CN116779240A - Preparation method of magnesium diboride superconducting wire and magnesium diboride superconducting wire - Google Patents

Preparation method of magnesium diboride superconducting wire and magnesium diboride superconducting wire Download PDF

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Publication number
CN116779240A
CN116779240A CN202311031618.XA CN202311031618A CN116779240A CN 116779240 A CN116779240 A CN 116779240A CN 202311031618 A CN202311031618 A CN 202311031618A CN 116779240 A CN116779240 A CN 116779240A
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China
Prior art keywords
powder
ingot
superconducting wire
magnesium diboride
diboride superconducting
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CN202311031618.XA
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CN116779240B (en
Inventor
王明江
郭强
朱燕敏
严凌霄
武博
史一功
刘向宏
冯勇
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Xi'an Juneng Superconducting Wire Technology Co ltd
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Xi'an Juneng Superconducting Wire Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00Superconductive or hyperconductive conductors, cables, or transmission lines
    • H01B12/02Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00Superconductive or hyperconductive conductors, cables, or transmission lines

Abstract

The application discloses a preparation method of a magnesium diboride superconducting wire and the magnesium diboride superconducting wire, wherein the preparation method comprises the following steps: machining a plurality of holes on the Nb ingot, wherein the holes comprise a central hole and an edge hole; inserting a Cu rod into the central hole, and sleeving the Nb ingot into the NCu30 alloy pipe to obtain a composite ingot; vacuumizing and heating the composite ingot; uniformly mixing Mg powder and C coated B powder to obtain precursor powder; filling precursor powder into the edge holes of the composite ingot under vacuum and heating state to obtain a powder-filled composite ingot; carrying out cold rotary forging and cold drawing on the powder-filled composite ingot to obtain a multi-core composite wire; and performing high Wen Chengxiang heat treatment on the multi-core composite wire to obtain the magnesium diboride superconducting wire. According to the application, mg powder and B powder are filled into holes of an Nb ingot in a high-temperature vacuum environment, so that each matrix of the wire is kept in good close contact, and a core wire structure with uniform deformation is obtained, thereby improving the integrity and current carrying capacity of the magnesium diboride superconducting wire.

Description

Preparation method of magnesium diboride superconducting wire and magnesium diboride superconducting wire
Technical Field
The application relates to the technical field of metal processing, in particular to a preparation method of a magnesium diboride superconducting wire and the magnesium diboride superconducting wire.
Background
Based on the basic superconducting physical properties of the superconducting material itself, titanium niobium (NbTi) and three tin niobium (Nb 3 Sn), magnesium diboride (MgB) 2 )、REBCO(REBa 2 Cu 3 O 7-x ) Bismuth-based superconductor (Bi) 2 Sr 2 Ca 2 Cu 3 O 7-x ) Superconducting wires/ribbons exhibit their respective irreplaceable advantages under different engineering application conditions. For practical use of NbTi and Nb 3 Sn wires have superior metal forming characteristics, making them attractive for mass production and commercial engineering applications. However, nbTi and Nb are considered to increase nonlinearly with decrease in temperature in terms of energy consumption required to obtain low temperature from ordinary temperature 3 The energy consumed by Sn wires when run in a low temperature environment (4.2K) places a significant burden on the cost of their engineering applications. Due to the practical use of MgB 2 、REBa 2 Cu 3 O 7-x 、Bi 2 Sr 2 Ca 2 Cu 3 O 7-x The high temperature superconducting wire/strip can work in an environment higher than 20K, so the development of the high temperature superconducting wire/strip greatly improves the application value of the superconducting technology. Practical MgB 2 The transition temperature of the superconducting wire reaches 39K, and the preparation cost of the wire is low, so that the superconducting wire has remarkable advantages in the working environment of a refrigerator or liquid hydrogen (20K) manufacture.
Currently, mgB is put into practical use 2 Powder for superconducting wireThe Powder in tube technology (Powder in tube) is used for preparing the metal auxiliary matrix, and the metal auxiliary matrix is usually copper (Cu), niobium (Nb), nickel (Ni), monel alloy (NCu 30) and the like, and a secondary assembly process is adopted in the preparation process. Because the composite wire is cold formed, the plastic deformation between the metal substrates is performed independently of each other. More importantly, the powder needs to be deformed together with the metal matrix, and the powder is not rigid, so that the deformation process is not compliant with a metal plastic deformation mode. The above problems will result in a large non-uniformity in the deformation of the wire core wire, which will further affect the core wire structural integrity and current carrying properties.
Disclosure of Invention
The embodiment of the application provides a preparation method of a magnesium diboride superconducting wire and the magnesium diboride superconducting wire, which are used for solving the problem of MgB in the prior art 2 The uneven deformation of the superconducting wire core leads to the problem that the structural integrity and current carrying performance of the wire core are affected.
In one aspect, an embodiment of the present application provides a method for preparing a magnesium diboride superconducting wire, including:
machining a plurality of holes on the Nb ingot, the holes including a center hole and an edge hole;
inserting a Cu rod into the central hole, and sleeving the Nb ingot into an NCu30 alloy pipe to obtain a composite ingot;
vacuumizing and heating the composite ingot;
uniformly mixing Mg powder and C coated B powder to obtain precursor powder;
filling the precursor powder into the edge holes of the composite ingot under vacuum and heating state to obtain a powder-filled composite ingot;
carrying out cold rotary forging and cold drawing on the powder-filled composite ingot to obtain a multi-core composite wire;
and performing high Wen Chengxiang heat treatment on the multi-core composite wire to obtain the magnesium diboride superconducting wire.
On the other hand, the embodiment of the application also provides a magnesium diboride superconducting wire, which is prepared by adopting the method.
The preparation method of the magnesium diboride superconducting wire and the magnesium diboride superconducting wire have the following advantages:
1. the application adopts high-purity Nb ingot processed with holes as a stable matrix, and fills Mg powder and B powder which are uniformly mixed into the holes. The method ensures that secondary assembly of subcomponents is not needed in the wire preparation process, shortens the wire preparation period, simultaneously continuously carries out deformation of the Nb matrix during wire processing, is beneficial to further improving the deformation uniformity of the wire core wire, and correspondingly improves the superconducting current carrying performance of the wire.
2. In the application, the precursor powder tubing process is carried out in a vacuum heating environment, and in the process of loading the powder into the Nb ingot, the gas adsorbed on the surface of the powder is desorbed under the action of vacuum and high temperature, and the process can effectively improve the uniformity of the density of the tubing powder.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic cross-sectional view of a magnesium diboride superconducting wire in a preparation process according to an embodiment of the present application.
Reference numerals illustrate: 1-NCu30 alloy tube, 2-Nb ingot, 3-hole, 4-Cu bar.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The embodiment of the application provides a preparation method of a magnesium diboride superconducting wire, which comprises the following steps:
s100, machining a plurality of holes 3 on the Nb ingot 2, wherein the holes 3 include a center hole and an edge hole.
Illustratively, nb ingot 2 is a cylindrical structure, which can be made of high purity Nb, 99.9% purity. In machining the hole 3, a deep hole drilling technique may be used to machine a cylindrical central hole along the axis of the Nb ingot 2, and a plurality of edge holes parallel to the central hole are machined around the central hole, the edge holes also being cylindrical.
In the embodiment of the application, the diameters of the central hole and the edge hole are different, the diameter of the central hole is 20 mm-100 mm, and the diameter of the edge hole is 5 mm-80 mm.
S110, inserting a Cu rod 4 into the central hole, and sleeving the Nb ingot 2 into the NCu30 alloy tube 1 to obtain a composite ingot.
Illustratively, the Cu bar 4 is made of oxygen-free copper with a purity of 99.9%, and the Cu bar 4 is shaped and sized to match the central hole so that the Cu bar 4 is in close contact with the central hole after insertion. The NCu30 alloy tube 1 has an outer diameter of 15mm to 50mm and a wall thickness of 1mm to 20mm, and has been annealed.
In an embodiment of the application, the Nb ingot 2 is also pickled before the Cu bar 4 is inserted into the central hole to ensure sufficient cleanliness of the Nb ingot 2 and the holes 3 thereon.
And S120, vacuumizing and heating the composite ingot.
Illustratively, the composite ingot may be evacuated and heated using a vacuum powder tubing apparatus.
S130, uniformly mixing Mg powder and C coated B powder to obtain precursor powder.
Illustratively, the Mg powder and the C-coated B powder may be mixed in a glove box. After mixing in a glove box to obtain precursor powder, the precursor powder is filled into a stainless steel material tank, and the material tank is connected with the vacuum powder tubing equipment. The valve is arranged on the charging bucket and can be opened in a manual control or electric driving mode, and when the valve is opened, precursor powder in the charging bucket can be poured out.
In the embodiment of the application, the mass ratio of Mg powder to C coated B powder in precursor powder is calculated according to the atomic number ratio of Mg to B=1 to 2, the average particle size of the Mg powder is 100 mu m, the purity is 99.9%, the average particle size of the C coated B powder is 2 mu m, and the mass fraction of C in the precursor powder is 2% -10%.
And S140, filling the precursor powder into the edge holes of the composite ingot under the vacuum and heating states to obtain a powder-filled composite ingot.
Illustratively, the application adopts the vacuum powder tubing technology to desorb the adsorbed gas on the surface of the micron-sized powder, so that the tubing powder gap is in a vacuum state, and the density of the tubing powder is further increased.
In the specific preparation process, the composite ingot can be firstly put into vacuum powder tubing equipment, and the vacuum powder tubing equipment can automatically perform vacuumizing and heating operations after the vacuum and heating procedures are started. In the vacuumizing and heating process, production personnel can prepare precursor powder, the charging bucket can be connected to vacuum powder tubing equipment after the preparation is finished, at the moment, a valve of the charging bucket is in a closed state, and meanwhile, the vacuum powder tubing equipment can also vacuumize and heat the charging bucket, so that the charging bucket and the precursor powder therein reach a certain temperature. After the vacuum degree and temperature inside the vacuum powder tubing equipment (including the vacuum degree and temperature of the composite ingot and the charging bucket) reach the set values, the valve of the charging bucket can be opened in a manual or electric drive control mode, and the precursor powder is charged into the edge holes.
In the embodiment of the application, the charging bucket is arranged above the composite ingot after being connected to the vacuum powder tubing equipment, the vacuum powder tubing equipment is internally provided with a pipeline connected with the charging bucket, the lower end of the pipeline is arranged right above the composite ingot, and when a valve on the charging bucket is opened, precursor powder in the charging bucket in a turnover state (namely, a discharge hole is downward) enters the pipeline under the action of gravity and finally is filled into the edge hole.
Further, the vacuum powder tubing apparatus also taps the precursor powder after it is loaded into the edge hole. In particular, the vacuum powder tubing apparatus may be continuously vibrated during the process of filling the precursor powder. Meanwhile, after the operation of filling the precursor powder is finished, the welding device in the vacuum powder tubing equipment is used for carrying out electron beam welding on the two ends of the hole, so that the precursor powder is prevented from leaking out.
It will be appreciated that the precursor powder will be filled into all the holes 3 during filling, and that since the Cu rods 4 have been inserted into the central holes, the central holes will be filled with a small amount of precursor powder, and a substantial part of the precursor powder will be filled into the edge holes.
And S150, performing cold rotary forging and cold drawing on the powder-filled composite ingot to obtain a multi-core composite wire.
Illustratively, the pass processing amount in the cold rotary forging process is 10% -20%, the pass processing amount in the cold drawing process is 10% -20%, the cross section of the shaped multi-core composite wire is circular, and the diameter is 0.5 mm-5 mm.
And S160, performing high Wen Chengxiang heat treatment on the multi-core composite wire to obtain the magnesium diboride superconducting wire.
Illustratively, the high Wen Chengxiang heat treatment is completed after heat preservation for 1-5 hours at a temperature range of 500-700 ℃.
The embodiment of the application also provides a magnesium diboride superconducting wire, which is prepared by adopting the method.
Example 1
Step one, deep holes are processed on an Nb ingot with purity of 99.9% by adopting a deep hole drilling technology, and particularly through holes with the number of 24 are processed on the surface of the end part of the Nb ingot along the length direction, as shown in figure 1, wherein the diameter of a central hole is 45mm, and the diameter of an edge hole is 30mm.
Inserting a Cu rod with the diameter of 44.95mm into a central hole of the Nb ingot after pickling, then integrally sleeving the Nb ingot into an NCu30 alloy pipe with the wall thickness of 1mm, fixing the Nb ingot into vacuum powder tubing equipment, and starting the vacuum and heating procedures of the equipment.
Thirdly, in a glove box with a circulating argon gas with the purity of 99.999%, calculating and weighing Mg powder with the purity of 99.9% and the granularity of 80 mu m and amorphous B powder with the C content of 2% according to the atomic number ratio of Mg to B=1 to 2, uniformly mixing the weighed powder, filling the powder into a stainless steel charging bucket, finally sealing the charging bucket, connecting the charging bucket with vacuum powder tubing equipment, and simultaneously starting the vacuum and heating procedures of the equipment.
Step four, when the temperature in the equipment chamber reaches 200 ℃ and the vacuum degree reaches 10 -5 After Pa, starting a vibration program of vacuum powder tubing equipment, simultaneously opening a valve of a charging bucket, filling all holes of the Nb ingot with precursor powder with the same mass, and compacting the precursor powder under the assistance of the vibration function of the equipment.
And step five, taking out the powder-filled composite ingot obtained in the step four, and processing and forming the powder-filled composite ingot into round wires with the diameter of phi 0.8mm by adopting cold rotary forging and cold drawing methods, wherein the pass processing amount in the processing process is 10%.
Step six, the wire rod obtained in the step five is subjected to heat preservation for 3 hours at 500 ℃ in a vacuum environment to obtain MgB with superconducting performance 2 A superconducting wire.
Example two
Firstly, deep holes are processed on an Nb ingot with purity of 99.9% by adopting a deep hole drilling technology, and particularly 45 through holes are processed on the surface of the end part of the Nb ingot along the length direction, wherein the diameter of a central hole is 65mm, and the diameter of an edge hole is 50mm.
Inserting a Cu rod with the diameter of 64.95mm into a central hole of the Nb ingot after pickling, then integrally sleeving the Nb ingot into an NCu30 alloy pipe with the wall thickness of 5mm, fixing the Nb ingot into vacuum powder tubing equipment, and starting the vacuum and heating procedures of the equipment.
Thirdly, in a glove box with a circulating argon gas with the purity of 99.999%, calculating and weighing Mg powder with the purity of 99.9% and the granularity of 100 mu m and amorphous B powder with the C content of 6% according to the atomic number ratio of Mg to B=1 to 2, uniformly mixing the weighed powder, filling the powder into a stainless steel tank, sealing the tank, connecting the tank with vacuum powder tubing equipment, and starting the vacuum and heating procedures of the equipment.
Step four, waiting for the temperature in the equipment chamberReaching 300 ℃ and vacuum degree of 10 -4 After Pa, starting a vibration program of vacuum powder tubing equipment, simultaneously opening a valve of a charging bucket, filling all holes of the Nb ingot with precursor powder with the same mass, and compacting the precursor powder under the assistance of the vibration function of the equipment.
Step five, taking out the powder-filled composite ingot obtained in the step four, and processing and forming the powder-filled composite ingot into a powder with the diameter of being equal to that of the powder-filled composite ingot by adopting cold rotary forging and cold drawing methodsThe number of passes in the process was 15%.
Step six, the wire rod obtained in the step five is subjected to heat preservation at 600 ℃ for 2 hours in a vacuum environment to obtain MgB with superconducting performance 2 A superconducting wire.
Example III
Firstly, deep holes are processed on an Nb ingot with purity of 99.9% by adopting a deep hole drilling technology, and specifically through holes with the number of 73 are processed on the surface of the end part of the Nb ingot along the length direction, wherein the diameter of a central hole is 80mm, and the diameter of an edge hole is 70mm.
Inserting a Cu rod with the diameter of 79.95mm into a central hole of the Nb ingot after pickling, then sleeving the whole Nb ingot into an NCu30 alloy pipe with the wall thickness of 10mm, fixing the Nb ingot into vacuum powder tubing equipment, and starting the vacuum and heating procedures of the equipment.
Thirdly, in a glove box with a circulating argon gas with the purity of 99.999%, calculating and weighing Mg powder with the purity of 99.9% and the granularity of 150 mu m and amorphous B powder with the C content of 10% according to the atomic number ratio of Mg to B=1 to 2, uniformly mixing the weighed powder, filling the powder into a stainless steel tank, sealing the tank, connecting the tank with vacuum powder tubing equipment, and starting the vacuum and heating procedures of the equipment.
Step four, when the temperature in the equipment chamber reaches 400 ℃ and the vacuum degree reaches 10 -3 After Pa, starting a vibration program of vacuum powder tubing equipment, simultaneously opening a valve of a charging bucket, filling all holes of the Nb ingot with precursor powder with the same mass, and simultaneously placing the precursor powder in the equipmentCompaction is performed with the aid of a vibration function.
Step five, taking out the powder-filled composite ingot obtained in the step four, and processing and forming the powder-filled composite ingot into a powder with the diameter of being equal to that of the powder-filled composite ingot by adopting cold rotary forging and cold drawing methodsThe number of passes in the process was 20%.
Step six, the wire rod obtained in the step five is subjected to heat preservation at 700 ℃ for 1h in a vacuum environment to obtain MgB with superconducting performance 2 A superconducting wire.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (10)

1. A method for preparing a magnesium diboride superconducting wire, comprising:
machining a plurality of holes (3) in a Nb ingot (2), the holes (3) comprising a central hole and an edge hole;
inserting a Cu rod (4) into the central hole, and sleeving the Nb ingot (2) into the NCu30 alloy tube (1) to obtain a composite ingot;
vacuumizing and heating the composite ingot;
uniformly mixing Mg powder and C coated B powder to obtain precursor powder;
filling the precursor powder into the edge holes of the composite ingot under vacuum and heating state to obtain a powder-filled composite ingot;
carrying out cold rotary forging and cold drawing on the powder-filled composite ingot to obtain a multi-core composite wire;
and performing high Wen Chengxiang heat treatment on the multi-core composite wire to obtain the magnesium diboride superconducting wire.
2. The method for preparing a magnesium diboride superconducting wire according to claim 1, wherein the composite ingot is vacuumized and heated by vacuum powder tubing equipment.
3. The method of preparing a magnesium diboride superconducting wire as claimed in claim 2, wherein the precursor powder is mixed uniformly and then fed into a charging tank, and the charging tank is connected with the vacuum powder tubing apparatus.
4. A method of producing a magnesium diboride superconducting wire according to claim 3, wherein the Mg powder and the C-coated B powder are mixed in a glove box.
5. A method of preparing a magnesium diboride superconducting wire as claimed in claim 3 wherein the precursor powder is charged into the edge holes by opening the valve of the charging tank when the vacuum and temperature inside the vacuum powder loading apparatus reach set values.
6. The method of preparing a magnesium diboride superconducting wire as claimed in claim 5, wherein said vacuum powder loading apparatus further taps said precursor powder after said precursor powder is loaded into said edge holes.
7. The method for producing a magnesium diboride superconducting wire according to claim 1, wherein the mass ratio of Mg powder to C-coated B powder in the precursor powder is 1:2.
8. A method of producing a magnesium diboride superconducting wire according to claim 1, characterized in that the Nb ingot (2) is also acid washed before inserting the Cu rod (4) into the central bore.
9. A method of preparing a magnesium diboride superconducting wire as claimed in claim 1 wherein the diameters of the central and edge holes are different.
10. A magnesium diboride superconducting wire, characterized in that it is prepared by the method according to any one of claims 1 to 9.
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JPS6467819A (en) * 1987-09-07 1989-03-14 Univ Tokai Manufacture of superconducting wire
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JP2003217370A (en) * 2002-01-23 2003-07-31 Hitachi Cable Ltd Magnesium diboride superconductive wire
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CN103956221A (en) * 2014-05-16 2014-07-30 宝胜科技创新股份有限公司 Method for preparing C-mixed multi-core MgB2 super-conduction wires through solution coating method
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CN111952008A (en) * 2020-08-24 2020-11-17 西部超导材料科技股份有限公司 Method for preparing NbTi/Cu superconducting wire by powder metallurgy method
CN113963854A (en) * 2021-11-30 2022-01-21 西北有色金属研究院 Kilometer-level MgB with rectangular cross section2Method for producing superconducting wire
CN114864177A (en) * 2022-05-23 2022-08-05 合肥夸夫超导科技有限公司 Internal tin method Nb 3 Preparation method of Sn precursor wire

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6467819A (en) * 1987-09-07 1989-03-14 Univ Tokai Manufacture of superconducting wire
JP2003217370A (en) * 2002-01-23 2003-07-31 Hitachi Cable Ltd Magnesium diboride superconductive wire
CN1411004A (en) * 2002-12-03 2003-04-16 西北有色金属研究院 Magnesium boride super conductive wire and its preparation method
EP1894906A1 (en) * 2006-08-28 2008-03-05 Bruker BioSpin AG Superconducting element containing MgB2
CN102522153A (en) * 2011-10-25 2012-06-27 西北有色金属研究院 Preparation method of multi-core MgB2 superconducting wire
CN103956221A (en) * 2014-05-16 2014-07-30 宝胜科技创新股份有限公司 Method for preparing C-mixed multi-core MgB2 super-conduction wires through solution coating method
CN104916373A (en) * 2015-05-18 2015-09-16 中国科学院电工研究所 Preparation method of magnesium diboride wire rod or strip
CN107170526A (en) * 2017-04-28 2017-09-15 西部超导材料科技股份有限公司 The preparation method of the tin superconducting wire timber-used copper niobium compound bar of high critical current densities niobium three
CN111952008A (en) * 2020-08-24 2020-11-17 西部超导材料科技股份有限公司 Method for preparing NbTi/Cu superconducting wire by powder metallurgy method
CN113963854A (en) * 2021-11-30 2022-01-21 西北有色金属研究院 Kilometer-level MgB with rectangular cross section2Method for producing superconducting wire
CN114864177A (en) * 2022-05-23 2022-08-05 合肥夸夫超导科技有限公司 Internal tin method Nb 3 Preparation method of Sn precursor wire

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