CN108682509A - A method of preparing iron-based superconducting composite strip - Google Patents
A method of preparing iron-based superconducting composite strip Download PDFInfo
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- CN108682509A CN108682509A CN201810255629.9A CN201810255629A CN108682509A CN 108682509 A CN108682509 A CN 108682509A CN 201810255629 A CN201810255629 A CN 201810255629A CN 108682509 A CN108682509 A CN 108682509A
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
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Abstract
A method of iron-based superconducting composite strip is prepared, the specific steps are:(a) iron-based superconducting precursor powder is inserted in inner layer metal pipe, by being machined into single band;(b) outer layer metal capsule is machined, inner layer metal band is filled in the outer layer metal jacket processed carry out it is compound;(c) complex is machined and is heat-treated, obtain iron-based superconducting composite strip.
Description
Technical field
The present invention relates to a kind of methods preparing iron-based superconducting composite strip.
Background technology
Breakthrough of the high temperature superconducting materia in forceful electric power application field depends on superconductor and superconducting line, band process work
The development of skill.The iron-based superconducting material found in 2008 is because it has a high upper critical field simultaneously, less anisotropy and higher
The characteristics such as superconducting transition temperature and evoked the research boom in worldwide, be expected in hyperconductive cable, transformer, superconducting magnetic
Body etc. is used widely.Currently, it is metallic sheath tube method (PIT to prepare the more mature method of iron-based superconducting line, band
Method).The ripe powder of synthesis iron base superconduction under the high temperature conditions first, then ripe powder is fitted into metal tube, then the metal tube is carried out
A series of mechanical processings, finally by being thermally treated resulting in iron-based superconducting line, strip product.Since there are weak in iron-based superconducting material
Joint efficiency, therefore the general method using rolling or compacting prepares iron-based superconducting tape, improves texture degree to improve current-carrying
Performance.Since silver has iron-based superconducting material enough chemical reaction inertia, and it also has the good capacity of heat transmission and prolongs
Malleability, therefore silver-colored pipe is typically chosen in PIT methods as sheath material.However, can a kind of superconductor industrially extensive
Higher current density can be carried using it is depended not only on, additionally depends on whether it has very high tensile strength, if
Smaller radius can be bent to and keep high current simultaneously.Although silver-colored jacket has the advantages that above-mentioned, its mechanical strength is very
It is weak.Studies have shown that the irreversible stress value σ of silver-colored jacket iron-based superconducting tapeirrOnly 35Mpa
[Supercond.Sci.Tech.28,035007 (2015)], are easy under high-intensity magnetic field due to being occurred not by forceful electric power magnetic force
Reversible destruction, therefore the electric power application such as be not suitable for superconducting coil, hyperconductive cable.In addition, by swaging, drawing, rolling mill practice
There are a large amount of hole and crackles in the band core of the iron-based superconducting tape of preparation, seriously hinder superconducting critical current density Jc
Raising.Therefore, the consistency of iron-based superconducting core is improved, reducing hole and crackle becomes the primary study of iron-based superconducting line strips
Direction.Surpass currently, hot isostatic pressing method (HIP methods) and pressure sintering (HP methods) are respectively used to improve in iron-based superconducting wire and band
The consistency of core is led, superconducting critical current density of the band that wherein prepared by pressure sintering at 4.2K temperature and the magnetic fields 10T is more than
0.1MA/cm2, reach practical horizontal.However, the above method cannot be used for preparing the long line of superconduction, jacket machinery is not solved
The weak problem of intensity, is not suitable for large-scale industrial production and application.Therefore, it is necessary to the compound one layer of hardness of Ag jacket outer layers compared with
High jacket improves mechanical strength.At present generally complex superconducting wire strip is prepared using following two techniques:
1. inner layer sleeve and outer layer sleeve are first carried out compound, processing, multiple tube is obtained;Superconducting precursor powder is inserted again multiple
It closes in pipe and is machined and is heat-treated, obtain final wire strip, such as patent:200610114264.5
200710121109.0。
2. first inserting front axle shell in inner tube, then the inner tube equipped with front axle shell is filled in outer layer sleeve, it is most laggard
Row mechanical processing obtains wire strip, such as patent:200910241918.4.
There are disadvantages for both the above technique:Since jacket is generally closed using softer Ag or Ag in iron-based superconducting line strips
Gold, and the hardness of outer layer jacket, ductility and internal layer jacket gap are larger, it is uneven to be easy to cause superconducting core for first compound reprocessing
Even disconnected core.Secondly, directly multiple tube is machined, it is difficult to form the superconducting core of highly-textured degree wherein.It is above to lack
Point will seriously affect the current-carrying performance of iron-based superconducting tape.
Therefore, it is necessary to develop a kind of iron-based recombination line, band preparation process, superconducting core consistency and critical electricity are being improved
While current density, the mechanical strength of wire rod, band is improved, production cost is reduced, makes that it is suitable for hyperconductive cable and superconducting magnetics
The preparation of body.
Invention content
The purpose of the present invention is being directed to above-mentioned prior art the problem of iron-based superconducting line strips produce, one is proposed
Kind prepare high mechanical properties, high critical current densities iron-based superconducting composite strip method.The method of the present invention is simple for process, at
This is cheap, is suitable for large-scale production.
The purpose of the present invention is what is be achieved through the following technical solutions.
A method of preparing iron-based superconducting composite strip, which is characterized in that the processing step of the preparation method is as follows:
(1) iron-based superconducting precursor powder is inserted in inner layer metal pipe, is processed into single band;
(2) outer layer metal capsule is machined so that single band can be inserted in outer after processing in step (1)
In layer metal capsule;
(3) the single band that step (1) obtains is completely nested in the outer layer metal jacket obtained through step (2), to this
There is the compound jacket of inside and outside layer metal tube to be machined, obtains composite strip;
(4) composite strip that step (3) obtains is heat-treated, obtains iron-based superconducting composite strip.
Iron-based superconducting precursor powder in step (1) is the iron with Fe (Se, Te, S) or FeAs superconducting layers in crystal structure
Base superconducting compound, or be the iron-based superconducting compound with Fe (Se, Te, S) or FeAs superconducting layers in the crystal structure
With the mixture of dopant material;
Inner layer metal Guan Weiyin pipes in step (1) or silver alloy pipe;
The thickness of single band in step (1) is 0.1-3.0mm, width 0.5-15mm;
The material of outer layer metal jacket in step (2) be nickel, copper, silver, gold, tungsten, tantalum, hafnium, molybdenum, vanadium, chromium, titanium, manganese,
One kind in niobium, zirconium, cobalt, cadmium, zinc, aluminium, or more any one in the alloy of metal, Huo Zhetie or chromium content<10%
Ferrous alloy;
The thickness of composite strip in step (3) is 0.1-5mm;
In step (4), the temperature of heat treatment is 200 DEG C -1400 DEG C, and heat treatment time is 0.1~200h, and pressure is
0.01Pa-500Mpa。
Compared with the prior art, the present invention has the following advantages:
(1) for the method for the present invention using hard metal as outer jacket, the iron-based superconducting composite strip of preparation has high machinery
Intensity;Internal layer Ag or Ag alloy strip steel rolled stock is first prepared, ensure that the texture degree of band core, then band and the progress of outer layer jacket is compound
Processing, improves the consistency of band core so that band core is uniformly and continuous, to improve critical current density.
(2) the method for the present invention simple process and low cost is honest and clean, independent of high-tension apparatus, is suitable for large-scale production.
Description of the drawings
Fig. 1 is the Ba in the embodiment of the present invention 10.6K0.4Fe2As2Superconducting composite strip;
Fig. 2 is Ba in the embodiment of the present invention 10.6K0.4Fe2As2Superconducting composite strip transmits critical current under the magnetic fields 1-27T
Density is with magnetic induction intensity change curve.
Specific implementation mode
Below in conjunction with drawings and examples further describe the present invention.
Embodiment 1
Prepare Ba0.6K0.4Fe2As2Front axle shell is uniformly mixed with Sn powder, obtains mixture by superconducting precursor powder.By the mixing
Object is inserted in Ag pipes, and both ends clamp.By Ag pipes by swaging, to be processed into thickness be 0.4mm for drawing, flat rolling, width is
The single band of 3mm.Hastelloy pipe is taken, it is 1.7mm that it is prepared into thickness by flat rolling, and width is the outsourcing of 3mm
Casing.Above-mentioned Ag bands are inserted in outside the Hastelloy after processing in canning tube again, form complex.The complex is passed through flat
Rolling system prepares the composite strip that thickness is 0.8mm.The band is finally placed in 0.1Mpa, argon atmosphere, is sintered at 800 DEG C
0.5 hour, iron-based superconducting composite strip is prepared, as shown in Figure 1.The present embodiment system is measured using micro Vickers hardness tester
The Vickers hardness of the superconducting core of standby iron-based superconducting composite strip reaches 210, illustrates it with high-compactness;Utilize northeastern Japan
The low temperature high-intensity magnetic field test system in university's superconductor high-intensity magnetic field laboratory (HFLSM) measures, and iron-based manufactured in the present embodiment is super
Composite strip is led in 4.2K, the magnetic fields 10T lower critical current density reaches 8.0 × 104A/cm2, as shown in Figure 2.
Embodiment 2
Prepare Sr0.6K0.4Fe2As2Superconducting precursor powder.Front axle shell is inserted in Ag/Sn compo pipes, both ends clamp.By the Ag/
Sn compo pipes are by swaging, to be processed into thickness be 0.1mm for drawing, rolling, and width is the single band of 0.5mm.Meng Naier is taken to close
Jin Guan is machined it.Above-mentioned Ag/Sn alloy strip steel rolled stocks are inserted in the monel alloy casing after processing again, composition
Complex.The complex is prepared into the composite strip that thickness is 0.1mm by cold-press process.The band is finally placed in 880
DEG C, be sintered 200 hours under 0.01Pa pressure, prepare iron-based superconducting composite strip.
Embodiment 3
Prepare SmO0.88F0.12FeAs superconducting precursor powders.Front axle shell is inserted in Ag/Mn alloy sleeves, both ends clamp.It should
Ag/Mn alloy sleeves are by swaging, to be processed into thickness be 0.2mm for drawing, rolling, hot pressing, and width is the single band of 15mm.It takes
Tantalum pipe carries out hot rolling to it.Above-mentioned Ag/Mn alloy strip steel rolled stocks are inserted in the tantalum pipe after processing again, form complex.It should
Complex goes out the composite strip that thickness is 5mm by aperture rolling.Finally the band is placed in hot isostatic pressing stove, in argon gas
Atmosphere, 1400 DEG C, be sintered 0.1 hour under 500Mpa pressure, prepare iron-based superconducting composite strip.
Embodiment 4
Prepare BaFe1.84Co0.16As2Superconducting precursor powder.Front axle shell is inserted in Ag pipes, both ends clamp.The Ag pipes are passed through
It is 3mm to be machined into thickness, and width is the single band of 6mm.Ferrous alloy pipe is taken, it is machined.It again will be upper
It states in the ferrous alloy pipe after Ag bands are inserted in processing, forms complex.It is for thickness is gone out by flat rolling by the complex
The composite strip of 2mm.Finally the band is placed under argon atmosphere, 100Mpa axial compressive forces, 850 DEG C be sintered 50 hours, prepare
Go out iron-based superconducting composite strip.
Embodiment 5
Prepare FeTe0.5Se0.5Superconducting precursor powder.Front axle shell is inserted in Ag/Mg alloy sleeves, both ends clamp.By the Ag/
Mg alloy sleeves are by swaging, to be processed into thickness be 0.3mm for drawing, rolling, and width is the single band of 5mm.Nickel tube is taken, to it
It is machined.Above-mentioned Ag/Mg alloy strip steel rolled stocks are inserted in the nickel tube after processing again, form complex.The complex is led to
Flat rolling is crossed for the composite strip that thickness is 0.6mm is gone out.Finally the band is placed under argon atmosphere, 0.1Mpa, 750 DEG C of burnings
Knot 1 hour, prepares iron-based superconducting composite strip.
Embodiment 6
Prepare Sr2VO3FeAs superconducting precursor powders.Front axle shell is inserted in Ag/Mg/Ni compo pipes, both ends clamp.By the Ag/
Mg/Ni compo pipes are by swaging, to be processed into thickness be 1mm for drawing, flat rolling, and width is the single band of 3.5mm.Take molybdenum
Pipe, is machined it.Above-mentioned Ag/Mg/Ni bands are inserted in the molybdenum tube after processing again, form complex.This is answered
Zoarium prepares the composite strip that thickness is 0.9mm by hot rolling.Finally the band is placed in hot pressing furnace in 160Mpa axial directions
Under pressure, argon atmosphere, 1000 DEG C be sintered 10 hours, prepare iron-based superconducting composite strip.
Embodiment 7
Prepare Ba0.6K0.4Fe2As2Front axle shell is uniformly mixed with Sn powder, obtains mixture by superconducting precursor powder.By the mixing
Object is inserted in Ag/Sn compo pipes, and both ends clamp.By the Ag/Mg compo pipes by swaging, drawing, rolling be processed into thickness and be
0.2mm, width are the single band of 2mm.Copper pipe is taken, it is machined.Above-mentioned Ag/Mg alloy strip steel rolled stocks are inserted in again and are added
In copper pipe after work, complex is formed.The complex is obtained into the composite strip that thickness is 0.5mm by flat rolling.Finally
The band is placed in 500 DEG C, is sintered 20 hours under 0.01Pa pressure, iron-based superconducting composite strip is prepared.
Embodiment 8
Prepare Ba0.7K0.3Fe2As2Front axle shell is uniformly mixed with Sn powder, obtains mixture by superconducting precursor powder.By the mixing
Object is inserted in Ag compo pipes, and both ends clamp.By the Ag compo pipes by swaging, to be processed into thickness be 0.3mm for drawing, rolling, wide
Degree is the single band of 1.5mm.Niobium pipe is taken, it is machined.After above-mentioned Ag/Mn alloy strip steel rolled stocks are inserted in processing again
In niobium pipe, complex is formed.The complex is obtained into the composite strip that thickness is 0.8mm by flat rolling.Finally by the band
Material is placed in 600 DEG C, is sintered 3 hours under 0.01Pa pressure, prepares iron-based superconducting composite strip.
Claims (7)
1. a kind of method preparing iron-based superconducting composite strip, which is characterized in that steps are as follows for the preparation method:
(1) iron-based superconducting precursor powder is inserted in inner layer metal pipe, is processed into single band;
(2) outer layer metal capsule is machined so that the single band in step (1) can be inserted in the outer layer after processing
In metal capsule;
(3) the single band that step (1) obtains is packed into completely in the outer layer metal jacket that step (2) obtains, to this have it is inside and outside
The compound jacket of layer metal tube is machined, and composite strip is obtained;
(4) composite strip that step (3) obtains is heat-treated, obtains iron-based superconducting composite strip.
2. preparation method as described in claim 1, which is characterized in that the iron-based superconducting precursor powder in the step (1) is crystalline substance
Iron-based superconducting compound with Fe (Se, Te, S) or FeAs superconducting layers in body structure, or to have in the crystal structure
Fe (Se, Te, S) or the iron-based superconducting compound of FeAs superconducting layers and the mixture of dopant material.
3. preparation method as described in claim 1, which is characterized in that inner layer metal Guan Weiyin pipes or silver in the step (1)
Compo pipe.
4. preparation method as described in claim 1, which is characterized in that the thickness of the single band in the step (1) is
0.1-3.0mm, width 0.5-15mm.
5. preparation method as described in claim 1, which is characterized in that the material of the outer layer metal jacket in the step (2)
In alloy for nickel, copper, silver, gold, tungsten, tantalum, hafnium, molybdenum, vanadium, chromium, titanium, manganese, niobium, zirconium, cobalt, cadmium, zinc, aluminium, or more metal
Any one, Huo Zhetie or chromium content<10% ferrous alloy.
6. preparation method as described in claim 1, which is characterized in that the thickness of the composite strip in the step (3) is
0.1-5mm。
7. preparation method as described in claim 1, which is characterized in that the temperature being heat-treated in the step (4) is 200 DEG C-
1400 DEG C, heat treatment time is 0.1~200h, pressure 0.01Pa-500Mpa.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109903927A (en) * | 2019-01-30 | 2019-06-18 | 中国科学院电工研究所 | A kind of preparation method of the iron-based superconducting line strips of compound jacket |
CN110931160A (en) * | 2019-10-23 | 2020-03-27 | 中国科学院电工研究所 | Iron-based superconducting precursor powder, preparation method thereof and iron-based superconducting wire strip |
CN113614858A (en) * | 2019-03-28 | 2021-11-05 | 株式会社藤仓 | Oxide superconducting wire |
CN114242333A (en) * | 2021-12-23 | 2022-03-25 | 上海交通大学 | Iron-selenium-tellurium-sulfur superconducting target material and preparation method and application thereof |
CN114360807A (en) * | 2022-01-17 | 2022-04-15 | 中国科学院电工研究所 | Iron-based superconducting multi-core wire and preparation method and application thereof |
CN114566326A (en) * | 2022-03-29 | 2022-05-31 | 中国科学院电工研究所 | Method for obtaining composite sheathed iron-based superconducting wire strip by extrusion molding |
CN114566326B (en) * | 2022-03-29 | 2024-07-30 | 中国科学院电工研究所 | Method for obtaining composite coated iron-based superconducting wire strip through extrusion forming |
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CN109903927A (en) * | 2019-01-30 | 2019-06-18 | 中国科学院电工研究所 | A kind of preparation method of the iron-based superconducting line strips of compound jacket |
CN113614858A (en) * | 2019-03-28 | 2021-11-05 | 株式会社藤仓 | Oxide superconducting wire |
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CN110931160B (en) * | 2019-10-23 | 2021-03-19 | 中国科学院电工研究所 | Iron-based superconducting precursor powder, preparation method thereof and iron-based superconducting wire strip |
CN114242333A (en) * | 2021-12-23 | 2022-03-25 | 上海交通大学 | Iron-selenium-tellurium-sulfur superconducting target material and preparation method and application thereof |
CN114242333B (en) * | 2021-12-23 | 2023-03-14 | 上海交通大学 | Iron-selenium-tellurium-sulfur superconducting target material and preparation method and application thereof |
CN114360807A (en) * | 2022-01-17 | 2022-04-15 | 中国科学院电工研究所 | Iron-based superconducting multi-core wire and preparation method and application thereof |
CN114360807B (en) * | 2022-01-17 | 2024-04-16 | 中国科学院电工研究所 | Iron-based superconducting multi-core wire rod and preparation method and application thereof |
CN114566326A (en) * | 2022-03-29 | 2022-05-31 | 中国科学院电工研究所 | Method for obtaining composite sheathed iron-based superconducting wire strip by extrusion molding |
CN114566326B (en) * | 2022-03-29 | 2024-07-30 | 中国科学院电工研究所 | Method for obtaining composite coated iron-based superconducting wire strip through extrusion forming |
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