CN110580985A - Method for preparing high critical current niobium-tin superconducting strand in external blocking mode - Google Patents
Method for preparing high critical current niobium-tin superconducting strand in external blocking mode Download PDFInfo
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- CN110580985A CN110580985A CN201810596177.0A CN201810596177A CN110580985A CN 110580985 A CN110580985 A CN 110580985A CN 201810596177 A CN201810596177 A CN 201810596177A CN 110580985 A CN110580985 A CN 110580985A
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- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
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Abstract
The invention discloses a method for preparing a high critical current niobium-tin superconducting strand in an external blocking mode. Inserting Nb rods into a drilled copper ingot or densely assembling CuNb rods and compounding the CuNb rods with a copper matrix to obtain a CuNb composite ingot, adding copper covers at two ends of the composite ingot, welding and carrying out hot extrusion to obtain the CuNb composite rod; removing copper at the center of the CuNb composite rod, inserting the Sn alloy rod into the CuNb composite rod, and cutting to length after drawing to obtain a sub-component; the sub-components are arranged according to layers and then are packaged into a Ta pipe in a bundling manner, then the Ta pipe is packaged into an oxygen-free copper pipe to obtain a niobium three-tin (Nb3Sn) superconducting strand blank, and the niobium three-tin superconducting strand with high critical current is obtained by performing multi-pass drawing. The method solves the problem that the RRR of the folded yarn is reduced because Sn penetrates through the Nb barrier layer, and simultaneously the content of Nb and Sn in the folded yarn can be further increased by adding the Ta barrier layer, so that the critical current level of the folded yarn is improved.
Description
Technical Field
The invention relates to the technical field of superconducting material processing, in particular to a method for preparing a high critical current niobium-tin superconducting strand in an external blocking mode.
background
the Residual Resistance Ratio (RRR) is an important performance index of a superconducting strand, a copper matrix in the strand plays a stabilizing role in a superconductor, when the superconductor is locally quenched due to some reason in use, most of current can be bypassed, the superconductor generates heat due to resistance rise, the generated heat can be rapidly dissipated to surrounding liquid helium, the temperature of the superconductor is reduced to be below the critical temperature again, and the superconducting state is recovered. For the Nb3Sn superconducting strand, long-time heat treatment is needed to ensure the diffusion of Sn and the sufficient reaction of Nb and Sn, so as to generate a Nb3Sn superconducting phase and finally obtain superconducting performance. During the heat treatment, once Sn diffuses into the copper matrix, the matrix is polluted, so that the RRR of the strand is greatly reduced, and the stability of the superconductor is reduced.
In order to avoid the contamination of the copper matrix during the heat treatment and to ensure a high RRR, the superconducting strand is usually prepared by an external barrier method, and a barrier layer is added to separate the copper matrix from the superconducting region. At present, Nb is used as a barrier material in many cases, but Nb as a reactive barrier layer reacts with Sn during heat treatment to form Nb3Sn, i.e., a Nb barrier layer needs to have a certain thickness. However, the Nb barrier layer is unevenly deformed and unevenly thick during the bundle drawing process, and there is still a risk that Sn penetrates into the matrix from the weak portion of the barrier layer to cause a decrease in the RRR of the superconducting wire. In addition, the reactive barrier layer limits the increase of the Sn content, so that the critical current of the wire is difficult to further increase.
Disclosure of Invention
The invention aims to provide a method for preparing a high critical current niobium tri-tin superconducting strand in an external barrier mode, which solves the problems of copper matrix pollution and reduction of RRR (resistance random resistance) of a superconducting wire rod caused by the reaction of a Nb barrier layer and Sn, and particularly removes a reactive Nb barrier layer and adds a non-reactive Ta barrier layer outside a sub-component instead.
In order to achieve the purpose of the invention, the method for preparing the high critical current niobium-tin superconducting strand by the external barrier mode comprises the following steps:
(1) inserting Nb rods into a drilled copper ingot or combining CuNb rods with a copper matrix in a close-packed manner to obtain a CuNb composite ingot, wherein the central area of the composite ingot is oxygen-free copper, the composite ingot is wrapped by a copper sheath, copper covers are arranged at two ends of the composite ingot, and the CuNb composite rod is obtained by welding and hot extrusion;
(2) Removing the copper at the center of the CuNb composite rod obtained in the step (1) to obtain a CuNb composite tube, inserting the Sn alloy rod into the CuNb composite tube, and cutting to length after drawing to obtain a sub-component;
(3) And (3) bundling the sub-components obtained in the step (2) according to the layer arrangement, then loading the sub-components into a Ta tube, then loading the tube into an oxygen-free copper tube to obtain a niobium three-tin (Nb3Sn) superconducting strand blank, and then carrying out multi-pass drawing to obtain the high critical current niobium three-tin superconducting strand.
In the step (1), the cross-sectional area of Nb can account for 40% -65% of the total cross-sectional area of the CuNb composite ingot.
In the step (1), the cross section area of the oxygen-free copper in the central area can account for 20% -35% of the total cross section area of the CuNb composite ingot.
In the step (2), the cross-sectional area of the removed central copper can account for 15% -30% of the total cross-sectional area of the CuNb composite rod.
in the step (2), the Sn alloy may be any one of pure Sn, SnTi, or SnCu.
Preferably, when the Sn alloy is SnTi or SnCu, the mass fraction of Ti or Cu is 1 to 3 percent of that of the Sn alloy.
In the step (2), the shape of the sub-components can be circular or hexagonal.
In the step (3), the number of the sub-components can be 1+3 XnX (n-1), wherein n is the number of the sub-components.
The invention has the beneficial effects that: according to the invention, the CuNb composite rod with high Nb content can be prepared by assembling, welding and hot extrusion, then the Sn alloy rod is loaded through drilling, the high Sn content subcomponent is prepared by drawing, and finally, a Ta barrier layer is added outside the subcomponent during blank assembly, so that the risk of Sn diffusing to a substrate is completely blocked, the problem of reduction of the RRR of the folded yarn caused by Sn penetrating through the original Nb barrier layer is solved, and meanwhile, the Nb and Sn content in the folded yarn can be further increased by adding the non-reactive Ta barrier layer, thereby improving the critical current level of the folded yarn.
Drawings
FIG. 1 is a schematic diagram of a final blank in a method for preparing a high critical current niobium tri-tin superconducting strand by an external barrier method according to the present invention;
Wherein, 1 is an oxygen-free copper pipe, 2 is a subcomponent, and 3 is a Ta barrier layer.
Detailed Description
The method for preparing the high critical current niobium-tin superconducting strand by the external barrier mode specifically comprises the following steps:
Step 1: inserting Nb rods into a drilled copper ingot or compounding CuNb rods with a copper matrix in a close-packed manner to obtain a CuNb composite ingot, wherein the ratio of the cross-sectional area of Nb to the total cross-sectional area of the CuNb composite ingot is 40-65%; the central area of the composite ingot is oxygen-free copper, the proportion of the cross section area to the total cross section area of the CuNb composite ingot is 20-35%, the outer part of the composite ingot is wrapped by a copper sheath, copper covers are added at two ends of the composite ingot, and the CuNb composite rod is obtained by welding and hot extrusion;
Step 2: removing central copper from the CuNb composite rod obtained in the step 1 to obtain a CuNb composite tube, wherein the ratio of the cross section area of the removed central copper to the total cross section area of the CuNb composite rod is 15-30%; inserting a pure Sn rod or an SnTi alloy rod containing 1-3% of Ti or an SnCu alloy rod containing 1-3% of Cu into the CuNb composite tube, and cutting to length after drawing to obtain a subcomponent 2;
And step 3: arranging the circular or hexagonal sub-components 2 obtained in the step 2 according to layers, wherein the number of the sub-components is 1+3 XnX (n-1), and n is the number of the sub-components; the arranged sub-components 2 are bundled and loaded into a Ta barrier layer 3, then the obtained product is loaded into an oxygen-free copper tube 1 to obtain a Nb3Sn final blank, and the final blank is drawn for multiple times as shown in figure 1, so that the high critical current Nb3Sn superconducting strand can be obtained.
the method of the invention adopts the non-reactive Ta blocking layer to replace the reactive Nb blocking layer, eliminates the risk of the blocking layer being penetrated by the reaction, prevents the RRR from being reduced, enables the Sn content in the wire rod to be further increased and improves the comprehensive performance of the superconducting wire rod.
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "either" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
Step 1: uniformly distributed through holes are drilled on the oxygen-free copper ingot by adopting a deep hole drilling method, Nb rods are inserted into the drilled copper ingot, and the cross section area of the Nb rods accounts for 40% of the total cross section area of the CuNb composite ingot; drilling holes in the central area of the composite ingot, wherein the oxygen-free copper cross section area in the central area accounts for 20% of the total cross section area of the CuNb composite ingot, adding copper covers at two ends, and welding and hot extruding to obtain a CuNb composite rod;
Step 2: removing central copper from the CuNb composite rod obtained in the step 1 to obtain a CuNb composite tube, wherein the cross section area of the removed central copper accounts for 15% of the total cross section area of the CuNb composite rod; inserting a pure Sn rod into the CuNb composite tube, drawing to be circular, and cutting to length to obtain a sub-component;
And step 3: arranging the sub-components which are obtained in the step 2 and have the circular shapes according to 5 layers, wherein the number of the sub-components is 61; and (3) putting the arranged sub-component bundles into a Ta tube, then putting the Ta tube into an oxygen-free copper tube to obtain a Nb3Sn blank, and then carrying out multi-pass drawing to obtain the high-critical-current Nb3Sn superconducting strand.
The Nb3Sn superconducting strand prepared by the method is verified to use the non-reactive Ta barrier layer to replace the reactive Nb barrier layer, the risk that the barrier layer is penetrated by reaction is avoided, RRR (resistance random response) is not reduced, the Nb content and the Sn content in the strand can be further increased by adding the non-reactive Ta barrier layer, the critical current level of the superconducting strand is improved, and the comprehensive performance is better.
example 2
step 1: placing a Nb rod into a small hexagonal copper pipe, stacking the Nb rod and a hexagonal oxygen-free copper rod in an oxygen-free copper clad to obtain a CuNb composite ingot, wherein the cross section area of the Nb rod accounts for 50% of the total cross section area of the CuNb composite ingot, the hexagonal oxygen-free copper rod is stacked in the central area of the composite ingot, the cross section area of the copper rod accounts for 30% of the total cross section area of the CuNb composite ingot, adding copper covers at two ends of the composite ingot, and welding and hot extruding to obtain the CuNb composite rod;
Step 2: removing central copper from the CuNb composite rod obtained in the step 1 to obtain a CuNb composite tube, wherein the ratio of the cross section area of the removed central copper to the total cross section area of the CuNb composite rod is 20%; inserting a SnTi alloy rod containing 1% of Ti by mass into the CuNb composite tube, drawing to a hexagonal shape, and cutting to length to obtain a subcomponent;
And step 3: arranging the six-square-shaped sub-components obtained in the step 2 according to 6 layers, wherein the number of the sub-components is 91; and (3) putting the arranged sub-component bundles into a Ta tube, then putting the Ta tube into an oxygen-free copper tube to obtain a Nb3Sn blank, and then carrying out multi-pass drawing to obtain the high critical current Nb3Sn superconducting strand.
The Nb3Sn superconducting strand prepared by the method is verified to use the non-reactive Ta barrier layer to replace the reactive Nb barrier layer, the risk that the barrier layer is penetrated by reaction is avoided, RRR (resistance random response) is not reduced, the Nb content and the Sn content in the strand can be further increased by adding the non-reactive Ta barrier layer, the critical current level of the superconducting strand is improved, and the comprehensive performance is better.
Example 3
step 1: electroplating oxygen-free copper on the surface of the Nb rod to obtain a CuNb single core rod, stacking the CuNb single core rod and the hexagonal oxygen-free copper rod in an oxygen-free copper sheath, wherein the cross section area of Nb in the CuNb single core rod accounts for 65% of the total cross section area of the CuNb composite ingot; stacking a hexagonal oxygen-free copper rod in the central area of the composite ingot, wherein the proportion of the cross section area of the copper rod to the total cross section area of the CuNb composite ingot is 35%, adding copper covers at two ends, and welding and hot extruding to obtain the CuNb composite rod;
Step 2: removing central copper from the CuNb composite rod obtained in the step 1 to obtain a CuNb composite tube, wherein the cross section area of the removed central copper accounts for 30% of the total cross section area of the CuNb composite rod; inserting a SnCu alloy rod containing 3% of Cu by mass into the CuNb composite tube, drawing to be circular, and cutting to length to obtain a subcomponent;
and step 3: arranging the sub-components which are obtained in the step 2 and have the circular shapes according to 8 layers, wherein the number of the sub-components is 169; and (3) putting the arranged sub-component bundles into a Ta tube, then putting the Ta tube into an oxygen-free copper tube to obtain a Nb3Sn final blank, and then carrying out multi-pass drawing to obtain the high-critical-current Nb3Sn superconducting strand.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for preparing a high critical current niobium-tin superconducting strand in an external blocking mode is characterized by comprising the following steps:
(1) Inserting Nb rods into a drilled copper ingot or combining CuNb rods with a copper matrix in a close-packed manner to obtain a CuNb composite ingot, wherein the central area of the composite ingot is oxygen-free copper, the composite ingot is wrapped by a copper sheath, copper covers are arranged at two ends of the composite ingot, and the CuNb composite rod is obtained by welding and hot extrusion;
(2) Removing the copper at the center of the CuNb composite rod obtained in the step (1) to obtain a CuNb composite tube, inserting the Sn alloy rod into the CuNb composite tube, and cutting to length after drawing to obtain a sub-component;
(3) And (3) bundling the sub-components obtained in the step (2) according to layer arrangement, then loading the sub-components into a Ta tube, then loading the Ta tube into an oxygen-free copper tube to obtain a niobium three-tin superconducting strand blank, and then carrying out multi-pass drawing to obtain the high critical current niobium three-tin superconducting strand.
2. The method for preparing the high critical current niobium tri-tin superconducting strand by the external barrier method according to claim 1, wherein in the step (1), the cross-sectional area of Nb accounts for 40-65% of the total cross-sectional area of the CuNb composite ingot.
3. The method for preparing the high critical current niobium tri-tin superconducting strand in the external barrier mode according to claim 1, wherein in the step (1), the cross-sectional area of the oxygen-free copper in the central region accounts for 20% -35% of the total cross-sectional area of the CuNb composite ingot.
4. the method for preparing the high critical current niobium tri-tin superconducting strand by the external barrier method according to claim 1, wherein in the step (2), the cross-sectional area of the removed central copper accounts for 15% -30% of the total cross-sectional area of the CuNb composite rod.
5. The method for preparing the high critical current niobium tri-tin superconducting strand by the external barrier method according to claim 1, wherein in the step (2), the Sn alloy is any one of pure Sn, SnTi or SnCu.
6. The method for preparing the high critical current niobium three-tin superconducting strand by the external barrier method according to claim 1, wherein in the step (2), the Sn alloy is SnTi or SnCu, wherein the mass fraction of Ti or Cu is 1% -3% of the Sn alloy.
7. The method for preparing the high critical current niobium tri-tin superconducting strand in the external barrier mode according to claim 1, wherein in the step (2), the shape of the sub-components is circular or hexagonal.
8. The method for preparing the high critical current niobium tri-tin superconducting yarn in the external barrier mode according to claim 1 or 7, wherein in the step (3), the number of the sub-components is 1+3 xn x (n-1), wherein n is the number of the sub-component layers.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113096881A (en) * | 2021-04-16 | 2021-07-09 | 西部超导材料科技股份有限公司 | Preparation method of high-strength high-critical-current niobium-tin superconducting strand |
| CN114664495A (en) * | 2022-05-23 | 2022-06-24 | 西部超导材料科技股份有限公司 | Internal stabilization type bronze Nb method3Sn superconducting wire and preparation method thereof |
| CN115295242A (en) * | 2022-09-30 | 2022-11-04 | 西部超导材料科技股份有限公司 | Preparation method of niobium-tin superconducting strand with high critical current density |
| CN115295243A (en) * | 2022-09-30 | 2022-11-04 | 西部超导材料科技股份有限公司 | Preparation method of element-doped high-critical-current-density niobium-tin superconducting strand |
| CN116453757A (en) * | 2023-06-09 | 2023-07-18 | 西安聚能超导线材科技有限公司 | Nb with low copper ratio 3 Preparation method of Sn superconducting wire |
| CN116612930A (en) * | 2023-07-20 | 2023-08-18 | 西安聚能超导线材科技有限公司 | Nb (Nb) alloy 3 Sn superconducting wire preparation method and superconducting wire |
| CN117265617A (en) * | 2023-11-16 | 2023-12-22 | 西安聚能超导线材科技有限公司 | Preparation method of barrier layer, barrier layer and niobium-three-tin superconducting wire |
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| CN116612930A (en) * | 2023-07-20 | 2023-08-18 | 西安聚能超导线材科技有限公司 | Nb (Nb) alloy 3 Sn superconducting wire preparation method and superconducting wire |
| CN116612930B (en) * | 2023-07-20 | 2023-09-15 | 西安聚能超导线材科技有限公司 | Nb (Nb) alloy 3 Sn superconducting wire preparation method and superconducting wire |
| CN117265617A (en) * | 2023-11-16 | 2023-12-22 | 西安聚能超导线材科技有限公司 | Preparation method of barrier layer, barrier layer and niobium-three-tin superconducting wire |
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