WO2004013871A1 - 超電導線材の製造方法 - Google Patents
超電導線材の製造方法 Download PDFInfo
- Publication number
- WO2004013871A1 WO2004013871A1 PCT/JP2003/009704 JP0309704W WO2004013871A1 WO 2004013871 A1 WO2004013871 A1 WO 2004013871A1 JP 0309704 W JP0309704 W JP 0309704W WO 2004013871 A1 WO2004013871 A1 WO 2004013871A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal pipe
- raw material
- material powder
- wire
- heat treatment
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 106
- 239000002184 metal Substances 0.000 claims abstract description 106
- 239000000843 powder Substances 0.000 claims abstract description 105
- 239000002994 raw material Substances 0.000 claims abstract description 86
- 238000010438 heat treatment Methods 0.000 claims abstract description 76
- 238000011049 filling Methods 0.000 claims abstract description 26
- 238000007789 sealing Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000012856 packing Methods 0.000 claims description 34
- 239000002887 superconductor Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000005491 wire drawing Methods 0.000 claims description 15
- 238000002788 crimping Methods 0.000 claims description 5
- 238000005219 brazing Methods 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 34
- 229910052709 silver Inorganic materials 0.000 description 34
- 239000004332 silver Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 29
- 238000007872 degassing Methods 0.000 description 27
- 230000007547 defect Effects 0.000 description 19
- 230000008961 swelling Effects 0.000 description 19
- 239000013078 crystal Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
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- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 235000013580 sausages Nutrition 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0801—Manufacture or treatment of filaments or composite wires
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
- Y10S505/704—Wire, fiber, or cable
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49014—Superconductor
Definitions
- the present invention relates to a method for manufacturing a superconducting wire.
- the present invention relates to a method for manufacturing a superconducting wire capable of improving a critical current density (Jc) by suppressing expansion and a decrease in bonding during sintering, even for a long wire.
- Jc critical current density
- a technique of forming an oxide superconductor such as a Bi2223 phase into a long tape-shaped wire by a powder-in-tube method is known.
- a raw material powder for the superconducting phase is filled in a metal pipe such as silver.
- the metal pipe filled with the raw material powder is drawn to form a clad wire.
- Multiple clad wires are bundled, inserted into a metal pipe such as silver, and drawn to form a multi-core wire.
- This multifilamentary wire is rolled into a tape-shaped wire.
- the primary heat treatment is performed on the tape-shaped wire to generate the desired superconducting phase.
- the tape-shaped wire is rolled again and subjected to a secondary heat treatment to join the superconducting phase crystal grains.
- These two times of plastic working and heat treatment may be performed only once, but are generally performed in an atmosphere containing 7 to 21% by volume of oxygen.
- a tape-shaped wire having a large number of superconducting filaments in a metal sheath is obtained.
- the gas remaining in the raw material powder is generated in the above-described first heat treatment and second heat treatment stages, causing voids between crystals of the superconductor, and bonding of the gas and the raw material powder.
- the amorphous phase is segregated, which inhibits the bonding between the crystals of the superconductor and lowers the critical current density.
- defects such as swelling occur due to local gas collection.
- Japanese Patent Application Laid-Open No. 6-342607 discloses that after the wire drawing, a heat treatment at 550 ° C. to 760 ° C. is performed in a reduced pressure atmosphere to remove the adsorbed gas from the raw material powder.
- heat treatment is performed after wire drawing, and gas is released because the density of the raw material powder in the metal pipe increases due to wire drawing and the air permeability deteriorates.
- JP-A-6-176635 discloses filling a metal pipe with an oxide powder in a vacuum or in an atmosphere having a humidity of 30% or less.
- this technique can leave air in the metal pipe. The remaining air is generated in the first heat treatment and the second heat treatment, thereby causing swelling and inhibiting the bonding between crystals to lower the critical current density.
- a rod-shaped molding made of oxide superconductor powder is performed while heating to 200 ° C. to 800 ° C. and reducing the pressure to 1/10 3 Torr (0.13 Pa) or less. It discloses that the body is vacuum sealed in a metal pipe.
- the metal pipe is filled with a rod-shaped body instead of a powder, so it has poor air permeability, and there is a problem that it is not possible to perform sufficient degassing to the center of the metal pipe.
- the rod-shaped compact may be deformed non-uniformly in the wire drawing process, causing voids and the like in the metal pipe to lower the critical current density.
- a main object of the present invention is to provide a method of manufacturing a superconducting wire rod capable of improving the critical current density by sufficiently performing degassing in a metal pipe.
- a metal pipe is filled with a raw material powder of an oxide superconductor at a packing density of 10% or more and 40% or less, and then the pipe end is sealed under reduced pressure, and the raw material powder is sealed. It is characterized in that a drawn metal pipe is drawn.
- the method for producing a superconducting wire of the present invention comprises the steps of: filling a metal pipe with a raw material powder composed of an oxide superconductor or a raw material powder composed of a precursor that becomes an oxide superconductor by heat treatment; Heating the filled metal pipe to 400 ° C. or more and 800 ° C. or less, depressurizing the inside of the heated metal pipe to lOOPa or less, A step of sealing the opening at the end of the metal pipe in a state in which the metal powder is filled, and a step of drawing the metal pipe in which the raw material powder is sealed. Then, the packing density of the raw material powder is set to 10% or more and 40% or less.
- heat treatment is performed at 400 ° C or more and 800 ° C or less.
- a step may be provided.
- an adsorbed gas steam, carbon, hydrocarbon, etc.
- a process from mixing to sintering a process from mixing to sintering.
- Gases such as excess oxygen are included.
- first heat treatment and second heat treatment after the wire is formed, voids are created between the crystals of the superconductor, And the segregation of the amorphous phase. These voids and the amorphous phase hinder the bonding between the crystals, thereby reducing the critical current density.
- the gas released from the raw material powder was not discharged from the metal pipe but stayed in the pipe, causing defects such as swelling of the wire rod.
- the present invention provides a degassing process in which a raw material powder of a superconductor is first filled in a metal pipe, and then a gas contained in the raw material powder and water that is a source of the gas are vaporized and exhausted from the metal pipe. (Decompression). At this time, the packing density of the raw material powder is specified so as to realize good air permeability so that the raw material powder does not hinder the release of gas to the outside of the metal pipe.
- the end of the metal pipe is sealed while the metal pipe ⁇ is depressurized, so that the inside of the degassed pipe is In addition, it is possible to prevent moisture and carbon dioxide in the air from newly entering.
- heat treatment is performed at 400 ° C or more and 800 ° C or less.
- FIG. 1 (A) is a schematic view of a vacuum sealing device for sealing a metal pipe by heating and bonding
- FIG. 1 (B) is an enlarged sectional view of a lid.
- FIG. 2 is a graph showing the number of defects such as swelling and the critical current density in Test Example 1 with respect to the packing density.
- FIG. 3 is a graph showing the number of generated defects such as blisters and the critical current density with respect to the heating temperature in the degassing treatment in Test Example 2. .
- FIG. 4 is a schematic view of a vacuum sealing device for performing sealing by heating a metal pipe and pressing an exhaust nozzle by compression, and is a type that vertically supports the metal pipe.
- FIG. 5 is a schematic view of a vacuum sealing device that heats a metal pipe and seals by compression of an exhaust nozzle, and is a type that horizontally supports a metal pipe.
- FIG. 6 is a graph showing the number of generated defects such as swelling versus the packing density and the critical current density in Test Example 3.
- the manufacturing process of the superconducting wire is usually performed by “preparation of raw material powder ⁇ preparation of clad wire ⁇ preparation of multi-core wire ⁇ rolling to produce tape-shaped wire ⁇ heat treatment”. If necessary, repeat rolling and heat treatment several times. For example, following “Preparation of multifilamentary wire”, “Preparation of tape-shaped spring material by primary rolling ⁇ -Next heat treatment ⁇ Secondary rolling of tape-shaped wire ⁇ Secondary heat treatment” is performed.
- the method for producing a superconducting wire of the present invention specifies the conditions for producing a clad wire, and “filling the adjusted raw material powder into a metal pipe ⁇ degassing (heating) ⁇ degassing (decompression) ⁇ Equipped with the process of “sealing of metal pipes ⁇ wire drawing with degassing”. Other steps may be performed in the same manner as in the related art.
- the raw material powder to be filled in the metal pipe is a raw material powder composed of an oxide superconductor or a raw material powder composed of a precursor that becomes an oxide superconductor by heat treatment.
- a powder (powder made of a precursor) obtained by mixing the composite oxide so as to have a predetermined composition ratio, and a powder obtained by sintering and pulverizing the mixed powder (powder made of an oxide superconductor) Specifically, for example, Bi2212, Bi2223 and the like can be mentioned. In the case of B12223, it is preferable to use a precursor as a raw material powder because sintering facilitates integration and the critical current density can be further improved.
- Bi2212 it is preferable to use a powder made of an oxide superconductor since the critical current density can be improved.
- a method for finally obtaining an M2223-based superconducting wire for example, using Bi, Pb, Sr, Ca, and Cu as starting materials, these powders are heated at 700 to 870 ° C for 10 to 40 hours in an air atmosphere or a reduced pressure atmosphere. Sintering at least once.
- a known nitrate aqueous solution spray pyrolysis method, a sol-gel method and the like can be mentioned. These methods can be obtained raw material powder ⁇ 2212 phase than ⁇ 2223 phase was mainly (Bi2212, Ca 2 Cu0 3, Ca 2 Pb0 4 of which mixtures).
- Those satisfying 8: 3 are preferred.
- Bi is preferably around 1.8
- Pb is around 0.3 to 0.4
- Sr is around 2
- Ca is around 2.2
- Cu is around 3.0.
- the raw material powder is subjected to a heat treatment at a temperature of 400 ° C or more and 800 ° C or less, so that the gas contained in the raw material powder and the water content of the gas can be reduced. Can be more effectively removed.
- Ag, Cu, Fe, Ni s Cr, Ti, Mo, N Pt, Pd, Rh, Ir, Ru, alloys are preferably based on metal or those metals selected from 0 s.
- Ag or an Ag alloy is preferable from the viewpoint of reactivity with an oxide superconductor and workability. (Filling density)
- the packing density when filling the raw material powder into the metal pipe is suitably from 10% to 40%. If the packing density is less than 10%, the amount of the raw material powder is too small and it is difficult to uniformly fill the metal pipe. On the other hand, if the packing density is over 40%, 3 009704
- Non-uniform deformation such as sausaging (split filaments are present in the cross section of the metal pipe) during hot spring processing.
- the packing density is defined as 100% of the theoretical density of the raw material powder to be filled, and the ratio (%) to the theoretical density.
- the theoretical density of the raw material powder to be filled is the sum of the product of the theoretical density of each constituent phase and its content in all constituent phases of the material powder, that is, ⁇ 'X fii: The theoretical density of constituent phase i of the raw material powder, fi : Content ratio of constituent phase i of the raw material powder).
- the ultimate pressure in the degassing process (reduced pressure), the ultimate pressure is set to 100 Pa or less. If the ultimate pressure is over lOOPa, the residual gas is large and the degassing effect is small.
- the rate of pressure reduction from normal pressure to ultimate pressure is preferably 2 kPa / min or less. At more than 2 kPa / min, the raw material powder in the metal pipe cannot follow the change in pressure, and may soar from the pipe and erupt.
- the metal pipe is heated to some extent and then gradually exhausted.
- the degassing treatment (heating) is preferably performed by heating the metal pipe filled with the raw material powder to 400 ° C or more and 800 ° C or less.
- the temperature is 400 ° C or more, the degassing effect can be more effectively obtained.
- the higher the temperature the more reliably the gas can be discharged.
- the temperature exceeds 800 ° C, the raw material powder may be decomposed. Therefore, in the present invention, the temperature is set to 800 ° C or less.
- Degassing may be performed at atmospheric pressure, but temperature rise to 400 ° C is performed at atmospheric pressure, and gradually exhausted from over 400 ° C to 400 ° C or more and 800 ° C or less It is preferable to perform the heat treatment under reduced pressure, more preferably in a vacuum, since the degassing effect is high.
- the reason for reducing the pressure after raising the temperature to at least 400 ° C at atmospheric pressure (normal pressure) is that if the pressure is reduced at the same time as the temperature is raised, the raw material powder may be ejected from the metal pipe with the release of gas.
- the time for maintaining the temperature between 400 ° C and 800 ° C can be changed as appropriate depending on the diameter and length of the metal pipe. Good. For example, when the inner diameter of the metal pipe is 20 to 30 mra and the length is 500 to 1500 mm, it is preferably 2 to 10 hours.
- the opening at the end of the metal pipe is sealed in a state where the pressure is reduced to 100Pa or less as described above. That is, in addition to suppressing the intrusion of new gas by reducing the pressure inside the metal pipe, new gas can enter the pipe by sealing the opening at the end of the metal pipe. Is more reliably prevented. Since the wire drawing is performed while the metal pipe is sealed, a sealing method that can withstand the wire drawing and is applicable to vacuum encapsulation is suitable. Specific examples include methods such as electron beam welding, brazing, and pressure bonding of an exhaust nozzle welded to a metal pipe.
- the wire drawing is performed in a state where the end of the metal pipe filled with the raw material powder is sealed as described above.
- a raw material powder of Bi2212, Ca 2 Cu0 3, Ca 2 Pb0 consists of a mixture of such 4 oxide superconductor.
- the packing density is defined as 100% of the theoretical density of the raw material powder to be filled.
- the packing density was changed as follows. The packing density of 30% or more and 40% or less was obtained by filling the raw material powder with a granulated powder by a wet granulator. A packing density of more than 40% was obtained by filling a raw material powder into a rod by CIP (hydrostatic press). (2) Immediately before filling the silver powder, the raw material powder or its molded body is subjected to a heat treatment at 700 ° C for 10 hours while evacuating to about 100Pa in some cases.
- the silver components were removed and the silver pipe was filled in a glove box that had been cleaned by flowing dry air gas.
- the heat treatment before filling may be performed in an inert gas such as nitrogen or argon or in dry air from which moisture has been removed, in addition to evacuation.
- the same effect can be obtained by filling the silver pipe in an inert gas or in a vacuum.
- a silver pipe having a thickness of 2 mm and an inner diameter of 30 mm with a silver lid welded to the opening at one end was used.
- the wire is drawn with the silver lid still in place to prevent air from entering the silver pipe, and the wire is turned into a wire to obtain a clad wire. Subsequent procedures are the same as the conventional manufacturing method.
- Bundle a plurality of clad wires and insert them into a silver pipe (outside diameter 36 mm, inside diameter 30 mm), and seal the opening at the end of the pipe with a silver lid in a vacuum.
- 55 clad wires were used.
- wire-drawing is performed with the silver lid still on, and the wire is converted into a wire to obtain a multi-core wire.
- the wire was drawn to a diameter of 1.6 mm.
- the packing density was more than 50%, a defect occurred during the drawing process, and a long wire could not be obtained. As shown in FIG. 2, when the packing density exceeded 40%, swelling occurred, and the critical current density decreased. At a packing density of less than 10%, no defects such as swelling occurred, but the critical current density varied greatly in the length direction of the superconducting wire, and the critical current density over the entire length was lowered. This is considered to be because if the filling density was less than 10%, the raw material powder was difficult to uniformly fill the metal pipe, and the filaments after the wire drawing became uneven in the length direction.
- the superconducting wire was degassed by changing the heating temperature in various ways, and the presence of defects such as swelling and the critical current density were examined.
- the superconducting wire was obtained as follows.
- the filling density of each sample when filling the raw material powder into the silver pipe was 25%. 2 Heat the silver pipe filled with the raw material powder to a predetermined temperature (0 ° C to 650 ° C in this example, see Fig. 3 described later) to perform degassing. In this example, the temperature is raised to 400 ° C. under the atmospheric pressure, the gas is gradually exhausted from 400 ° C. or more, and heating is performed while reducing the pressure.
- FIG. 1 (A) is a schematic diagram of a vacuum sealing device for sealing a metal pipe by heating and brazing
- FIG. 1 (B) is an enlarged sectional view of a lid.
- the vacuum sealing device 10 includes a lift cylinder 12 for holding a metal pipe 1 in a vacuum vessel 11, a heater 13 arranged to cover the outer circumference of the pipe 1 supported by the cylinder 12, and a pipe 1 at one end. And an up / down operating rod 14 that supports the lid 3 b and is arranged to face the cylinder 12. Further, an exhaust port 15 is provided for exhausting gas generated by heating and air during depressurization.
- a procedure for sealing the metal pipe 1 from the degassing process by the vacuum sealing device 10 will be described.
- the vacuum vessel 11 is opened, the lid 3a is welded to one end, and the metal pipe 1 filled with the raw material powder 2 is placed in the lift cylinder 12, and the lid 3b is placed at the tip of the lifting operation rod 14 to vacuum.
- the metal pipe 1 is arranged on the inner peripheral side of the heater 13 by moving the lift cylinder 12 up and down to an appropriate position, and the pipe 1 is heated by the heater 13.
- the exhaust valve 16 is opened, and the air in the vacuum vessel 11 is exhausted by the vacuum pump 17 to reduce the pressure.
- the exhaust pipe 18 is provided with a flow rate adjusting meter 19, and the exhaust rate can be controlled by the meter 19 to adjust the pressure reduction rate.
- the pressure is reduced to the specified pressure, close the exhaust valve 16 and the meter valve 20.
- the lifting rod 14 is lowered, the lid 3b is arranged on the inner peripheral side of the high-frequency heating coil 21 provided above the heater 13, and the ring-shaped solder 3c (see FIG. 1 (B)).
- a heat-insulating shutter 22 is provided between the heater 13 and the high-frequency heating coil 21 so that the heat does not affect each other.
- the lift cylinder 12 is moved upward, and the lifting operation rod 14 is lowered to seal the opening la at the other end of the metal pipe 1.
- the lifting operation rod is a manual operation rod, but may be an automatic operation rod.
- wire-drawing is performed with the silver lid kept on, and the wire is turned into a multi-filament wire.
- the wire was drawn to a diameter of 1.6 mm.
- a primary heat treatment is performed to generate a Bi22 23- phase superconductor in the filament.
- intermediate rolling and additional heat treatment are performed to join the crystal grains of the Bi2223 phase to integrate the superconductor.
- FIGS. 4 and 5 are vacuum sealing devices by compression of exhaust nozzles, and both have almost the same basic configuration.
- Fig. 4 shows a type that supports metal pipes in the vertical direction
- Fig. 5 shows It is of the type that supports metal pipes horizontally. The procedure for sealing metal pipes with these devices is described in FIG.
- This device 30 includes a heater 31 arranged to cover the outer periphery of the metal pipe 1, an exhaust nozzle 32 attached to an opening la at an end of the pipe 1, and a vacuum pump 33 connected to the nozzle 32.
- a heater 31 arranged to cover the outer periphery of the metal pipe 1, an exhaust nozzle 32 attached to an opening la at an end of the pipe 1, and a vacuum pump 33 connected to the nozzle 32.
- the metal pipe 1 filled with the raw material powder is placed on the frame 34, and the opening at the end of the pipe 1 is opened. Weld the exhaust nozzle 32 to la. In this state, the metal pipe 1 is heated by the heater 31, and after heating, the gas present in the metal pipe 1 is exhausted by the vacuum pump 33 through the exhaust nozzle 32 to reduce the pressure.
- the decompression speed can be adjusted by controlling the flow rate exhausted by the flow control valve 35. The degree of vacuum can be checked with a vacuum gauge 36.
- the valve 37 When the pressure is reduced to a predetermined value, the valve 37 is closed and the connection with the vacuum pump 33 is released. Then, the opening at the end of the metal pipe is sealed by crimping the exhaust nozzle 32 with a crimping device (not shown). After crimping, the metal pipe 1 is removed from the device 30.
- the superconducting wire was manufactured by changing the packing density of the raw material powder in various ways, and the existence of defects such as swelling and the critical current density were examined.
- the superconducting wire was obtained in the same manner as in Test Example 2.
- the packing density is defined as 100% of the theoretical density of the raw material powder to be filled.
- the packing density was changed as follows.
- the packing density of 30% or more and 40% or less was obtained by filling the raw material powder with a granulated powder by a wet granulator.
- Packing densities of more than 40% were obtained by filling raw material powders into rods by CIP (hydrostatic pressing).
- the heating temperature for the degassing treatment was 640 ° C, the temperature was raised to 400 ° C under the atmospheric pressure, and the gas was gradually exhausted from 400 ° C or more and heated while reducing the pressure.
- the packing density is less than 10%, no swelling
- the critical current density varies greatly in the length direction of the material, and the entire length! : The critical current density has decreased. This is considered to be because if the packing density is less than 10%, the raw material powder is difficult to be uniformly filled in the metal pipe, and the filament after drawing becomes uneven in the length direction.
- the packing density is more than 40%, defects such as swelling occur very often, and the critical current density varies greatly in the length direction of the superconducting wire, and the critical current density over the entire length decreases. .
- the packing density is more than 40%, the permeability of the metal pipe deteriorates, it is not possible to perform uniform degassing to the center of the pipe, and the amount of residual impurities such as carbon and moisture increases. It is considered that swelling and other defects occur.
- the residual impurities precipitate as an amorphous phase between the crystals of the superconducting phase, and this amorphous phase easily interrupts the current path. Therefore, it is thought that the critical current density will decrease due to uneven deformation such as sausage in the subsequent wire drawing.
- a metal pipe filled with raw material powder is heated and degassed, and then the pressure is reduced, so that even a long superconducting wire can be used.
- an excellent effect that a high critical current density can be obtained by suppressing swelling and a decrease in bonding during sintering can be achieved.
- the raw material powder can be uniformly filled in the metal pipe, and the variation of the critical current density in the longitudinal direction of the superconducting wire can be reduced.
- by performing sufficient degassing it is possible to suppress the generation of an amorphous phase and uneven deformation in wire drawing, thereby improving the critical current density.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/510,349 US7293343B2 (en) | 2002-08-05 | 2003-07-30 | Method of manufacturing superconducting wire |
AU2003252739A AU2003252739B2 (en) | 2002-08-05 | 2003-07-30 | Method of producing superconductive wire material |
EP03766668A EP1528575A4 (en) | 2002-08-05 | 2003-07-30 | PROCESS FOR PRODUCING SUPERCONDUCTING METAL MATERIAL |
HK05109851A HK1077916A1 (en) | 2002-08-05 | 2005-11-04 | Method of manufacturing superconducting wire |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-227040 | 2002-08-05 | ||
JP2002227040 | 2002-08-05 |
Publications (1)
Publication Number | Publication Date |
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WO2004013871A1 true WO2004013871A1 (ja) | 2004-02-12 |
Family
ID=31492202
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/009704 WO2004013871A1 (ja) | 2002-08-05 | 2003-07-30 | 超電導線材の製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7293343B2 (ja) |
EP (1) | EP1528575A4 (ja) |
KR (1) | KR20050027141A (ja) |
CN (1) | CN1307654C (ja) |
AU (1) | AU2003252739B2 (ja) |
HK (1) | HK1077916A1 (ja) |
TW (1) | TWI270896B (ja) |
WO (1) | WO2004013871A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102083604A (zh) * | 2008-07-02 | 2011-06-01 | 陶氏环球技术公司 | 改进的使缆线脱气的方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100416714C (zh) * | 2003-09-17 | 2008-09-03 | 住友电气工业株式会社 | 超导装置和超导电缆 |
WO2005124793A1 (ja) * | 2004-06-22 | 2005-12-29 | Sumitomo Electric Industries, Ltd. | 超電導線材の製造方法 |
JP2006331687A (ja) * | 2005-05-23 | 2006-12-07 | Sumitomo Electric Ind Ltd | 超電導線材の製造方法、超電導多芯線材の製造方法および超電導機器 |
JP2008140769A (ja) * | 2006-11-06 | 2008-06-19 | Sumitomo Electric Ind Ltd | Bi2223超電導線材の製造方法 |
CN101339828B (zh) * | 2007-09-14 | 2010-11-17 | 朱水良 | 电力电缆加工方法 |
CN105405957B (zh) * | 2015-12-29 | 2018-09-21 | 北京英纳超导技术有限公司 | 一种铋系氧化物超导导线的制造方法 |
CN111014865A (zh) * | 2019-12-17 | 2020-04-17 | 西安聚能装备技术有限公司 | 一种粉末装管真空密封装置及密封方法 |
CN111952009B (zh) * | 2020-08-24 | 2022-04-08 | 西部超导材料科技股份有限公司 | 一种用粉末冶金法制备NbTi/Cu单芯棒的方法 |
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JPH05234437A (ja) * | 1992-02-20 | 1993-09-10 | Sumitomo Metal Ind Ltd | 酸化物超伝導線材の製造方法 |
JPH05282936A (ja) * | 1992-03-31 | 1993-10-29 | Nippon Steel Corp | 酸化物超電導線材・テープの製造方法 |
JPH07105762A (ja) * | 1993-10-05 | 1995-04-21 | Mitsubishi Heavy Ind Ltd | 粉体の真空シール方法 |
JPH11185551A (ja) * | 1997-12-18 | 1999-07-09 | Fujikura Ltd | 酸化物超電導線材の製造方法 |
JP2001184956A (ja) * | 1999-12-28 | 2001-07-06 | Sumitomo Electric Ind Ltd | 超電導線材の製造方法 |
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US3922769A (en) * | 1974-06-07 | 1975-12-02 | Gte Sylvania Inc | Method for making composite wire |
EP0304094B1 (en) * | 1987-08-21 | 1992-08-05 | Mitsubishi Materials Corporation | Process for fabricating superconducting ceramics materials |
US5004722A (en) * | 1989-01-19 | 1991-04-02 | International Superconductor Corp. | Method of making superconductor wires by hot isostatic pressing after bending |
JPH04292811A (ja) * | 1991-03-20 | 1992-10-16 | Sumitomo Electric Ind Ltd | 酸化物超電導線の製造方法 |
JPH06176635A (ja) | 1992-09-14 | 1994-06-24 | Toshiba Corp | 酸化物超電導線の製造方法 |
JPH06309967A (ja) | 1993-04-21 | 1994-11-04 | Mitsubishi Cable Ind Ltd | 酸化物超電導線の製造方法 |
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JP3534428B2 (ja) * | 1993-06-11 | 2004-06-07 | 住友電気工業株式会社 | 酸化物高温超電導線材の製造方法 |
-
2003
- 2003-07-30 CN CNB038102226A patent/CN1307654C/zh not_active Expired - Fee Related
- 2003-07-30 US US10/510,349 patent/US7293343B2/en not_active Expired - Lifetime
- 2003-07-30 KR KR1020057001969A patent/KR20050027141A/ko not_active Application Discontinuation
- 2003-07-30 AU AU2003252739A patent/AU2003252739B2/en not_active Ceased
- 2003-07-30 WO PCT/JP2003/009704 patent/WO2004013871A1/ja active Application Filing
- 2003-07-30 EP EP03766668A patent/EP1528575A4/en not_active Withdrawn
- 2003-08-01 TW TW092121120A patent/TWI270896B/zh not_active IP Right Cessation
-
2005
- 2005-11-04 HK HK05109851A patent/HK1077916A1/xx not_active IP Right Cessation
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JPH05234437A (ja) * | 1992-02-20 | 1993-09-10 | Sumitomo Metal Ind Ltd | 酸化物超伝導線材の製造方法 |
JPH05282936A (ja) * | 1992-03-31 | 1993-10-29 | Nippon Steel Corp | 酸化物超電導線材・テープの製造方法 |
JPH07105762A (ja) * | 1993-10-05 | 1995-04-21 | Mitsubishi Heavy Ind Ltd | 粉体の真空シール方法 |
JPH11185551A (ja) * | 1997-12-18 | 1999-07-09 | Fujikura Ltd | 酸化物超電導線材の製造方法 |
JP2001184956A (ja) * | 1999-12-28 | 2001-07-06 | Sumitomo Electric Ind Ltd | 超電導線材の製造方法 |
Non-Patent Citations (1)
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102083604A (zh) * | 2008-07-02 | 2011-06-01 | 陶氏环球技术公司 | 改进的使缆线脱气的方法 |
Also Published As
Publication number | Publication date |
---|---|
TW200406011A (en) | 2004-04-16 |
AU2003252739A1 (en) | 2004-02-23 |
HK1077916A1 (en) | 2006-02-24 |
CN1307654C (zh) | 2007-03-28 |
CN1653563A (zh) | 2005-08-10 |
US7293343B2 (en) | 2007-11-13 |
KR20050027141A (ko) | 2005-03-17 |
US20050172478A1 (en) | 2005-08-11 |
EP1528575A1 (en) | 2005-05-04 |
TWI270896B (en) | 2007-01-11 |
AU2003252739B2 (en) | 2008-08-21 |
EP1528575A4 (en) | 2007-02-07 |
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