CN116487110B - NbTi superconducting switch wire with high nickel content and preparation method thereof - Google Patents

NbTi superconducting switch wire with high nickel content and preparation method thereof Download PDF

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CN116487110B
CN116487110B CN202310741162.XA CN202310741162A CN116487110B CN 116487110 B CN116487110 B CN 116487110B CN 202310741162 A CN202310741162 A CN 202310741162A CN 116487110 B CN116487110 B CN 116487110B
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nbti
cuni
wire
superconducting switch
composite
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CN116487110A (en
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郭强
周子敬
王瑞龙
贾文兵
朱燕敏
张凯林
韩路洋
杨逸文
房元昆
蔡永森
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
    • H01B12/08Stranded or braided wires
    • 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
    • H01B12/10Multi-filaments embedded in normal conductors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E40/00Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

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Abstract

The invention discloses a NbTi superconducting switch wire with high nickel content and a preparation method thereof, comprising the following steps: s1: filling an NbTi bar into an Nb cylinder, filling the Nb cylinder into a drilling CuNi ingot, and preparing an NbTi/CuNi composite bar blank through degassing, vacuum electron beam welding, hot isostatic pressing and extrusion; s2: peeling, cold drawing and annealing the NbTi/CuNi composite rod blank; s3: carrying out cold continuous rolling, and alternately carrying out rounding with aging heat treatment to obtain an NbTi/CuNi composite wire; s4: and twisting, drawing and painting the NbTi/CuNi composite wire to obtain the NbTi superconducting switch wire. The invention solves the problems of high hardness, serious work hardening, frequent wire breakage, core breakage and low performance of NbTi superconducting switch wires with high Ni content in the drawing process. During the magnet excitation, no quench occurs.

Description

NbTi superconducting switch wire with high nickel content and preparation method thereof
Technical Field
The invention belongs to the technical field of superconducting material preparation, and relates to a NbTi superconducting switch wire with high nickel content and a preparation method thereof.
Background
The superconducting switch is a key component in the superconducting magnet, and the function of the superconducting switch mainly comprises the following steps: after the first superconducting magnet and the superconducting magnet are excited, the superconducting switch is closed, the power supply is cut off, and a lossless closed loop is formed between the superconducting switch and the magnet; secondly, in the operation process of the magnet, once the magnet is quenched, the superconducting switch can be automatically opened, so that the magnet is prevented from being damaged.
In the Cu-based binary alloy, ni and Cu are both in a face-centered cubic structure, and atomic radiuses are similar, so that a substitutional solid solution can be formed, and therefore, the CuNi alloy has relatively excellent cold processing performance, and meanwhile, the high resistance characteristic of the CuNi alloy can meet the performance requirement of a superconducting switch wire, so that the CuNi alloy is used as a matrix of an NbTi superconducting switch wire. However, along with the increase of the Ni content, the high-hardness CuNi alloy not only increases the risk of 'stuffy car' in the extrusion process, but also has the tearing morphology on the surface in the peeling process, so that the surface state of the material is seriously influenced, and meanwhile, wire breakage is easier to cause in the multi-pass cold drawing process, so that the development of the superconducting switch wire is challenged. The international general use of CuNi as NbTi superconducting switch wire matrix is because Cu and Ni are in face-centered cubic structure and have similar atomic radii, can form substitution solid solution, and has better cold processing performance. At present, the NbTi superconducting switch wire with high Ni content has the condition of quench for a plurality of times in the magnet excitation process.
Disclosure of Invention
The invention aims to solve the problem that the NbTi superconducting switch wire with high Ni content is quenched for a plurality of times in the magnet excitation process.
The applicant finds that under the condition that the diameter of the wire is unchanged, the problem can be effectively solved by increasing the number of the core wires and reducing the diameter of the core wires, but the processing difficulty of the superconducting wire is increased along with the increase of the number of the core wires, and the requirement on the collaborative deformation capability of the multi-core wires in the processing process is higher. And due to the high hardness and serious work hardening of the NbTi superconducting wire with high Ni content, the problems of frequent wire breakage, core breakage and low performance occur in the drawing process by using the conventional preparation process.
Thus, the present invention provides a high nickel content NbTi superconducting switch wire and method of making same to meet this need in the art.
In one aspect, the invention relates to a method for preparing a high nickel content NbTi superconducting switch wire, comprising the following steps: s1: respectively filling a plurality of NbTi rods into a plurality of Nb cylinders, filling the Nb cylinders into a drilling CuNi ingot, and preparing NbTi/CuNi composite rod blanks with diameters smaller than 90mm through degassing, vacuum electron beam welding of an upper cover and a lower cover, hot isostatic pressing and extrusion;
s2: peeling the NbTi/CuNi composite rod blank to remove a surface oxide layer, and then carrying out cold drawing annealing for multiple times;
s3: carrying out cold continuous rolling for a plurality of times, wherein the cold continuous rolling and aging heat treatment are alternately carried out for 1-8 times, and rounding is carried out to obtain an NbTi/CuNi composite wire;
s4: and twisting, drawing and painting the NbTi/CuNi composite wire to obtain the NbTi superconducting switch wire.
Further, in the preparation method of the NbTi superconducting switch wire with high nickel content, raw materials of the NbTi rod and the drilling CuNi ingot are in an annealing state;
the Ni content of the drilling CuNi ingot is 30-70 wt.%; the diameter of the drilling CuNi ingot is 100-200 mm;
the Nb content of the NbTi bars is 40-60 wt%, the diameter is 1-3 mm, and the number of the NbTi bars is 500-700;
the wall thickness of the Nb tube is 0.4-0.8 mm.
Further, in the preparation method of the NbTi superconducting switch wire with high nickel content, the temperature of the hot isostatic pressing is 600-900 ℃;
the extrusion temperature is 800-1100 ℃.
Further, in the preparation method of the NbTi superconducting switch wire with high nickel content provided by the invention, the multiple cold drawing anneals comprise the following steps: carrying out cold drawing for a plurality of times, wherein the processing rate of each cold drawing is 10-30%; annealing is carried out once when the cumulative processing rate reaches 100%, so that the hardness is lower than HV200;
the annealing temperature is 700-900 ℃.
In the preparation method of the NbTi superconducting switch wire with high nickel content, the inter-pass processing rate of cold continuous rolling is 10-15%.
Further, in the preparation method of the NbTi superconducting switch wire with high nickel content, the pitch of the twisting is 35-60 mm.
Further, in the preparation method of the NbTi superconducting switch wire with high nickel content, the drawing in the S4 is cold drawing, and heating is carried out in the drawing process;
the heating temperature is 500-700 ℃, and the wire running speed during heating is 10-30 m/min.
In the preparation method of the NbTi superconducting switch wire with high nickel content, the thickness of a paint film obtained after painting is 0.5-0.7 mm.
In another aspect, the invention relates to an NbTi superconducting switch wire prepared by the preparation method.
Compared with the prior art, the technical scheme provided by the invention has at least the following beneficial effects or advantages:
according to the invention, the NbTi rod and the drilling CuNi ingot are both annealed, the specifications of the NbTi rod, the drilling CuNi ingot and the Nb barrel are further limited, and the NbTi rod, the drilling CuNi ingot and the Nb barrel are matched with specific extrusion temperature and hot isostatic pressing temperature to optimize the deformation condition of the core wire. In the step S3, once the aging heat treatment is started, annealing cannot be performed, and the purpose is that omega precipitated in the high-temperature annealing process has great influence on the performance of the superconducting wire; the cold continuous rolling is selected because the process has large compressive stress and small tensile stress when reducing the material, and the wire breakage caused by necking can not occur in the process of reducing the material; because the shape of the material after cold continuous rolling is irregular, the material is also required to be drawn by a roller die and rounded after cold continuous rolling. In the steps S2-4, the problems of material work hardening, wire breakage and necking are solved; the pitch of the twist is defined to ensure that all the core wires are adequately transposed, reducing the eddy current loss of the superconducting wire.
Drawings
In order to more clearly illustrate the embodiments of the invention 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 invention, 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 high nickel content NbTi superconducting switch wire prepared in example 1 of the present invention.
Detailed Description
The following describes the technical aspects of the present invention with reference to examples, but the present invention is not limited to the following examples.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
The embodiment provides a specific implementation process of the NbTi superconducting switch wire with high nickel content.
Firstly, a drilling CuNi ingot with the Ni content of 30wt.% and the diameter of 100mm, 500 holes with the number of 500 and a small NbTi rod with the diameter of 1mm and a thickened Nb barrel with the wall thickness of 0.4mm are adopted as raw materials, wherein the drilling CuNi ingot and the NbTi rod are both in an annealed state. Then the NbTi bar is filled into a Nb barrel, then is filled into a drilling CuNi ingot, and is subjected to degassing, vacuum electron beam welding, hot isostatic pressing and extrusion to prepare the NbTi/CuNi composite bar blank, wherein the extrusion temperature is 800 ℃ and the hot isostatic pressing temperature is 600 ℃. Then peeling, cold drawing and annealing the obtained NbTi/CuNi composite rod blank, wherein cold working is deformedThe rate is 10%, the annealing temperature is 700 ℃, and when the cumulative processing rate reaches 100%, one annealing is needed to ensure that the hardness of the whole material is lower than HV200. And then carrying out cold continuous rolling on the NbTi/CuNi composite rod blank, and simultaneously carrying out heat treatment alternately with ageing for 1 time, wherein the inter-pass processing rate of the cold continuous rolling is 10 percent, and because the shape of the material after the cold continuous rolling is irregular, the material is required to be subjected to roller die wire drawing and rounding after the cold continuous rolling, so as to obtain the NbTi/CuNi composite wire. And twisting NbTi/CuNi composite wires, wherein the twisting pitch is 35mm, and then carrying out final drawing, wherein an induction heating furnace is additionally arranged during drawing, the heating temperature is controlled to be 500 ℃, and the wire running speed of the wires in the induction heating furnace is controlled to be 10m/min. Finally, insulating painting is carried out on the wire, and the thickness of a paint film is 0.5mm, so that the NbTi superconducting switch wire is obtained. No broken wire and broken core problem occur in the whole preparation process, and the wire is tested to have Jc of more than or equal to 3900A/mm under the conditions of 0.5T and 4.2K 2 During the magnet excitation, no quench occurs.
Example 2
The embodiment provides a specific implementation process of the NbTi superconducting switch wire with high nickel content.
Firstly, a drilling CuNi ingot with the Ni content of 40wt.% and the diameter of 120mm, 630 drilling holes, 630 small NbTi bars with the diameter of 1.5mm and a thickened Nb barrel with the wall thickness of 0.5mm are adopted as raw materials, wherein the drilling CuNi ingot and the NbTi bars are in an annealed state. Then the NbTi bar is filled into a Nb barrel, then is filled into a drilling CuNi ingot, and is subjected to degassing, vacuum electron beam welding, hot isostatic pressing and extrusion to prepare the NbTi/CuNi composite bar blank, wherein the extrusion temperature is 900 ℃ and the hot isostatic pressing temperature is 700 ℃. And then peeling, cold drawing and annealing the obtained NbTi/CuNi composite rod blank, wherein the cold working deformation rate is 15%, the annealing temperature is 800 ℃, and when the cumulative working rate reaches 100%, one annealing is needed to ensure that the hardness of the whole material is lower than HV200. Then cold continuous rolling is carried out on the NbTi/CuNi composite rod blank, and meanwhile, the cold continuous rolling and the aging heat treatment are alternately carried out for 3 times, the inter-pass processing rate of the cold continuous rolling is 12 percent, and because the shape of the material after the cold continuous rolling is irregular, the roller die wire drawing and the material returning are also needed after the cold continuous rollingAnd (5) rounding to obtain the NbTi/CuNi composite line. And twisting NbTi/CuNi composite wires, wherein the twisting pitch is 40mm, and then carrying out final drawing, wherein an induction heating furnace is additionally arranged during drawing, the heating temperature is controlled at 600 ℃, and the wire running speed of the wires in the induction heating furnace is controlled at 20m/min. Finally, insulating painting is carried out on the wire, and the thickness of a paint film is 0.6mm, so that the NbTi superconducting switch wire is obtained. No broken wire and broken core problem occur in the whole preparation process, and the wire is tested to have Jc of more than or equal to 3900A/mm under the conditions of 0.5T and 4.2K 2 During the magnet excitation, no quench occurs.
Example 3
The embodiment provides a specific implementation process of the NbTi superconducting switch wire with high nickel content.
Firstly, drilling CuNi ingots with the Ni content of 60wt.% and the diameter of 150mm, 650 small-specification NbTi bars with the hole number of 650 and the diameter of 2mm and a thickened Nb barrel with the wall thickness of 0.7mm are adopted as raw materials, wherein the drilling CuNi ingots and the NbTi bars are in an annealed state. Then the NbTi bar is filled into a Nb barrel, then is filled into a drilling CuNi ingot, and is subjected to degassing, vacuum electron beam welding, hot isostatic pressing and extrusion to prepare the NbTi/CuNi composite bar blank, wherein the extrusion temperature is 1000 ℃ and the hot isostatic pressing temperature is 800 ℃. And then peeling, cold drawing and annealing the obtained NbTi/CuNi composite rod blank, wherein the cold working deformation rate is 20%, the annealing temperature is 800 ℃, and when the cumulative working rate reaches 100%, one annealing is needed to ensure that the hardness of the whole material is lower than HV200. And then carrying out cold continuous rolling on the NbTi/CuNi composite rod blank, and simultaneously carrying out 6 times of alternating heat treatment with aging, wherein the inter-pass processing rate of the cold continuous rolling is 15 percent, and because the shape of the material subjected to the cold continuous rolling is irregular, a roller die is adopted to draw wires and round the material after the cold continuous rolling, so that the NbTi/CuNi composite wire is obtained. And twisting NbTi/CuNi composite wires, wherein the twisting pitch is 50mm, and then carrying out final drawing, wherein an induction heating furnace is additionally arranged during drawing, the heating temperature is controlled to be 650 ℃, and the wire running speed of the wires in the induction heating furnace is controlled to be 25m/min. Finally, insulating painting is carried out on the wire, and the thickness of a paint film is 0.6mm, so that the NbTi superconducting switch wire is obtained. No broken wire or broken core occurs in the whole preparation processThe problem is that, through test, the Jc of the wire rod at 0.5T and 4.2K is more than or equal to 3900A/mm 2 During the magnet excitation, no quench occurs.
Example 4
The embodiment provides a specific implementation process of the NbTi superconducting switch wire with high nickel content.
Firstly, a drilling CuNi ingot with the Ni content of 70wt.% and the diameter of 2000mm, 700 holes, 700 small-specification NbTi bars with the diameter of 3mm and a thickened Nb barrel with the wall thickness of 0.8mm are adopted as raw materials, wherein the drilling CuNi ingot and the NbTi bars are in an annealed state. Then the NbTi bar is filled into a Nb barrel, then is filled into a drilling CuNi ingot, and is subjected to degassing, vacuum electron beam welding, hot isostatic pressing and extrusion to prepare the NbTi/CuNi composite bar blank, wherein the extrusion temperature is 1100 ℃ and the hot isostatic pressing temperature is 900 ℃. And then peeling, cold drawing and annealing the obtained NbTi/CuNi composite rod blank, wherein the cold working deformation rate is 30%, the annealing temperature is 900 ℃, and when the cumulative working rate reaches 100%, one annealing is needed to ensure that the hardness of the whole material is lower than HV200. And then carrying out cold continuous rolling on the NbTi/CuNi composite rod blank, and simultaneously carrying out 8 times of alternating heat treatment with aging, wherein the inter-pass processing rate of the cold continuous rolling is 15 percent, and because the shape of the material subjected to the cold continuous rolling is irregular, a roller die is adopted to draw wires and round the material after the cold continuous rolling, so that the NbTi/CuNi composite wire is obtained. And twisting NbTi/CuNi composite wires, wherein the twisting pitch is 60mm, and then carrying out final drawing, wherein an induction heating furnace is additionally arranged during drawing, the heating temperature is controlled at 700 ℃, and the wire running speed of the wires in the induction heating furnace is controlled at 30m/min. Finally, insulating painting is carried out on the wire, and the thickness of a paint film is 0.7mm, so that the NbTi superconducting switch wire is obtained. No broken wire and broken core problem occur in the whole preparation process, and the wire is tested to have Jc of more than or equal to 3900A/mm under the conditions of 0.5T and 4.2K 2 During the magnet excitation, no quench occurs.
As described above, the basic principles, main features and advantages of the present invention are better described. The above examples and description are merely illustrative of preferred embodiments of the present invention, and the present invention is not limited to the above examples, and various changes and modifications to the technical solution of the present invention by those skilled in the art should fall within the scope of protection defined by the present invention without departing from the spirit and scope of the present invention.

Claims (9)

1. The preparation method of the NbTi superconducting switch wire with high nickel content is characterized by comprising the following steps of: s1: respectively filling a plurality of NbTi rods into a plurality of Nb cylinders, filling the Nb cylinders into a drilling CuNi ingot, and preparing NbTi/CuNi composite rod blanks with diameters smaller than 90mm through degassing, vacuum electron beam welding of an upper cover and a lower cover, hot isostatic pressing and extrusion;
s2: peeling the NbTi/CuNi composite rod blank to remove a surface oxide layer, and then carrying out cold drawing annealing for multiple times;
s3: carrying out cold continuous rolling for a plurality of times, wherein the cold continuous rolling and aging heat treatment are alternately carried out for 1-8 times, and then rounding is carried out to obtain an NbTi/CuNi composite wire;
s4: twisting, drawing and painting the NbTi/CuNi composite wire to obtain the NbTi/CuNi composite wire;
the raw materials of the NbTi bar and the drilling CuNi ingot are in an annealing state;
the Ni content of the drilling CuNi ingot is 30-70 wt%.
2. The preparation method of claim 1, wherein the diameter of the drilling CuNi ingot is 100-200 mm;
the Nb content in the NbTi bars is 40-60 wt%, the diameter is 1-3 mm, and the number of the NbTi bars is 500-700; the wall thickness of the Nb tube is 0.4-0.8 mm.
3. The method according to claim 1, wherein the hot isostatic pressing is performed at a temperature of 600-900 ℃;
the extrusion temperature is 800-1100 ℃.
4. The method of manufacturing according to claim 1, wherein the multiple cold drawing anneals comprise: carrying out cold drawing for a plurality of times, wherein the processing rate of each cold drawing is 10-30%; annealing is carried out once when the cumulative processing rate reaches 100%, so that the hardness is lower than HV200;
the annealing temperature is 700-900 ℃.
5. The method according to claim 1, wherein the cold continuous rolling has an inter-pass working ratio of 10 to 15%.
6. The method of claim 1, wherein the pitch of the twist is 35 to 60mm.
7. The method according to claim 1, wherein the drawing in S4 is cold drawing, and heating is performed during the drawing;
the heating temperature is 500-700 ℃, and the wire running speed during heating is 10-30 m/min.
8. The preparation method according to claim 1, wherein the thickness of the paint film after painting is 0.5-0.7 mm.
9. An NbTi superconducting switch wire with high nickel content, characterized in that it is manufactured by the manufacturing method according to any one of claims 1-8.
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CN116759154B (en) * 2023-08-16 2023-11-17 西安聚能超导线材科技有限公司 Preparation method of superconducting wire with short production period and ultra-low copper ratio

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CuNi-NbTi超导开关线的研制;何牧;《低温物理学报》;第8卷(第1期);第72-77页 *

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