CN114360807B - Iron-based superconducting multi-core wire rod and preparation method and application thereof - Google Patents
Iron-based superconducting multi-core wire rod and preparation method and application thereof Download PDFInfo
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- CN114360807B CN114360807B CN202210048462.5A CN202210048462A CN114360807B CN 114360807 B CN114360807 B CN 114360807B CN 202210048462 A CN202210048462 A CN 202210048462A CN 114360807 B CN114360807 B CN 114360807B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 406
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 202
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005096 rolling process Methods 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 238000010618 wire wrap Methods 0.000 claims abstract description 22
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 20
- 238000005242 forging Methods 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 229910000856 hastalloy Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 3
- 229910000792 Monel Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910001026 inconel Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
- 238000003754 machining Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000002887 superconductor Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- RQCJDSANJOCRMV-UHFFFAOYSA-N [Mn].[Ag] Chemical compound [Mn].[Ag] RQCJDSANJOCRMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
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Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F6/00—Superconducting magnets; Superconducting coils
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
The invention relates to the technical field of superconducting wires, in particular to an iron-based superconducting multi-core wire, a preparation method and application thereof. According to the preparation method provided by the invention, a plurality of iron-based superconducting strips are put into a multi-core wire wrap to obtain a complex; the iron-based superconducting tape comprises a pre-textured iron-based superconducting core, and the cross section of the multi-core wire wrap is rectangular or square; rolling or drawing the composite body to obtain an initial multi-core wire rod, wherein hole rolling or four-roll rolling is adopted in the rolling, and a square hole die is adopted in the drawing; and carrying out heat treatment on the initial multi-core wire rod in a protective gas or vacuum environment to obtain the iron-based superconducting multi-core wire rod. The preparation method provided by the invention can effectively improve the texture degree of the superconducting phase grains in the iron-based superconducting multi-core wire rod, thereby improving the current transmission performance of the wire rod.
Description
Technical Field
The invention relates to the technical field of superconducting wires, in particular to an iron-based superconducting multi-core wire, a preparation method and application thereof.
Background
The iron-based superconducting material can be divided into a plurality of material systems according to the composition ratio and the crystal structure of the parent compound, wherein 1111 system (as SmFeAsO 1-x F x As representative) and 122 systems (in terms of Ba 1-x K x Fe 2 As 2 And Sr 1-x K x Fe 2 As 2 Is representative), the iron-based superconductor has higher superconducting transition temperature (58K and 38K at present) and the upper critical field of the iron-based superconductor and the iron-based superconductor can exceed 100T, and the iron-based superconductor has smaller anisotropism, has unique application advantages in the field of high field intensity electricity, and has stronger application potential in the fields of next generation high field Magnetic Resonance Imaging (MRI), superconducting energy storage systems (SMES), nuclear magnetic resonance spectrometer (NMR), future high-energy particle accelerators, controllable nuclear fusion devices and the like. In addition, the iron-based superconducting material can be prepared into wires and strips by adopting a powder tubing method with simpler process and lower cost.
At present, a typical process for preparing an iron-based superconducting multi-core wire by adopting a powder tubing method is to prepare an iron-based superconducting single-core round wire by adopting a round die drawing process, then cut the iron-based superconducting single-core round wire into a plurality of short samples with equal length, compound the short samples into a metal round tube, and prepare the multi-core round wire by adopting cold working processes such as rotary forging, drawing and the like. The wire rod obtained by the preparation method has the main problems that the grain orientation in the superconducting core is random, and the transmission critical current of the wire rod is obviously reduced due to wide-angle grain boundaries among grains. The current method for improving the grain orientation is to roll the multi-core round wire into a multi-core strip by adopting a flat roll rolling method, and the grain in the superconducting core is induced to be textured and oriented by mechanical deformation force in the process, so that the current carrying performance of the multi-core strip is improved.
However, from the practical point of view, the wire is more advantageous to twisting of the cable and winding of the magnet coils than the strip, and thus it is more advantageous to prepare the iron-based superconducting multi-core wire with high performance for future practical use.
Disclosure of Invention
In view of the above, the invention provides an iron-based superconducting multi-core wire, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an iron-based superconducting multi-core wire, which comprises the following steps:
filling a plurality of iron-based superconducting strips into a multi-core wire wrap to obtain a composite body; the iron-based superconducting tape comprises a textured iron-based superconducting core, and the cross section of the multi-core wire wrap is rectangular or square;
rolling or drawing the composite body to obtain an initial multi-core wire rod, wherein hole rolling or four-roll rolling is adopted in the rolling, and a square hole die is adopted in the drawing;
and carrying out heat treatment on the initial multi-core wire rod in a protective gas or vacuum environment to obtain the iron-based superconducting multi-core wire rod.
Preferably, the iron-based superconducting tape comprises a single core iron-based superconducting tape and/or a multi-core iron-based superconducting tape;
the preparation method of the single-core iron-based superconducting tape comprises the following steps of:
filling an iron-based superconducting material into a belt material sheath to obtain a sheath superconducting material;
sequentially performing rotary swaging, drawing and rolling on the sheath superconducting material to obtain a single-core iron-based superconducting tape;
the preparation method of the multi-core iron-based superconducting tape comprises the following steps:
filling an iron-based superconducting material into a belt material sheath to obtain a sheath superconducting material;
sequentially performing rotary swaging and drawing on the sheath superconducting material to obtain an iron-based superconducting round wire;
filling a plurality of iron-based superconducting round wires into a strip sheath to obtain sheath superconducting round wires, wherein the number of the iron-based superconducting round wires is more than or equal to 2;
and (3) sequentially performing rotary forging, drawing and rolling on the sheathed superconducting round wire to obtain the multi-core iron-based superconducting strip.
Preferably, the thickness of the iron-based superconducting tape is independently 0.1-10 mm, the width is independently 1-100 mm, and the length is independently 10-2000 mm.
Preferably, the wall thickness of the cross section of the multi-core wire rod sheath is 0.5-50 mm, the side length of the cross section of the multi-core wire rod sheath is 2-200 mm, and the length of the multi-core wire rod sheath is more than or equal to the length of the iron-based superconducting strip.
Preferably, the heat preservation temperature of the heat treatment is 500-1200 ℃, the heat preservation time of the heat treatment is 0.5-10 h, and the pressure of the protective gas is 0.1-200 MPa.
Preferably, the chemical composition of the iron-based superconducting material is AFe doped 2 As 2 And/or doping LnOFePn;
the doped AFe 2 As 2 Wherein A is Ba, sr, K, cs, ca or Eu, said doped AFe 2 As 2 The medium doping element is one or more of K, na, P and Co;
ln in the doped LnOFePn is La, ce, pr, nd, sm, gd, tb, dy, ho or Y, pn in the doped LnOFePn is P or As, and the doped element in the doped LnOFePn is F.
Preferably, the multi-core wire sheath material comprises copper, iron, nickel, silver, manganese, titanium, niobium, tantalum, an alloy containing the above metal elements as main components, stainless steel, low carbon steel, monel alloy, hastelloy alloy or Inconel alloy.
The invention provides the iron-based superconducting multi-core wire rod prepared by the preparation method, and the cross section of the iron-based superconducting multi-core wire rod is square, rectangular or parallelogram.
Preferably, the side length of the cross section of the iron-based superconducting multi-core wire is 0.5-5 mm.
The invention provides application of the iron-based superconducting multi-core wire in the iron-based superconducting cable or the iron-based superconducting magnet.
The invention provides a preparation method of an iron-based superconducting multi-core wire, which comprises the following steps: filling a plurality of iron-based superconducting strips into a multi-core wire wrap to obtain a composite body; the iron-based superconducting tape comprises a pre-textured iron-based superconducting core, and the cross section of the multi-core wire wrap is rectangular or square; rolling or drawing the composite body to obtain an initial multi-core wire rod, wherein hole rolling or four-roll rolling is adopted in the rolling, and a square hole die is adopted in the drawing; and carrying out heat treatment on the initial multi-core wire rod in a protective gas or vacuum environment to obtain the iron-based superconducting multi-core wire rod. The preparation method provided by the invention adopts the iron-based superconducting tape comprising the pre-textured iron-based superconducting core as a raw material, adopts the multi-core wire rod sheath with rectangular or square cross section to prepare the composite body, can ensure that the multi-core wire rod sheath and the iron-based superconducting tape have better matching degree, and adopts grooved rolling or four-roller rolling in the process of rolling and drawing the composite body, and adopts a square hole die to effectively control the cross section of the wire rod to form square, rectangular or parallelogram, thereby effectively reducing the degree of random transformation of grain orientation arrangement of the superconducting cores in the iron-based superconducting tape during rolling and drawing. Therefore, the invention not only can prepare the shape of the finished product into a wire rod, but also can further improve the volume percentage of the single-oriented crystal grains in the superconducting core compared with the traditional round die drawing process. The preparation method provided by the invention can effectivelyThe texture degree of superconducting phase grains in the iron-based superconducting multi-core wire is improved, so that the current transmission performance of the wire is improved. The results of the examples show that the iron-based superconducting multi-core wire product provided by the invention is detected by Electron Back Scattering Diffraction (EBSD), the volume percentage of grain boundaries with the grain boundary included angle smaller than 10 degrees in the superconducting core is more than or equal to 10%, the difference between two diagonal lines of the cross section of the wire product is at least 2%, the transmission critical current density of the wire at the temperature of 4.2K and the magnetic field strength of 10T is more than or equal to 1.2 multiplied by 10 4 A/cm 2 。
The preparation method provided by the invention is simple and feasible, has low cost, and is beneficial to the development of the iron-based superconducting cable and the superconducting magnet.
Drawings
FIG. 1 is a schematic view of an iron-based superconducting multi-core wire prepared in example 1 of the present invention;
FIG. 2 is a schematic view of an iron-based superconducting multi-core wire prepared in example 3 of the present invention;
1-iron-based superconducting cores, 2-single-core iron-based superconducting tapes, 3-tape jackets, 4-multi-core wire jackets and 5-multi-core iron-based superconducting tapes.
Detailed Description
The invention provides a preparation method of an iron-based superconducting multi-core wire, which comprises the following steps:
filling a plurality of iron-based superconducting strips into a multi-core wire wrap to obtain a composite body; the iron-based superconducting tape comprises a textured iron-based superconducting core, and the cross section of the multi-core wire wrap is rectangular or square;
rolling or drawing the composite body to obtain an initial multi-core wire rod, wherein hole rolling or four-roll rolling is adopted in the rolling, and a square hole die is adopted in the drawing;
and carrying out heat treatment on the initial multi-core wire rod in a protective gas or vacuum environment to obtain the iron-based superconducting multi-core wire rod.
In the present invention, the raw materials used are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, a plurality of iron-based superconducting strips are arranged in a multi-core wire wrap to obtain a composite body; the iron-based superconducting tape comprises a textured iron-based superconducting core, and the cross section of the multi-core wire wrap is rectangular or square.
In the present invention, the iron-based superconducting tape preferably includes a single core iron-based superconducting tape and/or a multi-core iron-based superconducting tape;
in the present invention, the method for producing a single core iron-based superconducting tape preferably comprises the steps of:
loading an iron-based superconducting material (hereinafter referred to as a first iron-based superconducting material) into a tape jacket (hereinafter referred to as a first tape jacket) to obtain a jacket superconducting material (hereinafter referred to as a first jacket superconducting material);
and (3) sequentially performing rotary swaging (hereinafter referred to as first rotary swaging), drawing (hereinafter referred to as first drawing) and rolling (hereinafter referred to as first rolling) on the first sheath superconducting material to obtain the single-core iron-based superconducting tape.
In the present invention, an iron-based superconducting material (hereinafter referred to as a first iron-based superconducting material) is packed into a tape jacket (hereinafter referred to as a first tape jacket) to obtain a jacket superconducting material.
In the present invention, the chemical composition of the first iron-based superconducting material is preferably a doped AFe 2 As 2 And/or doping LnOFePn.
In the present invention, the doped AFe 2 As 2 Preferably A is Ba, sr, K, cs, ca or Eu, said doped AFe 2 As 2 The medium doping element is preferably one or more of K, na, P and Co, more preferably K, na, P or Co. In the present invention, the doped AFe 2 As 2 When the medium doping element is K and/or Na, the doping AFe 2 As 2 The mass percentage of atoms of the medium doping element is preferably 2 to 18 percent. In the present invention, the doped AFe 2 As 2 When the medium doping element is P and/or Co, the doping AFe 2 As 2 The mass percentage of atoms of the medium doping element is preferably 4 to 36%.
In the present invention, ln in the doped LnOFePn is preferably La, ce, pr, nd, sm, gd, tb, dy, ho or Y, pn in the doped LnOFePn is preferably P or As, and the doping element in the doped LnOFePn is preferably F. In the invention, the atomic mass percentage of the doping element in the doped LnOFePN is preferably 3-22%.
In the present invention, the first iron-based superconducting material has a higher superconducting critical temperature and critical magnetic field.
In the present invention, the material of the first band wrap preferably includes one or more of silver, silver alloy, copper alloy, niobium, iron, and stainless steel. In a specific embodiment of the present invention, when the material of the first band jacket preferably includes two or more of silver, silver alloy, copper alloy, niobium, iron and stainless steel, the first band jacket is preferably a band jacket made of two or more of the foregoing materials and is used by nesting together.
In the present invention, the wall thickness of the first band wrap is preferably 0.5 to 50mm, more preferably 1 to 10mm.
In the present invention, the first band wrap is preferably circular in cross-sectional shape. In the present invention, the outer diameter of the first band wrap is preferably 8 to 50mm
In the invention, the belt material sheath can protect the iron-based superconducting core and has better electric conduction and heat conduction properties.
After the first sheath superconducting material is obtained, the first sheath superconducting material is subjected to first rotary forging, first drawing and first rolling in sequence, and a single-core iron-based superconducting strip is obtained.
The invention has no special requirements on the specific implementation process of the first rotary forging, the first drawing and the first rolling.
In the present invention, the thickness of the single core iron-based superconducting tape is preferably 0.1 to 10mm, more preferably 0.2 to 8mm.
In the present invention, the width of the single core iron-based superconducting tape is preferably 1 to 100mm, and preferably 3 to 82mm.
In the present invention, the length of the single core iron-based superconducting tape is preferably 10 to 2000mm, more preferably 20 to 1500mm.
In the invention, the preparation method of the multi-core iron-based superconducting tape comprises the following steps:
filling an iron-based superconducting material (hereinafter referred to as a second iron-based superconducting material) into a strip jacket (hereinafter referred to as a second strip jacket) to obtain a jacket superconducting material (hereinafter referred to as a second jacket superconducting material);
sequentially performing rotary swaging (hereinafter referred to as second rotary swaging) and drawing (hereinafter referred to as second drawing) on the second cladding superconducting material to obtain an iron-based superconducting round wire;
filling a plurality of iron-based superconducting round wires into a strip sheath (hereinafter referred to as a third strip sheath) to obtain sheath superconducting round wires, wherein the number of the iron-based superconducting round wires is more than or equal to 2;
and (3) sequentially performing rotary forging (hereinafter referred to as third rotary forging), drawing (hereinafter referred to as third drawing) and rolling (hereinafter referred to as third rolling) on the jacketed superconducting round wire to obtain the multi-core iron-based superconducting strip.
The invention loads the iron-based superconducting material (hereinafter referred to as a second iron-based superconducting material) into a strip sheath (hereinafter referred to as a second strip sheath) to obtain a sheath superconducting material (hereinafter referred to as a second sheath superconducting material);
in the present invention, the protection range of the second iron-based super-material is preferably the same as that of the first iron-based super-conductive material, and will not be described herein.
In the present invention, the protection range of the material and the size of the second strip material sheath is preferably the same as the protection range of the material and the size of the first iron strip material sheath, and will not be described herein.
After the second sleeve superconducting material is obtained, the second sleeve superconducting material is subjected to second rotary forging and second drawing in sequence, and the iron-based superconducting round wire is obtained.
The invention has no special requirements on the specific implementation process of the second rotary forging and the second drawing.
After the iron-based superconducting round wires are obtained, a plurality of iron-based superconducting round wires are arranged in a third belt material sheath to obtain sheath superconducting round wires, and the number of the iron-based superconducting round wires is more than or equal to 2.
In the invention, the number of the iron-based superconducting round wires is more than or equal to 2, and is preferably 3-200.
In the present invention, the protection range of the material and the size of the third strip sheath is preferably the same as the protection range of the material and the size of the first iron strip sheath, and will not be described herein.
After the wrapped superconducting round wire is obtained, the wrapped superconducting round wire is subjected to third rotary forging, third drawing and third rolling in sequence, and the multi-core iron-based superconducting strip is obtained.
The invention has no special requirements on the specific implementation process of the third rotary forging, the third drawing and the third rolling.
In the present invention, the thickness of the multicore iron-based superconducting tape is preferably 0.1 to 10mm, more preferably 0.2 to 8mm.
In the present invention, the width of the multicore iron-based superconducting tape is preferably 1 to 100mm, and preferably 3 to 82mm.
In the present invention, the length of the multi-core iron-based superconducting tape is preferably 10 to 2000mm, more preferably 20 to 1500mm.
In the invention, the iron-based superconducting tape comprises a textured iron-based superconducting core, which enables the superconducting core of the high iron-based superconducting multi-core wire to obtain better grain orientation.
In the present invention, the number of the iron-based superconducting tapes is not less than 2, preferably not less than 6.
In a specific embodiment of the invention, the number of iron-based superconducting tapes is preferably inner 13, 9, 6, 10 or 50.
In the present invention, the material of the multi-core wire sheath is preferably copper, iron, nickel, silver, manganese, titanium, niobium, tantalum, an alloy containing the above metal elements as a main component, stainless steel, low carbon steel, monel alloy, hastelloy alloy or Inconel alloy.
In the invention, the material of the multi-core wire wrap is preferably the material, so that the overall mechanical strength of the multi-core wire product can be further improved, and the multi-core wire wrap has better electric conductivity and heat conductivity.
In the invention, the cross section of the multi-core wire wrap is rectangular or square.
In the present invention, the thickness of the cross section of the multi-core wire wrap is preferably 0.5 to 50mm, more preferably 1 to 35mm.
In the present invention, the side length of the cross section of the multi-core wire wrap is preferably 2 to 200mm, more preferably 3.5 to 158mm.
In the invention, the length of the multi-core wire wrap is preferably equal to or greater than the length of the iron-based superconducting tape.
In the present invention, the inner dimensions of the multi-core wire wrap are preferably matched to the total dimensions of the encased iron-based superconducting tapes.
After the composite body is obtained, the present invention performs rolling (hereinafter referred to as fourth rolling) or drawing (hereinafter referred to as fourth drawing) of the composite body to obtain an initial multi-core wire rod, wherein the drawing adopts a square hole die.
In the present invention, it is preferable that both end surfaces of the multicore wire rod sheath are sealed before the fourth rolling or the fourth drawing.
In the present invention, the fourth rolling is a hole rolling or a four-roll rolling.
In the invention, a square hole die is adopted for drawing.
According to the preparation method provided by the invention, the multi-core wire rod sheath with square or rectangular cross section is preferably combined with the grooved rolling, four-roller rolling or square hole die drawing process, so that the cross section shape of the wire rod can be effectively controlled in the process of performing fourth rotary forging and fourth drawing on the composite body, meanwhile, the influence of the fourth rotary forging and fourth drawing on the arrangement of crystal grains in the superconducting core is effectively reduced, and the two diagonal deviation of the cross section of the finally prepared wire rod is less than or equal to 2%.
After the initial multi-core wire rod is obtained, the initial multi-core wire rod is subjected to heat treatment in a protective gas or vacuum environment to obtain the iron-based superconducting multi-core wire rod.
In the present invention, the heat treatment is preferably carried out at a holding temperature of 500 to 1200 ℃, more preferably 550 to 1100 ℃.
In the present invention, the heat-retaining time of the heat treatment is preferably 0.5 to 10 hours, more preferably 1 to 8 hours.
In the present invention, the heat treatment is performed in a protective gas or vacuum atmosphere.
In the present invention, the shielding gas is preferably an inert gas, more preferably Ar.
In the present invention, the pressure of the shielding gas is preferably 0.1 to 200MPa, more preferably 10 to 150MPa.
The invention provides the iron-based superconducting multi-core wire rod prepared by the preparation method, and the cross section of the iron-based superconducting multi-core wire rod is square, rectangular or parallelogram.
In the present invention, the side length of the cross section of the iron-based superconducting multi-core wire is preferably 0.5 to 5mm, more preferably 1 to 4.5mm.
In the invention, the volume percentage of grain boundaries with the included angle of the grain boundaries smaller than 10 degrees in the superconducting cores of the iron-based superconducting multi-core wire rod is more than or equal to 10 percent.
In the invention, the two diagonal deviations of the cross section of the iron-based superconducting multi-core wire rod are at least 2%,
the invention provides application of the iron-based superconducting multi-core wire in an iron-based superconducting cable or an iron-based superconducting magnet.
Compared with a strip, the iron-based superconducting multi-core wire provided by the invention is more beneficial to twisting of cables and winding of magnet coils.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
BaFe doped with K element 2 As 2 The iron-based superconducting material is filled into a pure silver metal pipe with the outer diameter of 8mm and the wall thickness of 1mm, and is subjected to rotary swaging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 0.3mm and the width of 4 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 100mm, stacking 13 short samples, and then placing the short samples into a pure copper square metal tube with the side length of 6mm, the wall thickness of 1mm and the length of 100 mm;
machining the multi-core composite body into a wire rod with the side length of 1.2mm by adopting a hole-type rolling mill, wherein the deviation of two diagonal lines on the cross section of the wire rod is 8%;
and (3) carrying out heat treatment on the wire rod in a vacuum environment, wherein the heat treatment temperature is 750 ℃, and the heat preservation time is 2 hours, so as to obtain the iron-based superconducting multi-core wire rod.
Through tests, the volume percentage content of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 15%, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 2.3 multiplied by 10 4 A/cm 2 。
Example 2
BaFe doped with K element 2 As 2 The iron-based superconducting powder is filled into a pure silver metal pipe with the outer diameter of 8mm and the wall thickness of 1.5mm, and is subjected to rotary forging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 0.3mm and the width of 2.8 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 100mm, stacking 9 short samples, and then placing the short samples into a copper-nickel alloy square metal tube with the side length of 5mm, the wall thickness of 1mm and the length of 100 mm;
machining the multi-core composite body into a wire rod with the side length of 0.6mm by adopting a hole-type rolling mill, wherein the deviation of two diagonal lines on the cross section of the wire rod is 10%;
and (3) carrying out heat treatment on the wire rod in argon with the pressure of 0.1MPa, wherein the heat treatment temperature is 850 ℃, and the heat preservation time is 1h, so as to obtain the iron-based superconducting multi-core wire rod.
Through tests, the volume percentage content of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 13 percent, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 2.1 multiplied by 10 4 A/cm 2 。
Example 3
SrFe doped with K element 2 As 2 The iron-based superconducting powder is filled into a pure silver metal pipe with the outer diameter of 14mm and the wall thickness of 1.5mm, the round wire with the diameter of 1.5mm is prepared after rotary forging and drawing, the round wire is cut into a short sample with the length of 200mm,7 short samples are compounded into a silver-manganese alloy pipe with the outer diameter of 8mm and the wall thickness of 1.5mm, and the silver-manganese alloy pipe is subjected to rotary forging, drawing and rolling to prepare an iron-based superconductive seven-core strip with the thickness of 0.4mm and the width of 4.8 mm;
cutting an iron-based superconductive seven-core strip into short samples with the length of 150mm, stacking 9 short samples, and then compounding the short samples into a pure iron square metal pipe with the side length of 9mm, the wall thickness of 2mm and the length of 150 mm;
machining the multi-core composite body into a wire rod with the side length of 2.0mm by adopting a hole-type rolling mill, wherein the deviation of two diagonal lines on the cross section of the wire rod is 5%;
and (3) carrying out heat treatment on the wire rod in 0.1MPA argon, wherein the heat treatment temperature is 900 ℃, and the heat preservation time is 1h, so as to obtain the iron-based superconducting multi-core wire rod.
Through tests, the volume percentage of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 11%, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 1.6x10 4 A/cm 2 。
Example 4
BaFe doped with Na element 2 As 2 The iron-based superconducting powder is filled into a pure silver metal pipe with the outer diameter of 8mm and the wall thickness of 1.5mm, and is subjected to rotary forging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 0.3mm and the width of 1.8 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 100mm, stacking 6 short samples, compounding, putting the short samples into a pure copper square metal pipe with the side length of 4mm, the wall thickness of 1mm and the length of 120mm, and sealing two ends of the wire;
machining the multi-core composite body into a wire rod with the side length of 1.0mm by adopting a hole-type rolling mill, wherein the deviation of two diagonal lines on the cross section of the wire rod is 8%;
and (3) carrying out heat treatment on the wire rod in 200MPa of argon, wherein the heat treatment temperature is 700 ℃, and the heat preservation time is 4 hours, so as to obtain the iron-based superconducting multi-core wire rod.
Through testing, the volume percentage content of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 11 percent, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 5.2 multiplied by 10 4 A/cm 2 。
Example 5
Filling the SmOFeAs iron-based superconducting powder doped with the F element into a pure iron metal tube with the outer diameter of 12mm and the wall thickness of 1.5mm, and performing rotary forging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 0.6mm and the width of 8 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 300mm, stacking 10 short samples, and then compositely loading the short samples into a rectangular Hastelloy alloy tube with the width multiplied by the length of 8.5 multiplied by 10.5mm, the wall thickness of 1mm and the length of 300 mm;
processing the multi-core composite body into a wire rod with the side length of 3.0 multiplied by 2% by adopting a four-high mill, wherein the deviation of two diagonal lines on the cross section of the wire rod is 2%;
and (3) carrying out heat treatment on the wire rod in a vacuum environment, wherein the heat treatment temperature is 1200 ℃, and the heat preservation time is 0.5h, so as to obtain the iron-based superconducting multi-core wire rod.
Through testing, the volume percentage content of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 18 percent, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 1.2 multiplied by 10 4 A/cm 2 。
Example 6
CaFe doped with K element 4 As 4 The iron-based superconducting powder is filled into a pure silver metal pipe with the outer diameter of 8mm and the wall thickness of 1mm, and is subjected to rotary swaging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 0.3mm and the width of 3.8 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 500mm, stacking 50 short samples, compounding, putting the short samples into a pure copper square metal pipe with the side length of 12mm, the wall thickness of 2mm and the length of 600mm, and sealing two ends of the wire;
machining the multi-core composite body into a wire rod with the side length of 2.0mm by adopting a square hole die drawing process, wherein the deviation of two diagonal lines on the cross section of the wire rod is 3%;
and (3) carrying out heat treatment on the wire rod in argon of 150MPa, wherein the heat treatment temperature is 600 ℃, and the heat preservation time is 1h, so as to obtain the iron-based superconducting multi-core wire rod.
Through testing, the obtained iron-based superThe volume percentage of grain boundary with the included angle of grain boundary less than 10 degrees in the superconducting core of the multi-core-conductive wire rod is 15 percent, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 2.8x10 4 A/cm 2 。
Example 7
BaFe doped with K element 2 As 2 The iron-based superconducting powder is filled into a pure silver metal pipe with the outer diameter of 50mm and the wall thickness of 5mm, and is subjected to rotary swaging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 10mm and the width of 100 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 2000mm, stacking 10 short samples, and then compounding and loading the short samples into a silver-tin alloy square metal tube with the side length of 200mm, the wall thickness of 50mm and the length of 100 mm;
machining the multi-core composite body into a wire rod with the side length of 1.5mm by adopting a hole rolling mill and a square hole die drawing process, wherein the deviation of two diagonal lines on the cross section is 3%;
and (3) carrying out heat treatment on the wire rod in argon of 15MPa, wherein the heat treatment temperature is 880 ℃, and the heat preservation time is 1h, so as to obtain the iron-based superconducting multi-core wire rod.
Through testing, the volume percentage content of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 18 percent, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 8.5x10 4 A/cm 2 。
Example 8
Filling the NdOFeAs iron-based superconducting powder doped with the F element into a pure nickel metal tube with the outer diameter of 5mm and the wall thickness of 0.5mm, and performing rotary forging, drawing and rolling to prepare an iron-based superconducting single-core strip with the thickness of 0.1mm and the width of 1 mm;
cutting an iron-based superconducting single-core strip into short samples with the length of 10mm, stacking 10 short samples, and then compounding and loading the short samples into a square pure niobium pipe with the side length of 2mm, the wall thickness of 0.5mm and the length of 15 mm;
processing the multi-core composite body into a wire rod with the side length of 0.5mm by adopting a four-high mill and a pass mill, wherein the deviation of two diagonal lines on the cross section is 10%;
and (3) carrying out heat treatment on the wire rod in a vacuum environment, wherein the heat treatment temperature is 500 ℃, and the heat preservation time is 10 hours, so as to obtain the iron-based superconducting multi-core wire rod.
Through testing, the volume percentage content of grain boundary with the included angle of grain boundary smaller than 10 degrees in the superconducting core of the obtained iron-based superconducting multi-core wire rod is 10 percent, and the transmission critical current density of the wire rod under the magnetic field intensity of 4.2K and 10T is 1.2 multiplied by 10 4 A/cm 2 。
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the iron-based superconducting multi-core wire is characterized by comprising the following steps of:
filling a plurality of iron-based superconducting strips into a multi-core wire wrap to obtain a composite body; the iron-based superconducting tape comprises a textured iron-based superconducting core, and the cross section of the multi-core wire wrap is rectangular or square;
rolling or drawing the composite body to obtain an initial multi-core wire rod, wherein hole rolling or four-roll rolling is adopted in the rolling, and a square hole die is adopted in the drawing;
performing heat treatment on the initial multi-core wire rod in a protective gas or vacuum environment to obtain the iron-based superconducting multi-core wire rod; the cross section of the iron-based superconducting multi-core wire is square, rectangular or parallelogram, and the side length of the cross section of the iron-based superconducting multi-core wire is 0.5-5 mm; the difference between two diagonal lines of the section of the wire rod is less than or equal to 2 percent; the volume percentage of grain boundaries with the included angle of the grain boundaries smaller than 10 degrees in the superconducting cores of the iron-based superconducting multi-core wire rod is more than or equal to 10 percent.
2. The method of manufacturing according to claim 1, characterized in that the iron-based superconducting tape comprises a single core iron-based superconducting tape and/or a multi-core iron-based superconducting tape;
the preparation method of the single-core iron-based superconducting tape comprises the following steps of:
filling an iron-based superconducting material into a belt material sheath to obtain a sheath superconducting material;
sequentially performing rotary swaging, drawing and rolling on the sheath superconducting material to obtain a single-core iron-based superconducting tape;
the preparation method of the multi-core iron-based superconducting tape comprises the following steps:
filling an iron-based superconducting material into a belt material sheath to obtain a sheath superconducting material;
sequentially performing rotary swaging and drawing on the sheath superconducting material to obtain an iron-based superconducting round wire;
filling a plurality of iron-based superconducting round wires into a strip sheath to obtain sheath superconducting round wires, wherein the number of the iron-based superconducting round wires is more than or equal to 2;
and (3) sequentially performing rotary forging, drawing and rolling on the sheathed superconducting round wire to obtain the multi-core iron-based superconducting strip.
3. The method of manufacturing according to claim 1 or 2, characterized in that the thickness of the iron-based superconducting tape is independently 0.1-10 mm, the width is independently 1-100 mm, and the length is independently 10-2000 mm.
4. The preparation method according to claim 1, wherein the wall thickness of the cross section of the multi-core wire wrap is 0.5-50 mm, the side length of the cross section of the multi-core wire wrap is 2-200 mm, and the length of the multi-core wire wrap is equal to or greater than the length of the iron-based superconducting tape.
5. The method according to claim 1, wherein the heat treatment is carried out at a holding temperature of 500 to 1200 ℃, the holding time of the heat treatment is 0.5 to 10 hours, and the pressure of the shielding gas is 0.1 to 200MPa.
6. The method of claim 2, wherein the iron-based superconducting material has a chemical composition of AFe doped 2 As 2 And/or doping LnOFePn;
the doped AFe 2 As 2 Wherein A is Ba, sr, K, cs, caOr Eu, the doped AFe 2 As 2 The medium doping element is one or more of K, na, P and Co;
ln in the doped LnOFePn is La, ce, pr, nd, sm, gd, tb, dy, ho or Y, pn in the doped LnOFePn is P or As, and the doped element in the doped LnOFePn is F.
7. The method according to claim 1, wherein the multi-core wire sheath material comprises copper, iron, nickel, silver, manganese, titanium, niobium, tantalum, an alloy containing the above metal elements as a main component, stainless steel, low carbon steel, monel alloy, hastelloy alloy or Inconel alloy.
8. The iron-based superconducting multi-core wire rod prepared by the preparation method according to any one of claims 1 to 7, wherein the cross-sectional shape of the iron-based superconducting multi-core wire rod is square, rectangular or parallelogram; the side length of the cross section of the iron-based superconducting multi-core wire is 0.5-5 mm, and the two diagonal deviation of the cross section of the wire is less than or equal to 2%; the volume percentage of grain boundaries with the included angle of the grain boundaries smaller than 10 degrees in the superconducting cores of the iron-based superconducting multi-core wire rod is more than or equal to 10 percent.
9. Use of the iron-based superconducting multi-core wire of claim 8 in an iron-based superconducting cable or an iron-based superconducting magnet.
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| EP0503525A1 (en) * | 1991-03-15 | 1992-09-16 | ABBPATENT GmbH | Method for producing superconducting wires |
| DE4444937A1 (en) * | 1994-12-16 | 1996-06-27 | Siemens Ag | Elongate high Tc phase superconductor mfr. |
| CN1687998A (en) * | 2005-05-18 | 2005-10-26 | 北京英纳超导技术有限公司 | Superconductive cable assembly and preparing process thereof |
| CN101728018A (en) * | 2009-12-25 | 2010-06-09 | 清华大学 | High-temperature superconducting wire with additional metal shell and preparation method thereof |
| CN108682509A (en) * | 2018-03-27 | 2018-10-19 | 中国科学院电工研究所 | A method of preparing iron-based superconducting composite strip |
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| GB9805641D0 (en) * | 1998-03-18 | 1998-05-13 | Metal Manufactures Ltd | Superconducting tapes |
| GB9805644D0 (en) * | 1998-03-18 | 1998-05-13 | Metal Manufactures Ltd | Superconducting tapes |
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|---|---|---|---|---|
| EP0503525A1 (en) * | 1991-03-15 | 1992-09-16 | ABBPATENT GmbH | Method for producing superconducting wires |
| DE4444937A1 (en) * | 1994-12-16 | 1996-06-27 | Siemens Ag | Elongate high Tc phase superconductor mfr. |
| CN1687998A (en) * | 2005-05-18 | 2005-10-26 | 北京英纳超导技术有限公司 | Superconductive cable assembly and preparing process thereof |
| CN101728018A (en) * | 2009-12-25 | 2010-06-09 | 清华大学 | High-temperature superconducting wire with additional metal shell and preparation method thereof |
| CN108682509A (en) * | 2018-03-27 | 2018-10-19 | 中国科学院电工研究所 | A method of preparing iron-based superconducting composite strip |
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