CN102522153B - Preparation method of multi-core MgB2 superconducting wire - Google Patents

Preparation method of multi-core MgB2 superconducting wire Download PDF

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CN102522153B
CN102522153B CN201110327753XA CN201110327753A CN102522153B CN 102522153 B CN102522153 B CN 102522153B CN 201110327753X A CN201110327753X A CN 201110327753XA CN 201110327753 A CN201110327753 A CN 201110327753A CN 102522153 B CN102522153 B CN 102522153B
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core wire
oxygen
free copper
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core
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CN102522153A (en
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闫果
刘国庆
孙昱艳
焦高峰
冯建情
王庆阳
杨芳
李成山
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Northwest Institute for Non Ferrous Metal Research
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Abstract

The invention discloses a preparation method of a multi-core MgB2 superconducting wire. The method comprises: first, precursor power is prepared; second, the precursor power is placed in a Ta tube to prepare a tubulation complex; third, groove rolling is carried out on a single core wire; fourth, a NbTi/Cu composite rod and a plurality of single core wires are placed in an oxygen-free copper tube for assembling so as to obtain a secondary composite rod; fifth, rotary swaging and drawing are carried out on the secondary composite rod, groove rolling is carried out and rotary swaging and drawing are carried out again, so that a multi-core wire is obtained; and sixth, heat treatment is carried out on the multi-core wire to obtain a multi-core MgB2 superconducting wire. According to the invention, processes of rotary swaging, drawing and groove rolling are combined and employed; therefore, not only is density of the multi-core wire improved, but also connectivity between crystal grains can be improved; it is beneficial to prepare a multi-core MgB2 superconducting wire with high performances; and the prepared wire has high mechanical strength and can bear great stress and strain without obvious reduction of the superconductive current carrying performance, so that a superconducting wire practical requirement can be well met.

Description

A kind of multicore MgB 2The preparation method of superconducting wire
Technical field
The invention belongs to superconductor processing engineering technology field, be specifically related to a kind of multicore MgB 2The preparation method of superconducting wire.
Background technology
MgB 2Superconductor is since calendar year 2001 is found, because its critical temperature is 39K, has coherence length and greatly, do not have the advantages such as the weak connection of crystal boundary, scientist's concern extremely both at home and abroad, on a large amount of, the systematic research of having passed through 10 years is basic, find that element doping is to improve MgB 2The effective means of wire rod High-Field current capacity, and TiC doping is one of the most effective alloy of generally acknowledging at present.MgB 2The wire rod preparation that practical requirement is especially satisfied in the wire rod preparation is the emphasis of research always, at present, a plurality of producers (as U.S. Hype Tech company, Italian Columbus company etc.) have possessed mass in the world provides near practical km level MgB 2Multi-core wire.What U.S. Hype Tech company adopted is continuous pipeline forming (CTFF:Continuous Tube Forming Filling) technique, this technique needs complicated and expensive equipment as the basis, only has several scientific research institutions to adopt this technique both at home and abroad.What Italy Columbus company adopted is traditional powder tiretube process (PIT) technique, and this technique is simple, and is easy to operate, is to prepare at present the MgB2 wire rod to adopt maximum technique.
The CTFF technology prepares MgB 2Superconducting wire is directly with MgB 2Powder is placed on metal tape, and the method by continuous coating welded tube is prepared into wire rod, then heat-treats under argon shield.This techniqueflow once was used for the Bi based high-temperature superconductive strip, and technology is also relatively ripe, and process equipment is comparatively complicated, the high in cost of production shortcoming but exist, and only has at present a few studies unit to adopt this technique to prepare the MgB2 wire strip.Powder tiretube process (PIT) is preparation MgB 2One of major technique of wire rod, PIT technology processing MgB 2Wire rod mainly contains two kinds of technology paths, i.e. first position method (ex-situ) and in-situ method (in-situ).Ex-situ PIT technology adopts the MgB after being reacted into mutually 2Directly pack in metal tube as pioneer's powder, by the wire rod of swaging, drawing and rolling mill practice are prepared into certain size.The characteristics of this technology are that technique is simple, are fit to very much mass production.But due to MgB 2Material has the fragility of similar pottery, needs to use high-intensity Fe base sheath material in ex-situ PIT preparation process, to MgB 2The core silk applies enough stress constraints and connects to strengthen crystal grain.Simultaneously, can cause the MgB in wire rod in cold working process 2The core silk forms the gross imperfections such as crackle, causes the wire rod performance sharply to reduce.
In-situ PIT technology adopts Mg powder and B powder to press MgB 2The atomicity ratio pack in metal tube, be prepared into the wire rod of certain size by drawing, rolling mill practice, then heat-treat, finally generate MgB in wire rod 2Phase.The advantage of In-situ PIT technology is to be reacted into phase with B after the Mg fusing in heat treatment process, thereby can make formed micro-crack in the course of processing up, the MgB in final wire rod 2Superconducting phase crystal grain connects better.But because a lot of sheath materials comprise Nb commonly used, Fe etc., when heat treatment temperature is higher (greater than 750 degree), chemical reaction will occur with Mg or B in sheath material, generate certain thickness diffusion layer, the existence of this diffusion layer will be played inhibitory action to the wire rod critical current density, and because the carbon atom in the low TiC alloy of heat treatment temperature is difficult to replace boron position atom, and the TiC alloy can only be present in grain boundaries as the two-phase particle, is difficult to obviously improve the critical current density of wire rod under High-Field.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and a kind of employing drawing and groove rolling preparation multicore MgB that combines that swages is provided 2The method of superconducting wire.Adopt the wire rod of method of the present invention preparation to have higher mechanical strength, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of multicore MgB 2The preparation method of superconducting wire is characterized in that, the method comprises the following steps:
Step 1, magnesium powder, amorphous boron powder and the sodium rice TiC powder atomic ratio according to Mg: B: TiC=1: (2-x): x is mixed, then that mixture ground and mixed under argon shield is even, obtain Precursor Powder; The value of described x is 0.02～0.10;
Step 2, Precursor Powder described in step 1 is packed in Ta pipe after pickling processes, the Ta pipe that then Precursor Powder will be housed is packed in oxygen-free copper pipe after pickling processes, makes the tubulature complex;
Step 3, the complex of tubulature described in step 2 is carried out groove rolling, obtain having the single-core wire of circular cross-section, single-core wire is carried out successively scale, blocks and pickling; The pass reduction of described groove rolling is 10%～20%;
Step 4, the single-core wire after pickling in NbTi/Cu compound bar and 6 or 12 step 3 is placed in oxygen-free copper pipe after pickling processes carries out the secondary assembling and obtain the secondary compound bar; Described NbTi/Cu compound bar is by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material, the mass ratio of described oxygen-free copper and niobium titanium alloy is 1: 0.8～1.2, the residual resistivity of described oxygen-free copper is not less than 80, in described niobium titanium alloy, the quality percentage composition of niobium is 45%～55%, and surplus is titanium; NbTi/Cu compound bar in described secondary assembling process after pickling is placed in the oxygen-free copper pipe center after pickling processes, and the single-core wire after the pickling along the circumferential direction NbTi/Cu compound bar after the pickling is arranged in circular ring and packs in oxygen-free copper pipe after pickling processes; When the quantity of described single-core wire is 6, the size of described NbTi/Cu compound bar and single-core wire measure-alike; When the quantity of described single-core wire was 12, the diameter of described NbTi/Cu compound bar was 3 times of single-core wire diameter;
Step 5, the pass reduction with 10%～20% carry out swaging of 3～5 passages and drawing processing to the compound bar of secondary described in step 4, then with 10%～15% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 10～15 passages, secondary compound bar after groove rolling is swaged and drawing processing with 10%～15% pass reduction at last, obtain the Multi-core wire that diameter is 0.8mm～1.5mm;
Step 6, sealed at both ends being placed in tube furnace of Multi-core wire described in step 5 heat-treated, obtain multicore MgB 2Superconducting wire; Described heat treated process is: the speed with 300mL/min～500mL/min passes into argon gas in tube furnace, after argon gas passes into 1h～2h, be incubated 0.5h～3h after with the heating rate of 10 ℃/min～20 ℃/min, temperature in stove being risen to 650 ℃～850 ℃, then the rate of temperature fall with 10 ℃/min～20 ℃/min is cooled to room temperature with temperature in stove.
The quality purity of magnesium powder described in above-mentioned steps one is 99.8%, and the granularity of magnesium powder is-200 orders, and the quality purity of described amorphous boron powder is 99.999%, and the quality purity of described nano TiC powder is 99%.
The external diameter of Ta pipe described in above-mentioned steps two is 10mm～12mm, and wall thickness is 1.0mm～1.5mm, and in the Ta pipe, the mass content of Ta is not less than 99.9%.
The external diameter of oxygen-free copper pipe described in above-mentioned steps two is 12.5mm～15.5mm, and wall thickness is 1.0mm～1.5mm, and the residual resistivity of described oxygen-free copper pipe is not less than 80.
The diameter of single-core wire described in above-mentioned steps three is 3mm～8mm, when the single-core wire diameter is 3mm～5mm, adopts 12 single-core wires to carry out the secondary assembling, when the single-core wire diameter is 5mm～8mm, adopts 6 single-core wires to carry out secondary and assembles.
Described in above-mentioned steps three, the acid cleaning process of single-core wire is: it is to soak 5min～8min in 10%～15% nitric acid that the sealed at both ends protection of single-core wire is placed on mass concentration; then water washes away single-core wire remained on surface acid solution; with the absolute ethyl alcohol dehydration, dry under 50 ℃～60 ℃ conditions at last again.
Described in above-mentioned steps four, the residual resistivity of oxygen-free copper pipe is not less than 80, and the external diameter of oxygen-free copper pipe is 19mm～31mm, and wall thickness is 1.5mm～3mm.
The present invention compared with prior art has the following advantages:
1, the present invention adopts the technology that swage drawing and groove rolling combine, and not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire.
2, superconducting wire in the course of processing because wire rod is outside stressed larger, cause defective to develop to the center, the higher NbTi/Cu compound bar of superconducting wire center employing intensity of the present invention's preparation has limited the development of defective to a certain extent, improved the density of Multi-core wire, efficient hardening MgB 2The connectivity of crystal grain, simultaneously NbTi is a kind of cryogenic superconductor, can provide certain current capacity at less than the temperature of 9.8K, more be conducive to improve wire rod low temperature, in low critical current density after the match.
3, heat treatment of the present invention is carried out in 650 ℃～850 ℃ scopes, and the liquid phase in the Mg-B course of reaction can well be made the micro-crack that forms in the course of processing up, and metal Ta is to MgB simultaneously 2Material has chemical inertness preferably, has avoided Ta/MgB 2Dispersal behavior between the interface, and oxygen-free copper has good heat conduction, conductivity, can play to superconducting wire the static stabilization of shunting, heat radiation.
4, adopt the wire rod of method preparation of the present invention to have higher mechanical strength, more than the normal temperature lower yield strength reaches 129MPa, more than tensile strength reaches 258MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is that the embodiment of the present invention 1, embodiment 2 and embodiment 3 secondaries are assembled the structural representation of the secondary compound bar that obtains.
Fig. 2 is that the embodiment of the present invention 4, embodiment 5 and embodiment 6 secondaries are assembled the structural representation of the secondary compound bar that obtains.
Description of reference numerals:
The 1-single-core wire; The 2-NbTi/Cu compound bar; The 3-oxygen-free copper pipe.
Embodiment
Embodiment 1
7 core MgB 2The preparation of superconducting wire:
Step 1, (granularity is-200 orders with the magnesium powder, quality purity is 99.8%), amorphous boron powder (quality purity is 99.999%) and sodium rice TiC powder (quality purity is 99%) be according to Mg: B: TiC=1: the atomic ratio of 1.98: 0.02 mixes, then mixture ground and mixed under argon shield is even, obtain Precursor Powder;
Step 2, Precursor Powder described in step 1 is packed into (external diameter is 10mm for Ta pipe after the conventional method pickling processes, wall thickness is 1.0mm, the mass content of Ta is not less than 99.9%) in, the Ta pipe that then Precursor Powder will be housed is packed into, and (external diameter is 12.5mm for oxygen-free copper pipe after the conventional method pickling processes, wall thickness is 1.0mm, residual resistivity is not less than 80) in, make the tubulature complex;
Step 3, the pass reduction with 10% carry out groove rolling to the complex of tubulature described in step 2, the diameter that obtains having circular cross-section is the single-core wire 1 of 5mm, length according to 1.0m is carried out scale, is blocked single-core wire 1, then it is to soak 8min in 10% nitric acid that the sealed at both ends protection of single-core wire 1 after blocking is placed on mass concentration, then water washes away single-core wire 1 remained on surface acid solution, with the absolute ethyl alcohol dehydration, dry under 50 ℃ of conditions at last again;
step 4, be that NbTi/Cu compound bar 2 after the conventional method pickling of 5mm is (by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material with diameter, wherein the mass ratio of oxygen-free copper and niobium titanium alloy is 1: 0.8, the residual resistivity of oxygen-free copper is not less than 80, in niobium titanium alloy, the quality percentage composition of niobium is 45%, surplus is titanium) (residual resistivity is not less than 80 to be placed in oxygen-free copper pipe 3 after the conventional method pickling processes, external diameter is 19mm, wall thickness is 1.5mm) in, single-core wire 1 after pickling in 6 step 3 along the circumferential direction is arranged in circular ring around NbTi/Cu compound bar 2 packs in oxygen-free copper pipe 3, obtain secondary compound bar (as shown in Figure 1),
Step 5, the pass reduction with 20% carry out swaging of 3 passages and drawing processing to the compound bar of secondary described in step 4, then with 10% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 15 passages, secondary compound bar after groove rolling is swaged and drawing processing with 10% pass reduction at last, obtaining diameter is 7 core wires of 0.8mm;
Step 6, sealed at both ends being placed in tube furnace of 7 core wires described in step 5 heat-treated, obtain 7 core MgB 2Superconducting wire; Described heat treated process is: the speed with 300mL/min passes into argon gas in tube furnace, after argon gas passes into 2h, be incubated 3h after with the heating rate of 10 ℃/min, temperature in stove being risen to 650 ℃, then the rate of temperature fall with 10 ℃/min is cooled to room temperature with temperature in stove.
The technology that the present embodiment adopts swage drawing and groove rolling to combine not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire, the wire rod of preparation has higher mechanical strength, and the normal temperature lower yield strength reaches 148MPa, tensile strength reaches 282MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
Embodiment 2
7 core MgB 2The preparation of superconducting wire:
Step 1, (granularity is-200 orders with the magnesium powder, quality purity is 99.8%), amorphous boron powder (quality purity is 99.999%) and sodium rice TiC powder (quality purity is 99%) be according to Mg: B: TiC=1: the atomic ratio of 1.9: 0.1 mixes, then mixture ground and mixed under argon shield is even, obtain Precursor Powder;
Step 2, Precursor Powder described in step 1 is packed into (external diameter is 12mm for Ta pipe after the conventional method pickling processes, wall thickness is 1.5mm, the mass content of Ta is not less than 99.9%) in, the Ta pipe that then Precursor Powder will be housed is packed into, and (external diameter is 15.5mm for oxygen-free copper pipe after the conventional method pickling processes, wall thickness is 1.5mm, residual resistivity is not less than 80) in, make the tubulature complex;
Step 3, the pass reduction with 20% carry out groove rolling to the complex of tubulature described in step 2, the diameter that obtains having circular cross-section is the single-core wire 1 of 8mm, length according to 1.5m is carried out scale, is blocked single-core wire 1, then it is to soak 5min in 15% nitric acid that the sealed at both ends protection of single-core wire 1 after blocking is placed on mass concentration, then water washes away single-core wire 1 remained on surface acid solution, with the absolute ethyl alcohol dehydration, dry under 60 ℃ of conditions at last again;
step 4, be that NbTi/Cu compound bar 2 after the conventional method pickling of 8mm is (by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material with diameter, wherein the mass ratio of oxygen-free copper and niobium titanium alloy is 1: 1.2, the residual resistivity of oxygen-free copper is not less than 80, in niobium titanium alloy, the quality percentage composition of niobium is 55%, surplus is titanium) (residual resistivity is not less than 80 to be placed in oxygen-free copper pipe 3 after the conventional method pickling processes, external diameter is 31mm, wall thickness is 3mm) in, single-core wire 1 after pickling in 6 step 3 along the circumferential direction is arranged in circular ring around NbTi/Cu compound bar 2 packs in oxygen-free copper pipe 3, obtain secondary compound bar (as shown in Figure 1),
Step 5, the pass reduction with 10% carry out swaging of 5 passages and drawing processing to the compound bar of secondary described in step 4, then with 15% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 10 passages, secondary compound bar after groove rolling is swaged and drawing processing with 15% pass reduction at last, obtaining diameter is 7 core wires of 1.5mm;
Step 6, sealed at both ends being placed in tube furnace of 7 core wires described in step 5 heat-treated, obtain 7 core MgB 2Superconducting wire; Described heat treated process is: the speed with 500mL/min passes into argon gas in tube furnace, after argon gas passes into 1h, be incubated 0.5h after with the heating rate of 20 ℃/min, temperature in stove being risen to 850 ℃, then the rate of temperature fall with 15 ℃/min is cooled to room temperature with temperature in stove.
The technology that the present embodiment adopts swage drawing and groove rolling to combine not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire, the wire rod of preparation has higher mechanical strength, and the normal temperature lower yield strength reaches 129MPa, tensile strength reaches 258MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
Embodiment 3
7 core MgB 2The preparation of superconducting wire:
Step 1, (granularity is-200 orders with the magnesium powder, quality purity is 99.8%), amorphous boron powder (quality purity is 99.999%) and sodium rice TiC powder (quality purity is 99%) be according to Mg: B: TiC=1: the atomic ratio of 1.95: 0.05 mixes, then mixture ground and mixed under argon shield is even, obtain Precursor Powder;
Step 2, Precursor Powder described in step 1 is packed into (external diameter is 11mm for Ta pipe after the conventional method pickling processes, wall thickness is 1.2mm, the mass content of Ta is not less than 99.9%) in, the Ta pipe that then Precursor Powder will be housed is packed into, and (external diameter is 14mm for oxygen-free copper pipe after the conventional method pickling processes, wall thickness is 1.2mm, residual resistivity is not less than 80) in, make the tubulature complex;
Step 3, the pass reduction with 15% carry out groove rolling to the complex of tubulature described in step 2, the diameter that obtains having circular cross-section is the single-core wire 1 of 6mm, length according to 1.0m is carried out scale, is blocked single-core wire 1, then it is to soak 6min in 12% nitric acid that the sealed at both ends protection of single-core wire 1 after blocking is placed on mass concentration, then water washes away single-core wire 1 remained on surface acid solution, with the absolute ethyl alcohol dehydration, dry under 55 ℃ of conditions at last again;
step 4, be that NbTi/Cu compound bar 2 after the conventional method pickling of 6mm is (by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material with diameter, wherein the mass ratio of oxygen-free copper and niobium titanium alloy is 1: 1, the residual resistivity of oxygen-free copper is not less than 80, in niobium titanium alloy, the quality percentage composition of niobium is 50%, surplus is titanium) (residual resistivity is not less than 80 to be placed in oxygen-free copper pipe 3 after the conventional method pickling processes, external diameter is 22mm, wall thickness is 1.5mm) in, single-core wire 1 after pickling in 6 step 3 along the circumferential direction is arranged in circular ring around NbTi/Cu compound bar 2 packs in oxygen-free copper pipe 3, obtain secondary compound bar (as shown in Figure 1),
Step 5, the pass reduction with 15% carry out swaging of 4 passages and drawing processing to the compound bar of secondary described in step 4, then with 12% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 12 passages, secondary compound bar after groove rolling is swaged and drawing processing with 13% pass reduction at last, obtaining diameter is 7 core wires of 1mm;
Step 6, sealed at both ends being placed in tube furnace of 7 core wires described in step 5 heat-treated, obtain 7 core MgB 2Superconducting wire; Described heat treated process is: the speed with 400mL/min passes into argon gas in tube furnace, after argon gas passes into 1.5h, be incubated 2h after with the heating rate of 15 ℃/min, temperature in stove being risen to 750 ℃, then the rate of temperature fall with 20 ℃/min is cooled to room temperature with temperature in stove.
The technology that the present embodiment adopts swage drawing and groove rolling to combine not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire, the wire rod of preparation has higher mechanical strength, and the normal temperature lower yield strength reaches 143MPa, tensile strength reaches 274MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
Embodiment 4
13 core MgB 2The preparation of superconducting wire:
Step 1, (granularity is-200 orders with the magnesium powder, quality purity is 99.8%), amorphous boron powder (quality purity is 99.999%) and sodium rice TiC powder (quality purity is 99%) be according to Mg: B: TiC=1: the atomic ratio of 1.9: 0.1 mixes, then mixture ground and mixed under argon shield is even, obtain Precursor Powder;
Step 2, Precursor Powder described in step 1 is packed into (external diameter is 12mm for Ta pipe after the conventional method pickling processes, wall thickness is 1.5mm, the mass content of Ta is not less than 99.9%) in, the Ta pipe that then Precursor Powder will be housed is packed into, and (external diameter is 15.5mm for oxygen-free copper pipe after the conventional method pickling processes, wall thickness is 1.5mm, residual resistivity is not less than 80) in, make the tubulature complex;
Step 3, the pass reduction with 20% carry out groove rolling to the complex of tubulature described in step 2, the diameter that obtains having circular cross-section is the single-core wire 1 of 3mm, length according to 1.5m is carried out scale, is blocked single-core wire 1, then it is to soak 5min in 15% nitric acid that the sealed at both ends protection of single-core wire 1 after blocking is placed on mass concentration, then water washes away single-core wire 1 remained on surface acid solution, with the absolute ethyl alcohol dehydration, dry under 60 ℃ of conditions at last again;
step 4, be that NbTi/Cu compound bar 2 after the conventional method pickling of 9mm is (by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material with diameter, wherein the mass ratio of oxygen-free copper and niobium titanium alloy is 1: 1.2, the residual resistivity of oxygen-free copper is not less than 80, in niobium titanium alloy, the quality percentage composition of niobium is 55%, surplus is titanium) (residual resistivity is not less than 80 to be placed in oxygen-free copper pipe 3 after the conventional method pickling processes, external diameter is 19mm, wall thickness is 1.5mm) in, single-core wire 1 after pickling in 12 step 3 along the circumferential direction is arranged in circular ring around NbTi/Cu compound bar 2 packs in oxygen-free copper pipe 3, obtain secondary compound bar (as shown in Figure 2),
Step 5, the pass reduction with 15% carry out swaging of 5 passages and drawing processing to the compound bar of secondary described in step 4, then with 15% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 10 passages, secondary compound bar after groove rolling is swaged and drawing processing with 15% pass reduction at last, obtaining diameter is 13 core wires of 0.8mm;
Step 6, sealed at both ends being placed in tube furnace of 13 core wires described in step 5 heat-treated, obtain 13 core MgB 2Superconducting wire; Described heat treated process is: the speed with 500mL/min passes into argon gas in tube furnace, after argon gas passes into 1h, be incubated 0.5h after with the heating rate of 20 ℃/min, temperature in stove being risen to 850 ℃, then the rate of temperature fall with 20 ℃/min is cooled to room temperature with temperature in stove.
The technology that the present embodiment adopts swage drawing and groove rolling to combine not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire, the wire rod of preparation has higher mechanical strength, and the normal temperature lower yield strength reaches 132MPa, tensile strength reaches 258MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
Embodiment 5
13 core MgB 2The preparation of superconducting wire:
Step 1, (granularity is-200 orders with the magnesium powder, quality purity is 99.8%), amorphous boron powder (quality purity is 99.999%) and sodium rice TiC powder (quality purity is 99%) be according to Mg: B: TiC=1: the atomic ratio of 1.95: 0.05 mixes, then mixture ground and mixed under argon shield is even, obtain Precursor Powder;
Step 2, Precursor Powder described in step 1 is packed into (external diameter is 11mm for Ta pipe after the conventional method pickling processes, wall thickness is 1.2mm, the mass content of Ta is not less than 99.9%) in, the Ta pipe that then Precursor Powder will be housed is packed into, and (external diameter is 14mm for oxygen-free copper pipe after the conventional method pickling processes, wall thickness is 1.2mm, residual resistivity is not less than 80) in, make the tubulature complex;
Step 3, the pass reduction with 10% carry out groove rolling to the complex of tubulature described in step 2, the diameter that obtains having circular cross-section is the single-core wire 1 of 4mm, length according to 1.2m is carried out scale, is blocked single-core wire 1, then it is to soak 6min in 12% nitric acid that the sealed at both ends protection of single-core wire 1 after blocking is placed on mass concentration, then water washes away single-core wire 1 remained on surface acid solution, with the absolute ethyl alcohol dehydration, dry under 55 ℃ of conditions at last again;
step 4, be that NbTi/Cu compound bar 2 after the conventional method pickling of 12mm is (by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material with diameter, wherein the mass ratio of oxygen-free copper and niobium titanium alloy is 1: 1, the residual resistivity of oxygen-free copper is not less than 80, in niobium titanium alloy, the quality percentage composition of niobium is 47%, surplus is titanium) (residual resistivity is not less than 80 to be placed in oxygen-free copper pipe 3 after the conventional method pickling processes, external diameter is 25mm, wall thickness is 2mm) in, single-core wire 1 after pickling in 12 step 3 along the circumferential direction is arranged in circular ring around NbTi/Cu compound bar 2 packs in oxygen-free copper pipe 3, obtain secondary compound bar (as shown in Figure 2),
Step 5, the pass reduction with 20% carry out swaging of 4 passages and drawing processing to the compound bar of secondary described in step 4, then with 10% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 15 passages, secondary compound bar after groove rolling is swaged and drawing processing with 10% pass reduction at last, obtaining diameter is 13 core wires of 1.2mm;
Step 6, sealed at both ends being placed in tube furnace of 13 core wires described in step 5 heat-treated, obtain 13 core MgB 2Superconducting wire; Described heat treated process is: the speed with 400mL/min passes into argon gas in tube furnace, after argon gas passes into 1.5h, be incubated 1.5h after with the heating rate of 15 ℃/min, temperature in stove being risen to 750 ℃, then the rate of temperature fall with 15 ℃/min is cooled to room temperature with temperature in stove.
The technology that the present embodiment adopts swage drawing and groove rolling to combine not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire, the wire rod of preparation has higher mechanical strength, and the normal temperature lower yield strength reaches 142MPa, tensile strength reaches 271MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
Embodiment 6
13 core MgB 2The preparation of superconducting wire:
Step 1, (granularity is-200 orders with the magnesium powder, quality purity is 99.8%), amorphous boron powder (quality purity is 99.999%) and sodium rice TiC powder (quality purity is 99%) be according to Mg: B: TiC=1: the atomic ratio of 1.98: 0.02 mixes, then mixture ground and mixed under argon shield is even, obtain Precursor Powder;
Step 2, Precursor Powder described in step 1 is packed into (external diameter is 10mm for Ta pipe after the conventional method pickling processes, wall thickness is 1.0mm, the mass content of Ta is not less than 99.9%) in, the Ta pipe that then Precursor Powder will be housed is packed into, and (external diameter is 12.5mm for oxygen-free copper pipe after the conventional method pickling processes, wall thickness is 1mm, residual resistivity is not less than 80) in, make the tubulature complex;
Step 3, the pass reduction with 15% carry out groove rolling to the complex of tubulature described in step 2, the diameter that obtains having circular cross-section is the single-core wire 1 of 5mm, length according to 1.2m is carried out scale, is blocked single-core wire 1, then it is to soak 8min in 10% nitric acid that the sealed at both ends protection of single-core wire 1 after blocking is placed on mass concentration, then water washes away single-core wire 1 remained on surface acid solution, with the absolute ethyl alcohol dehydration, dry under 50 ℃ of conditions at last again;
step 4, be that NbTi/Cu compound bar 2 after the conventional method pickling of 15mm is (by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material with diameter, wherein the mass ratio of oxygen-free copper and niobium titanium alloy is 1: 0.8, the residual resistivity of oxygen-free copper is not less than 80, in niobium titanium alloy, the quality percentage composition of niobium is 45%, surplus is titanium) (residual resistivity is not less than 80 to be placed in oxygen-free copper pipe 3 after the conventional method pickling processes, external diameter is 31mm, wall thickness is 3mm) in, single-core wire 1 after pickling in 12 step 3 along the circumferential direction is arranged in circular ring around NbTi/Cu compound bar 2 packs in oxygen-free copper pipe 3, obtain secondary compound bar (as shown in Figure 2),
Step 5, the pass reduction with 10% carry out swaging of 3 passages and drawing processing to the compound bar of secondary described in step 4, then with 14% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 14 passages, secondary compound bar after groove rolling is swaged and drawing processing with 14% pass reduction at last, obtaining diameter is 13 core wires of 1.5mm;
Step 6, sealed at both ends being placed in tube furnace of 13 core wires described in step 5 heat-treated, obtain 13 core MgB 2Superconducting wire; Described heat treated process is: the speed with 300mL/min passes into argon gas in tube furnace, after argon gas passes into 2h, be incubated 3h after with the heating rate of 10 ℃/min, temperature in stove being risen to 650 ℃, then the rate of temperature fall with 10 ℃/min is cooled to room temperature with temperature in stove.
The technology that the present embodiment adopts swage drawing and groove rolling to combine not only can improve copper/niobium and niobium/MgB 2Between Compound Degree, increase the uniformity of core deformation of filament, and can improve the density of Multi-core wire, improve the connectivity of intergranule, more be conducive to prepare high performance multicore MgB 2Superconducting wire, the wire rod of preparation has higher mechanical strength, and the normal temperature lower yield strength reaches 139MPa, tensile strength reaches 268MPa, can carry larger ess-strain and superconduction current-carrying performance without obvious reduction, more meet the practical requirement of superconducting wire, satisfied the requirement of magnet preparation.
The above; it is only preferred embodiment of the present invention; be not that the present invention is done any restriction, every any simple modification, change and equivalent structure of above embodiment being done according to the invention technical spirit changes, and all still belongs in the protection range of technical solution of the present invention.

Claims (7)

1. multicore MgB 2The preparation method of superconducting wire is characterized in that, the method comprises the following steps:
Step 1, magnesium powder, amorphous boron powder and the nano TiC powder atomic ratio according to Mg: B: TiC=1: (2-x): x is mixed, then that mixture ground and mixed under argon shield is even, obtain Precursor Powder; The value of described x is 0.02～0.10;
Step 2, Precursor Powder described in step 1 is packed in Ta pipe after pickling processes, the Ta pipe that then Precursor Powder will be housed is packed in oxygen-free copper pipe after pickling processes, makes the tubulature complex;
Step 3, the complex of tubulature described in step 2 is carried out groove rolling, obtain having the single-core wire (1) of circular cross-section, single-core wire (1) is carried out successively scale, blocks and pickling; The pass reduction of described groove rolling is 10%～20%;
Step 4, the single-core wire (1) after pickling in NbTi/Cu compound bar (2) and 6 or 12 step 3 is placed in oxygen-free copper pipe (3) after pickling processes carries out the secondary assembling and obtain the secondary compound bar; Described NbTi/Cu compound bar (2) is by forming as the oxygen-free copper of cladding material with as the niobium titanium alloy of inner layer material, the mass ratio of described oxygen-free copper and niobium titanium alloy is 1: 0.8～1.2, the residual resistivity of described oxygen-free copper is not less than 80, in described niobium titanium alloy, the quality percentage composition of niobium is 45%～55%, and surplus is titanium; NbTi/Cu compound bar (2) in described secondary assembling process after pickling is placed in oxygen-free copper pipe (3) center after pickling processes, and the single-core wire after pickling (1) the along the circumferential direction NbTi/Cu compound bar (2) after the pickling is arranged in circular ring and packs in oxygen-free copper pipe (3) after pickling processes; When the quantity of described single-core wire (1) is 6, the size of described NbTi/Cu compound bar (2) and single-core wire (1) measure-alike; When the quantity of described single-core wire (1) was 12, the diameter of described NbTi/Cu compound bar (2) was 3 times of single-core wire (1) diameter;
Step 5, the pass reduction with 10%～20% carry out swaging of 3～5 passages and drawing processing to the compound bar of secondary described in step 4, then with 10%～15% pass reduction to through swage and drawing processing after the secondary compound bar carry out the groove rolling of 10～15 passages, secondary compound bar after groove rolling is swaged and drawing processing with 10%～15% pass reduction at last, obtain the Multi-core wire that diameter is 0.8mm～1.5mm;
Step 6, sealed at both ends being placed in tube furnace of Multi-core wire described in step 5 heat-treated, obtain multicore MgB 2Superconducting wire; Described heat treated process is: the speed with 300mL/min～500mL/min passes into argon gas in tube furnace, after argon gas passes into 1h～2h, be incubated 0.5h～3h after with the heating rate of 10 ℃/min～20 ℃/min, temperature in stove being risen to 650 ℃～850 ℃, then the rate of temperature fall with 10 ℃/min～20 ℃/min is cooled to room temperature with temperature in stove.
2. a kind of multicore MgB according to claim 1 2The preparation method of superconducting wire is characterized in that, the quality purity of the powder of magnesium described in step 1 is 99.8%, and the granularity of magnesium powder is-200 orders, and the quality purity of described amorphous boron powder is 99.999%, and the quality purity of described nano TiC powder is 99%.
3. a kind of multicore MgB according to claim 1 2The preparation method of superconducting wire is characterized in that, the external diameter of the pipe of Ta described in step 2 is 10mm～12mm, and wall thickness is 1.0mm～1.5mm, and in the Ta pipe, the mass content of Ta is not less than 99.9%.
4. a kind of multicore MgB according to claim 1 2The preparation method of superconducting wire is characterized in that, the external diameter of oxygen-free copper pipe described in step 2 is 12.5mm～15.5mm, and wall thickness is 1.0mm～1.5mm, and the residual resistivity of described oxygen-free copper pipe is not less than 80.
5. a kind of multicore MgB according to claim 1 2The preparation method of superconducting wire is characterized in that, the diameter of single-core wire described in step 3 (1) is 3mm～8mm.
6. a kind of multicore MgB according to claim 1 2The preparation method of superconducting wire; it is characterized in that; the acid cleaning process of single-core wire described in step 3 (1) is: it is to soak 5min～8min in 10%～15% nitric acid that the sealed at both ends protection of single-core wire (1) is placed on mass concentration; then water washes away single-core wire (1) remained on surface acid solution; with the absolute ethyl alcohol dehydration, dry under 50 ℃～60 ℃ conditions at last again.
7. a kind of multicore MgB according to claim 1 2The preparation method of superconducting wire is characterized in that, the residual resistivity of oxygen-free copper pipe described in step 4 (3) is not less than 80, and the external diameter of oxygen-free copper pipe (3) is 19mm～31mm, and wall thickness is 1.5mm～3mm.
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CN103956222A (en) * 2014-05-16 2014-07-30 宝胜科技创新股份有限公司 Method for preparing six-core MgB2 superconducting wire by magnesium diffusion method
CN105845278A (en) * 2016-04-12 2016-08-10 东南大学 Manufacturing method for practical multi-core MgB2 composite superconductive wire rods
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