-2212 superconducting wire, the diameter of the wire is increased due to the fact that the pressure of adsorbed gas and interstitial gas inside the strip is increased at high temperature, the connectivity of core wires inside the wire is damaged, and the critical current is reduced. Therefore, the method reduces or avoids the absorption of gas and gap gas in the powder tube filling process, and has very important significance for ensuring the specification and the size of the Bi-2223 superconducting strip and the Bi-2212 superconducting wire, and particularly improving the superconducting performance of the wire strip.
At present, the method for reducing the adsorbed gas and the interstitial gas generally comprises the steps of loading precursor powder into a tube, and simultaneously carrying out vacuum-pumping treatment on a silver or silver alloy tube at a certain heating temperature, wherein the heating temperature is usually lower than 400 ℃ so as to avoid influencing phase components of the precursor powder, so that the method can reduce the adsorbed gas and the interstitial gas to a certain extent, but the effect is not ideal. Therefore, the development of a new preparation method of the bismuth-based superconducting material can effectively reduce adsorbed gas of powder and gap gas in the process of pipe installation, ensure the size of the bismuth-based superconducting wire and strip, particularly improve the superconducting performance of the wire and strip, and has very important significance for meeting the requirements of application fields such as superconducting cables, high-field superconducting magnets, superconducting motors and the like on the size and the performance of the bismuth-based superconducting material.
In view of the above, the present inventors have conducted a great deal of scientific research and experiments to develop a preparation method of a bismuth-based high-temperature superconducting wire/tape, which is used to solve the above technical problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a bismuth-system high-temperature superconducting wire/strip, which can effectively reduce adsorbed gas and interstitial gas generated in the powder pipe loading process, remarkably improve the critical current of the bismuth-system superconducting wire/strip and meet the application requirements of application fields such as superconducting cables, high-field superconducting magnets, superconducting motors and the like on the size and performance of bismuth-system superconducting materials.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a bismuth-based high-temperature superconducting wire/strip comprises the following steps;
step one, mixing raw material powder and then carrying out pre-phase reaction to obtain a phase composition
Respectively mixing raw material powder containing Bi, Pb, Sr, Ca and Cu according to the mass percentage of elements in the chemical formula of the Bi-2223 or Bi-2212 superconducting material, and carrying out pre-phase reaction on the mixed raw material powder to obtain a phase composition;
step two, the phase composition obtained in the step one is filled into a silver tube to carry out phase forming heat treatment reaction and obtain precursor powder
The two ends of the silver pipe are hermetically welded by adopting silver plugs with holes left in the middle, two metal pipes are respectively welded in the holes in the middle of the two silver plugs, one metal pipe is connected with external gas to be used as a gas inlet pipe, the other metal pipe is used as a gas outlet pipe, and the gas is ensured to be always in a flowing state in the heat treatment process, so that precursor powder of the Bi-2223 or Bi-2212 superconducting material is obtained;
step three, after the two-phase heat treatment reaction, heating the silver tube filled with the precursor powder and simultaneously vacuumizing to obtain the Bi-2223 or Bi-2212 single core rod
Vacuumizing the silver tube while heating to remove heat treatment gas remained among the powders in the heat treatment process of the precursor powder, introducing oxygen into the silver tube from the metal tube at one end and discharging the oxygen through the metal tube at the other end, filling oxygen into gaps among the powders, stopping heating, and sealing and cutting the metal tubes at two ends of the silver tube to obtain the Bi-2223 or Bi-2212 single core rod;
step four, preparing Bi-2223 multi-core strip or Bi-2212 multi-core wire
And (3) drawing the Bi-2223 or Bi-2212 single-core rod obtained in the step three to obtain a sub-component with a cross section being a regular hexagon, and then assembling, drawing and rolling the sub-component to obtain the Bi-2223 multi-core strip or the Bi-2212 multi-core wire.
Further, in the first step, the phase composition obtained after pre-phase reaction of the raw material powder of Bi-2223 is Bi2Sr2CuOx，Ca2PbO4，(Sr,Ca)xCuyOzAnd CuO; the phase composition obtained after pre-reaction of the raw material powder of Bi-2212 is Bi2Sr2CuOxCaO and CuO.
Further, in the first step, the pre-reaction temperature of Bi-2223 and Bi-2212 is 600-700 ℃, the heat treatment time is 10-20 h, and the heat treatment atmosphere is air.
Furthermore, in the second step, after the phase forming heat treatment reaction, the precursor powder phase of Bi-2223 becomes (Bi, Pb)2Sr2CaCu2OxTrace amount of Bi2Sr2CuOx，(Sr,Ca)xCuyOzAnd CuO; the precursor powder phase of Bi-2212 is Bi2Sr2CaCu2Ox。
Further, in the second step, the reaction temperature of the precursor powder of the Bi-2223 and Bi-2212 superconducting materials is 750-840 ℃, the heat treatment time is 10-40 h, and the heat treatment atmosphere is air or N with the oxygen content of 0.1-10%2-O2And (4) mixing the gases.
Further, in the third step, oxygen is introduced into the silver tube, and the gas flow rate is 50 ml/min-500 ml/min.
Further, in the third step, the heating temperature of the silver tube is 400-600 ℃, and the oxygen introducing time is 5-10 h.
Further, in the third step, the vacuum degree of the silver tube is 1 multiplied by 10-3Pa～9×10-3Pa。
Further, in the fourth step, the number of core filaments of the Bi-2223 superconducting tape is 7, 18, 37, 55, 85, 121; the number of core wires of the Bi-2212 superconducting wire is 666, 990 and 1530.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the invention designs a preparation method of a bismuth-based high-temperature superconducting wire/strip, which divides the phase formation of Bi-2223 and Bi-2212 precursor powder into two processes, wherein the first step is a pre-phase reaction process, and the second step is a final phase formation reaction process of the precursor powder. The powder generated by the pre-forming phase reaction is filled into a silver tube for final phase reaction, so that the obtained precursor powder avoids the process of contacting with outside air, and further can avoid the gas adsorption caused by the contact of the powder; after the final phase reaction, the precursor powder is subjected to a long-time oxygen introducing process at high temperature, so that the interstitial gas among the powder can be replaced by oxygen, and the oxygen can freely enter and exit the silver tube in the heat treatment process, so that the strip bubbling or the wire thickening cannot be caused when the interstitial gas is oxygen. Therefore, the invention can avoid the adsorption gas of Bi-2223 and Bi-2212 precursor powder, and simultaneously uses oxygen which can freely enter and exit the silver matrix as gap gas, thereby fundamentally solving the technical problem that the strip material forms bubbles or the diameter is enlarged in the heat treatment process due to the adsorption gas and the gap gas caused by preparing Bi-2223 and Bi-2212 high-temperature superconducting wire materials by adopting a powder tube filling method, thereby ensuring the performance of the bismuth-system high-temperature superconducting wire/strip material prepared by adopting the method.
Drawings
FIG. 1 is a flow chart of a method of making a bismuth-based high temperature superconducting wire/tape of the present invention;
FIG. 2 is a schematic view showing the final phase formation and oxygen introduction of the precursor powder of the bismuth-based superconducting material in a silver tube in the preparation method of the present invention.
In the figure: 1 is a silver tube; 2 is a silver plug; 3 is an air inlet pipe; 4 is an exhaust pipe; a is precursor powder.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present invention. Rather, they are merely examples of apparatus consistent with certain aspects of the invention, as detailed in the appended claims.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the accompanying drawings and examples.
Example 1
As shown in fig. 1, the preparation method of the bismuth-based high-temperature superconducting wire/strip of the invention specifically comprises the following steps:
preparing nitrate solution of five elements of Bi, Pb, Sr, Ca and Cu according to the stoichiometric ratio of Bi-2223 superconducting material, preparing the nitrate solution into spray powder through spray thermal decomposition, and performing pre-phase heat treatment on the spray powder, wherein the heat treatment temperature is 630 ℃, the heat treatment time is 20 hours, the heat treatment atmosphere is air, and the phase composition is Bi2Sr2CuOx，Ca2PbO4，(Sr,Ca)xCuyOzAnd CuO;
and step two, filling the pre-formed phase powder obtained in the step one into a silver pipe, sealing and welding the silver pipe by adopting silver plugs with small holes in the middles at two ends of the silver pipe, and respectively welding two thin metal pipes through the small holes in the middles of the two silver plugs. Putting the silver tube into a furnace body for final phase-forming heat treatment reaction, wherein the heat treatment temperature is 820 ℃, the heat treatment time is 40h, and the heat treatment atmosphere is emptyGas and heat treatment atmosphere are introduced from the thin metal tube at one end of the silver tube, and are discharged from the thin metal tube at the other end. The phase composition obtained in this step is (Bi, Pb)2Sr2CaCu2OxTrace amount of Bi2Sr2CuOx，(Sr,Ca)xCuyOzAnd a Bi-2223 precursor powder of CuO;
step three, after the final heat treatment of the Bi-2223 precursor powder is finished, vacuumizing the silver tube to 5 multiplied by 10-3Pa, pumping out air atmosphere introduced in the final phase-forming heat treatment process of the precursor powder, then heating a silver tube to 500 ℃, introducing high-purity oxygen into the silver tube, wherein the gas flow is 50ml/min, the heating and oxygen introducing time is 10h, and finally sealing and shearing thin metal tubes at two ends of the silver tube to obtain a Bi-2223 single core rod;
and step four, drawing the Bi-2223 single core rod to obtain the sub-component with the cross section being in a regular hexagon. And further assembling, drawing and rolling 37 sub-components to obtain the Bi-2223 strip.
The 50m strip prepared in the embodiment is subjected to Bi-2223 phase forming heat treatment, the critical current is tested under the conditions of 77K and 0T to reach 115A, and no bubbling occurs in the whole strip.
Example 2
The invention relates to a preparation method of a bismuth-based high-temperature superconducting wire/strip, which comprises the following steps:
preparing nitrate solution of five elements of Bi, Pb, Sr, Ca and Cu according to the stoichiometric ratio of Bi-2212 superconducting material, preparing the nitrate solution into spray powder through spray thermal decomposition, and performing pre-phase heat treatment on the spray powder, wherein the heat treatment temperature is 600 ℃, the heat treatment time is 16h, and the heat treatment atmosphere is air to obtain a phase composition of Bi2Sr2CuOxPre-phase powders of CaO and CuO;
and step two, filling the pre-formed phase powder obtained in the step one into a silver pipe, sealing and welding the silver pipe by adopting silver plugs with small holes in the middles at two ends of the silver pipe, and respectively welding two thin metal pipes through the small holes in the middles of the two silver plugs. Putting the silver tube into the furnace body for final phase heat formationThe heat treatment temperature is 780 ℃, the heat treatment time is 20 hours, and the heat treatment atmosphere is N with the oxygen content of 5 percent2-O2The mixed gas and the heat treatment atmosphere are introduced from the thin metal pipe at one end of the silver pipe, and are discharged from the thin metal pipe at the other end. This step results in a phase composition of Bi2Sr2CaCu2OxBi-2212 precursor powder of (a);
step three, after the final heat treatment of the Bi-2212 precursor powder is finished, vacuumizing the silver tube to 1 x 10-3Pa, pumping out the air atmosphere introduced in the final phase-forming heat treatment process of the precursor powder, then heating a silver tube to 600 ℃, introducing high-purity oxygen into the silver tube, wherein the gas flow is 500ml/min, the heating and oxygen introducing time is 5h, and finally sealing and shearing the thin metal tubes at the two ends of the silver tube to obtain the Bi-2212 single core rod;
and step four, drawing the Bi-2212 single core rod to obtain a sub-component with a cross section in a regular hexagon, and then assembling and drawing twice to obtain the Bi-2212 wire with the core wire number of 666.
The 50-meter wire prepared in the embodiment is subjected to Bi-2212 texture forming heat treatment, the critical current reaches 1050A when the test is carried out under the conditions of 4.2K and 0T, the diameter deviation of the whole wire is within the range of +/-0.005 mm, the wire belongs to the normal precision range, and the wire is not thickened.
Example 3
The invention relates to a preparation method of a bismuth-based high-temperature superconducting wire/strip, which comprises the following steps:
step one, adding Bi2O3，Pb(NO3)2，SrCO3，CaCO3The five CuO compounds are weighed according to the stoichiometric ratio of the Bi-2223 superconducting material and react with nitric acid to prepare nitrate solution, the nitrate solution is prepared into coprecipitation powder by an oxalate coprecipitation method, the coprecipitation powder is subjected to pre-phase heat treatment, the heat treatment temperature is 700 ℃, the heat treatment time is 10 hours, the heat treatment atmosphere is air, and the phase composition is Bi2Sr2CuOx，Ca2PbO4，(Sr,Ca)xCuyOzAnd CuO as a pre-formed powderGrinding;
and step two, filling the preformed phase powder obtained in the step one into a silver pipe, and hermetically welding the silver pipe at two ends of the silver pipe by adopting a silver plug with a small hole in the middle. Two thin metal pipes are respectively welded in the small holes in the middle of the two silver plugs. Putting the silver tube into a furnace body for final phase-forming heat treatment reaction, wherein the heat treatment temperature is 750 ℃, the heat treatment time is 10 hours, and the heat treatment atmosphere is N with the oxygen content of 0.1 percent2-O2The mixed gas and the heat treatment atmosphere are introduced from the thin metal pipe at one end of the silver pipe, and are discharged from the thin metal pipe at the other end. The phase composition obtained in this step is (Bi, Pb)2Sr2CaCu2OxTrace amount of Bi2Sr2CuOx，(Sr,Ca)xCuyOzAnd a Bi-2223 precursor powder of CuO;
step three, after the final heat treatment of the Bi-2223 precursor powder is finished, vacuumizing the silver tube to 9 x 10-3Pa, pumping out air atmosphere introduced in the final phase-forming heat treatment process of the precursor powder, then heating a silver tube to 400 ℃, introducing high-purity oxygen into the silver tube, wherein the gas flow is 300ml/min, the heating and oxygen introducing time is 7h, and finally sealing and shearing thin metal tubes at two ends of the silver tube to obtain a Bi-2223 single core rod;
and step four, drawing the Bi-2223 single core rod to obtain the sub-component with the cross section being in a regular hexagon. And further assembling, drawing and rolling 85 sub-components to obtain the Bi-2223 strip.
The 50m strip produced in the example was subjected to a Bi-2223 heat treatment for phase formation, and the critical current reached 118A in the test at 77K and 0T, and no blistering occurred in the whole strip.
Example 4
The invention relates to a preparation method of a bismuth-based high-temperature superconducting wire/strip, which comprises the following steps:
step one, adding Bi2O3，Pb(NO3)2，SrCO3，CaCO3CuO five compounds are weighed and mixed according to the stoichiometric ratio of the Bi-2212 superconducting material, and the mixed powder is fully and uniformly mixed and then is subjected to pre-phase heat treatmentThe heat treatment temperature is 700 ℃, the heat treatment time is 20h, the heat treatment atmosphere is air, and the obtained phase composition is Bi2Sr2CuOxPre-phase powders of CaO and CuO;
and step two, filling the pre-formed phase powder obtained in the step one into a silver pipe, sealing and welding the silver pipe by adopting silver plugs with small holes in the middles at two ends of the silver pipe, and respectively welding two thin metal pipes through the small holes in the middles of the two silver plugs. And (3) putting the silver tube into a furnace body for final phase-forming heat treatment reaction, wherein the heat treatment temperature is 840 ℃, the heat treatment time is 40 hours, the heat treatment atmosphere is air, the heat treatment atmosphere is introduced from the thin metal tube at one end of the silver tube, and the thin metal tube at the other end of the silver tube is discharged. This step results in a phase composition of Bi2Sr2CaCu2OxBi-2212 precursor powder of (a);
step three, after the final heat treatment of the Bi-2212 precursor powder is finished, vacuumizing the silver tube to 2 x 10-3Pa, pumping out the air atmosphere introduced in the final phase-forming heat treatment process of the precursor powder, then heating a silver tube to 500 ℃, introducing high-purity oxygen into the silver tube, wherein the gas flow is 150ml/min, the heating and oxygen introducing time is 6h, and finally sealing and shearing the thin metal tubes at the two ends of the silver tube to obtain the Bi-2212 single core rod;
and step four, drawing the Bi-2212 single core rod to obtain a sub-component with a cross section of a regular hexagon, and then assembling and drawing twice to obtain the Bi-2212 wire with the core wire number of 1530.
The 50-meter wire prepared in the embodiment is subjected to Bi-2212 texture forming heat treatment, the critical current reaches 1087A when the test is carried out under the conditions of 4.2K and 0T, the diameter deviation of the whole wire is within the range of +/-0.005 mm, the wire belongs to the normal precision range, and the wire is not thickened.
Example 5
The invention relates to a preparation method of a bismuth-based high-temperature superconducting wire/strip, which comprises the following steps:
firstly, nitrate of five elements of Bi, Pb, Sr, Ca and Cu is prepared into nitrate solution according to the stoichiometric ratio of Bi-2223 superconducting material, and the nitrate solution is prepared into nitrate solution through spray thermal decompositionSpraying powder, and pre-phase heat treating the sprayed powder at 680 deg.C for 12 hr in air to obtain Bi phase2Sr2CuOx，Ca2PbO4，(Sr,Ca)xCuyOzAnd CuO;
and step two, filling the pre-formed phase powder obtained in the step one into a silver pipe, sealing and welding the silver pipe by adopting silver plugs with small holes in the middles at two ends of the silver pipe, and respectively welding two thin metal pipes through the small holes in the middles of the two silver plugs. Putting the silver tube into a furnace body for final phase-forming heat treatment reaction, wherein the heat treatment temperature is 800 ℃, the heat treatment time is 24 hours, and the heat treatment atmosphere is N with the oxygen content of 10 percent2-O2The mixed gas and the heat treatment atmosphere are introduced from the thin metal pipe at one end of the silver pipe, and are discharged from the thin metal pipe at the other end. The phase composition obtained in this step is (Bi, Pb)2Sr2CaCu2OxTrace amount of Bi2Sr2CuOx，(Sr,Ca)xCuyOzAnd a Bi-2223 precursor powder of CuO;
step three, after the final heat treatment of the Bi-2223 precursor powder is finished, vacuumizing the silver tube to 7 x 10-3Pa, pumping out air atmosphere introduced in the final phase-forming heat treatment process of the precursor powder, then heating a silver tube to 600 ℃, introducing high-purity oxygen into the silver tube, wherein the gas flow is 350ml/min, the heating and oxygen introducing time is 6h, and finally sealing and shearing thin metal tubes at two ends of the silver tube to obtain a Bi-2223 single core rod;
and step four, drawing the Bi-2223 single core rod to obtain the sub-component with the cross section being in a regular hexagon. And further assembling, drawing and rolling 121 sub-components to obtain the Bi-2223 strip.
The 50m strip prepared in the embodiment is subjected to Bi-2223 phase forming heat treatment, the critical current reaches 120A when the test is carried out under the conditions of 77K and 0T, and no bubbling occurs in the whole strip.
Example 6
A preparation method of a bismuth-based high-temperature superconducting wire/strip specifically comprises the following steps:
step one, nitrate of five elements of Bi, Pb, Sr, Ca and Cu is prepared into nitrate solution according to the stoichiometric ratio of Bi-2212 superconducting material, the nitrate solution is prepared into co-precipitated powder through an oxalate co-precipitation method, the co-precipitated powder is subjected to pre-phase heat treatment, the heat treatment temperature is 650 ℃, the heat treatment time is 16 hours, the heat treatment atmosphere is air, and the phase composition is obtained2Sr2CuOxPre-phase powders of CaO and CuO;
and step two, filling the pre-formed phase powder obtained in the step one into a silver pipe, sealing and welding the silver pipe by adopting silver plugs with small holes in the middles at two ends of the silver pipe, and respectively welding two thin metal pipes through the small holes in the middles of the two silver plugs. And (3) putting the silver tube into a furnace body for final phase-forming heat treatment reaction, wherein the heat treatment temperature is 830 ℃, the heat treatment time is 10 hours, the heat treatment atmosphere is air, the heat treatment atmosphere is introduced from the thin metal tube at one end of the silver tube, and the thin metal tube at the other end of the silver tube is discharged. This step results in a phase composition of Bi2Sr2CaCu2OxBi-2212 precursor powder of (a);
step three, after the final heat treatment of the Bi-2212 precursor powder is finished, vacuumizing the silver tube to 1 x 10-3Pa, pumping out the air atmosphere introduced in the final phase-forming heat treatment process of the precursor powder, then heating a silver tube to 400 ℃, introducing high-purity oxygen into the silver tube, wherein the gas flow is 200ml/min, the heating and oxygen introducing time is 10h, and finally sealing and shearing the thin metal tubes at the two ends of the silver tube to obtain the Bi-2212 single core rod;
and step four, drawing the Bi-2212 single core rod to obtain a sub-component with a cross section in a regular hexagon, and then assembling and drawing twice to obtain the Bi-2212 wire with a core wire number of 990.
The 50-meter wire prepared in the embodiment is subjected to Bi-2212 texture forming heat treatment, the critical current reaches 1092A when the test is carried out under the conditions of 4.2K and 0T, the diameter deviation of the whole wire is within the range of +/-0.005 mm, the wire belongs to the normal precision range, and the wire is not thickened.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (9)

1. A preparation method of a bismuth-based high-temperature superconducting wire/strip is characterized by comprising the following steps;
step one, mixing raw materials and carrying out pre-phase reaction to obtain a phase composition
Raw materials containing Bi, Pb, Sr, Ca and Cu are respectively mixed according to the mass percentage of elements in the chemical formula of the Bi-2223 or Bi-2212 superconducting material, and the mixed raw material powder is subjected to pre-phase reaction to obtain phase composition powder;
step two, filling the phase composition powder obtained in the step one into a silver tube, carrying out phase forming heat treatment reaction and obtaining precursor powder
The two ends of the silver pipe are hermetically welded by adopting silver plugs with holes left in the middle, two metal pipes are respectively welded in the holes in the middle of the two silver plugs, one metal pipe is connected with external gas to be used as a gas inlet pipe, the other metal pipe is used as a gas outlet pipe, and the gas is ensured to be always in a flowing state in the heat treatment process, so that precursor powder of the Bi-2223 or Bi-2212 superconducting material is obtained;
step three, after the two-phase heat treatment reaction, heating the silver tube filled with the precursor powder and simultaneously vacuumizing to obtain the Bi-2223 or Bi-2212 single core rod
Vacuumizing the silver tube while heating to remove heat treatment gas remained among the powders in the heat treatment process of the precursor powder, introducing oxygen into the silver tube from the metal tube at one end and discharging the oxygen through the metal tube at the other end, filling oxygen into gaps among the powders, stopping heating, and sealing and cutting the metal tubes at two ends of the silver tube to obtain the Bi-2223 or Bi-2212 single core rod;
step four, preparing Bi-2223 multi-core strip or Bi-2212 multi-core wire
And (3) drawing the Bi-2223 or Bi-2212 single-core rod obtained in the step three to obtain a sub-component with a cross section being a regular hexagon, and then assembling, drawing and rolling the sub-component to obtain the Bi-2223 multi-core strip or the Bi-2212 multi-core wire.
2. The method as claimed in claim 1, wherein in the step one, the phase composition obtained from the pre-reaction of the raw material powder of Bi-2223 is Bi2Sr2CuOx，Ca2PbO4，(Sr,Ca)xCuyOzAnd CuO; the phase composition obtained after pre-reaction of the raw material powder of Bi-2212 is Bi2Sr2CuOxCaO and CuO.
3. The method for preparing a bismuth-based high-temperature superconducting wire/strip as claimed in claim 1, wherein in the first step, the pre-reaction temperature of Bi-2223 and Bi-2212 is 600-700 ℃, the heat treatment time is 10-20 h, and the heat treatment atmosphere is air.
4. The method for preparing a bismuth-based high-temperature superconducting wire/strip as claimed in claim 1, wherein in the second step, after the phase-forming heat treatment reaction, the precursor powder phase of Bi-2223 is (Bi, Pb)2Sr2CaCu2OxTrace amount of Bi2Sr2CuOx，(Sr,Ca)xCuyOzAnd CuO; the precursor powder phase of Bi-2212 is Bi2Sr2CaCu2Ox。
5. The method for preparing a bismuth-based high-temperature superconducting wire/tape as claimed in claim 1, wherein in the second step, Bi-2223 and Bi-2212 superconducting wires/tapes are preparedThe reaction temperature of the precursor powder is 750-840 ℃, the heat treatment time is 10-40 h, and the heat treatment atmosphere is air or N with the oxygen content of 0.1-10%2-O2And (4) mixing the gases.
6. The method for preparing a bismuth-based high-temperature superconducting wire/strip as claimed in claim 1, wherein in the third step, oxygen is introduced into the silver tube, and the gas flow rate is 50ml/min to 500 ml/min.
7. The method for preparing a bismuth-based high-temperature superconducting wire/strip as claimed in claim 1, wherein in the third step, the heating temperature of the silver tube is 400-600 ℃, and the oxygen introduction time is 5-10 h.
8. The method for preparing a bismuth-based high-temperature superconducting wire/tape as claimed in claim 1, wherein in the third step, the degree of vacuum of the silver tube is 1 x 10-3Pa～9×10-3Pa。
9. The method for preparing a bismuth-based high-temperature superconducting wire/tape as claimed in claim 1, wherein in the fourth step, the number of core filaments of the Bi-2223 superconducting tape is 7, 18, 37, 55, 85, 121; the number of core wires of the Bi-2212 superconducting wire is 666, 990 and 1530.
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