WO2005117032A1 - 粉末法Nb3Sn超伝導線材の製造方法 - Google Patents
粉末法Nb3Sn超伝導線材の製造方法 Download PDFInfo
- Publication number
- WO2005117032A1 WO2005117032A1 PCT/JP2005/008970 JP2005008970W WO2005117032A1 WO 2005117032 A1 WO2005117032 A1 WO 2005117032A1 JP 2005008970 W JP2005008970 W JP 2005008970W WO 2005117032 A1 WO2005117032 A1 WO 2005117032A1
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- WIPO (PCT)
- Prior art keywords
- powder
- superconducting wire
- sheath
- raw material
- producing
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/12—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- 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
- H10N60/0184—Manufacture or treatment of devices comprising intermetallic compounds of type A-15, e.g. Nb3Sn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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 producing a Nb Sn superconducting wire by a powder method
- Nb Sn wire As a superconducting wire used for a superconducting magnet for generating a high magnetic field, Nb Sn wire is used.
- Non-Patent Document 1 For example, see Non-Patent Document 1).
- Sn concentration that can be dissolved in bronze (15.8 mass% or less).
- Ta and Sn are subjected to a melt diffusion reaction at a high temperature, and the reaction product is pulverized to obtain a Ta—Sn alloy powder.
- a method is also known in which Nb or an Nb-based alloy sheath is filled as a core portion, the diameter is reduced, and then heat treatment is performed (for example, see Patent Document 1). With this method, there is no limit on the amount of Sn, and due to the interdiffusion of Ta and Nb, a high-quality Nb Sn layer thicker than the bronze and ECN methods is formed.
- FIG. 1 is a cross-sectional view schematically showing a state in which an Nb Sn superconducting wire is manufactured by a powder method.
- reference numeral 1 denotes a sheath (tubular body) made of Nb or an Nb-based alloy
- 2 denotes a powder core portion filled with the raw material powder.
- a raw material powder containing Sn is filled in the powder core portion 2 of the case 1, and is extruded and subjected to a diameter reducing process such as a wire drawing process, thereby forming a wire rod.
- the obtained wire is wound around a magnet or the like and subjected to heat treatment to form an NbSn superconducting layer at the interface between the sheath and the raw material powder.
- the raw material powder used at this time a powder obtained by mixing Ta powder or Nb powder and Sn powder, an intermetallic compound powder obtained by reacting both powders by heat treatment, and the like are used.
- an intermetallic compound powder it is used after the reaction by grinding with an automatic mortar, ball mill, jet mill, or the like.
- Ta powder used in the ECN method or the melt diffusion method is obtained by adding hydrogen to make it brittle and then mechanically pulverizing (hereinafter referred to as "H-added Ta powder”) or electron beam. (Hereinafter referred to as “EB powder”) and the like obtained while dissolving the same are known. Further, Sn powder obtained by an atomization method using water is generally employed.
- the heat treatment temperature for forming the superconducting layer can be reduced to about 750 ° C by adding Cu to the power source powder, which is set to a high temperature of 930 ° C or more. Wear.
- the ECN method and the melt diffusion method after adding a small amount of Cu powder to the raw material powder, heat treatment for the formation of intermetallic compounds is performed, or a thin layer of Cu is placed inside the sheath. I have.
- the force shown schematically is a single core. Is generally used in the form of a multicore material in which a plurality of single cores of the present invention are arranged in a Cu matrix.
- the powder method proposed so far has the following problems with the raw material powder.
- the sintered body becomes very hard after heat treatment for generating intermetallic compounds (hereinafter sometimes referred to as “MD heat treatment”).
- MD heat treatment intermetallic compounds
- the work time for which the crushing process is not easy is very long.
- the Sn concentration exceeds 50 atomic%, it becomes very difficult to grind the Ta—Sn powder.
- the particle size of the compound powder becomes so large that the sheath may be broken at the time of drawing with a small diameter, and this breakage has a problem that the superconductivity is greatly affected. In the worst case, the sheath may be broken, making the production of the superconducting wire itself difficult.
- the powder contains a large amount of oxygen gas or hydrogen gas, the processability and reactivity are deteriorated, and hydrogen is released during MD heat treatment, which is dangerous. You will have to wait until the gas is complete.
- the surface of Sn powder is very easily oxidized.
- the presence of such oxides on the surface will significantly reduce the reactivity during MD heat treatment.
- the structure of the powder obtained after each heat treatment varies, and the wire characteristics vary.
- Cu powder is generally mixed into the raw material powder used in the production of superconducting wire rods.
- the addition time of the Cu powder is before the MD heat treatment, a relatively large Cu— A Snii dyad will be generated. Since such a compound is very hard and brittle, the uniform processing of the wire is deteriorated.
- a raw material powder is filled in a sheath by a uniaxial press.
- Force With such a filling method, the force and pressure are at most about lOMPa, and the filling rate of the powder is only about 50%. If wire processing is performed in such a state, it is difficult to perform uniform force drawing in the longitudinal direction, and a part of the sheath material may be damaged.
- Non-patent literature 1 K. Tachkawa Filamentary Al superconductors, Plenum Press (1980) pl
- Non-patent document 2 W ⁇ . Neijmeijer et al., J ⁇ ess-commonMetal, Vol, 160 (1990) pl61
- Patent document 1 JP-A-11- No. 250749
- the present invention has been made under such a circumstance, and an object of the present invention is to provide a powder capable of performing uniform processing without causing any inconvenience during production as much as possible and exhibiting excellent superconducting properties.
- the method of the present invention which has achieved the above object, is that at least one kind of metal powder selected from Ta powder and Nb powder and Sn powder are obtained in a case of Nb or Nb-based alloy.
- An intermetallic compound powder or a mixed powder of the metal powder and the Sn powder is filled as a raw material powder, the sheath is reduced in diameter to form a wire, and the wire is heat-treated, whereby an interface between the sheath and the filled powder is obtained.
- At least one kind of metal powder selected from the Ta powder and the Nb powder is a powder in which fine primary particles are aggregated in a coral shape to form secondary particles.
- Nb Sn superconducting wire that can be used in powder method can be produced.
- FIG. 1 is a cross-sectional view schematically showing an Nb Sn wire obtained by a powder method.
- FIG. 2 is a scanning electron microscope photograph showing the particle shape of H-added Ta powder.
- FIG. 3 is a scanning electron microscope photograph showing the particle shape of EB-dissolved Ta powder.
- FIG. 4 is a scanning electron microscope photograph showing the particle shape of the reduced sodium powder.
- FIG. 5 is an electron micrograph instead of a drawing, showing an enlarged particle shape of the sodium reduced powder.
- Ta powder or fine powder of intermetallic compound obtained by agglomeration of Nb powder or a mixed powder of the above powder is used as one of the raw material powders. It was also found that the surface area of Ta powder or Nb powder was increased and the production rate of intermetallic compounds was improved.
- the term “coral-like” means a state in which fine powders are aggregated to form a porous mass.
- the following effects are also exhibited. That is, as the intermetallic compound powder becomes smaller, the resulting melt-diffusion powder becomes finer and the pulverization becomes extremely easy. Further, by using the melt-diffusion powder thus obtained, the sheath material is not damaged even when the diameter of the wire is reduced.
- K NbF may be reduced with Na, Mg, Ca or the like.
- the raw material powder used in the present invention is a Ta powder or a powder that can also obtain Nb powder power in which fine primary particles are aggregated in a coral shape.
- the hydrogen concentration is preferably 100 ppm or less.
- the powder After reducing 272 with Na, the powder is formed by reducing the H concentration by heat treatment.
- the Na reduction method is optimal.
- the Na reduction method produces fine primary particles (average particle size: 0.1 to 20 m) and produces Ta powder or Nb powder in which the primary particles aggregate in a coral form to form secondary particles. can do. Further, according to this method, the hydrogen concentration and the oxygen concentration can be reduced to the above-described levels.
- Commercially available powders include Na reduced powder manufactured by Rikibot Co., Ltd. and Starck Co., Ltd.
- the power at which the Sn powder is mixed with the raw material powder used in the present invention preferably has an oxygen concentration of 2000 ppm or less.
- Gas atomizing method can be applied.
- the procedure for preparing the raw material powder is not particularly limited, but the Ta—Sn compound powder is prepared by mixing, heat-treating and pulverizing the above-described Ta powder or Nb powder and Sn powder. After the powder or the Nb—Sn compound powder is prepared, it is preferable to add a Cu powder to obtain a raw material powder.
- the Cu powder and the Sn powder do not react during the MD heat treatment, and the heat treatment temperature is lowered during the NbSn formation heat treatment.
- the filling rate of the raw material powder into the sheath can be increased to 70% or more, and uniform processing is facilitated.
- the mixing ratio of unreacted Sn is 5% by mass or more after forming the metal compound powder.
- Unreacted Sn may be an unreacted Sn component in the metal compound powder, may be adjusted by adding Sn powder separately from the metal compound powder, or both may be used. Such unreacted Sn improves the slipperiness between particles during extrusion and wire drawing, and can improve workability.
- a Ta powder was prepared in which the primary particles obtained by the Na reduction method aggregated in a coral form to form secondary particles.
- the average particle size of the primary particles is 10 / zm or less
- the particle size of the secondary particles is 30 to 200 / ⁇
- the inert gas melting method (measurement device: LECO RH-404 (hydrogen ), TC-4364R (oxygen), measurement conditions: applied voltage 5000 W, analysis time 85 seconds)
- the hydrogen concentration in the powder was 56 ppm
- the oxygen concentration was 600 ppm.
- the average particle size of the primary particles was determined using an electron micrograph (5,000 times).
- FIG. 4 shows the particle structure of this Ta powder when observed at a high magnification.
- FIG. 5 shows the particle structure of the Ta powder shown in FIG. 4 when observed at a high magnification.
- Sn powder (80% having a particle size of 20 ⁇ m or less) atomized with nitrogen gas was prepared.
- the oxygen concentration in the Sn powder at this time was measured by the same method as above, and was 3D at 600 ppm.
- the resulting molded article had an outer diameter: 50 mm, inner diameter: is inserted into the 30 mm Nb- 7. 5 mass 0/0 Ta alloy sheet in over scan, more sheath outer diameter: 65 mm, inner diameter: 55 mm Inserted into an extruded billet made of oxygen-free copper.
- the extruded billet was extruded by a hydrostatic extruder, and then extruded by a die drawing to a wire diameter of lmm.
- This wire is heat-treated at 700 ° C for 10 hours in a vacuum to generate NbSn.
- Example 1 an intermetallic compound powder was prepared in the same manner as in Example 1, except that the EB dissolved powder shown in Fig. 2 having an average particle size of 325 mesh or less (45 ⁇ m or less) was used as the Ta powder. .
- the amount of powder that passed through a 150 m mesh was about 60%. there were.
- Example 1 a powder obtained by a Na reduction method as a Ta powder and having a hydrogen concentration of 1500 ppm and an oxygen concentration of 4000 ppm was prepared. Melt diffusion treatment was started using this Ta powder, but at a temperature of about 500 ° C, the furnace pressure increased due to the release of hydrogen. Heating was stopped for the safety of the heat treatment furnace. Thereafter, when the temperature decreased, the degassing stopped. After the pressure was recovered, the heat treatment was restarted, but the degassing temperature again increased around 500 ° C. Thereafter, the same process was repeated for 10 hours. In the end, it took three times as long as the setting of 5 hours, 15 hours for the treatment temperature to rise to 950 ° C.
- Sn powder a powder obtained by a water atomization method (having a particle size of 75 ⁇ m and passing through a mesh) was prepared. The oxygen concentration of this powder was 4000 ppm. After the Sn powder was mixed with the Ta powder in the same manner as in Experimental Example 1, the same heat treatment (melt diffusion treatment) was performed. The obtained compound powder is ground, the results analyzed by X-ray diffraction, the residual amount of Sn in the flour weekend 11 ⁇ 9 mass 0/0 very variation magnitude force ivy.
- the obtained intermetallic compound powder was processed into a wire in the same manner as in Experimental Example 1 and then subjected to a heat treatment to obtain a superconducting wire, and the critical current was measured.
- the critical current density was 450 ⁇ 150 AZmm 2 , and the average value was lower than that of Experimental Example 1 and the dispersion was very large.
- the present invention is not limited to this method. That is, a mixed powder of at least one metal powder selected from Ta powder and Nb powder and Sn powder can be used as a raw material powder, and this can be filled in the sheath. Even if such a raw material powder is used, there is no problem in the reactivity of Nb and Sn in the sheath when NbSn is generated by heat treatment.
- the average particle size of the primary particles of the Ta powder or Nb powder used in the present invention is preferably 20 m or less. Obtained ones are mentioned. Also, it is preferable to use Ta powder or Nb powder having a hydrogen concentration of 100 ppm or less and an oxygen concentration of 3000 pm or less! [0049] On the other hand, it is preferable to use a Sn powder having an oxygen concentration of 2000ppm or less. Examples of such Sn powder include those generated by inert gas atomization.
- the raw material powder may further contain Cu as a constituent element.
- at least one metal powder selected from Ta powder and Nb powder and Sn powder are mixed, heat-treated and pulverized to obtain a Ta—SnS compound powder or an Nb—Sn compound.
Abstract
Description
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/596,470 US7459030B2 (en) | 2004-05-25 | 2005-05-17 | Manufacturing method of Nb3Sn superconductive wire using powder technique |
EP05744120A EP1750287A1 (en) | 2004-05-25 | 2005-05-17 | METHOD FOR PRODUCING Nb<sb>3</sb>Sn SUPERCONDUCTIVE WIRE BY POWDER PROCESS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2004-155254 | 2004-05-25 | ||
JP2004155254 | 2004-05-25 |
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WO2005117032A1 true WO2005117032A1 (ja) | 2005-12-08 |
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PCT/JP2005/008970 WO2005117032A1 (ja) | 2004-05-25 | 2005-05-17 | 粉末法Nb3Sn超伝導線材の製造方法 |
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US (1) | US7459030B2 (ja) |
EP (1) | EP1750287A1 (ja) |
WO (1) | WO2005117032A1 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US7459031B2 (en) | 2004-09-15 | 2008-12-02 | Kabushiki Kaisha Kobe Seiko Sho | Method for producing Nb3Sn superconductive wire material using powder process |
US8832926B2 (en) * | 2008-08-08 | 2014-09-16 | Supramagnetics, Inc. | Method of manufacturing superconductor wire |
EP2236634B1 (en) | 2009-04-01 | 2016-09-07 | Bruker BioSpin AG | Sn based alloys with fine compound inclusions for Nb3Sn superconducting wires |
TWI685391B (zh) * | 2016-03-03 | 2020-02-21 | 美商史達克公司 | 三維部件及其製造方法 |
DE102019000906A1 (de) | 2019-02-08 | 2020-08-13 | Taniobis Gmbh | Pulver auf Basis von Niobzinnverbindungen für die Herstellung von supraleitenden Bauteilen |
DE102019000905A1 (de) * | 2019-02-08 | 2020-08-13 | Taniobis Gmbh | Pulver auf Basis von Niobzinnverbindungen für die Herstellung von supraleitenden Bauteilen |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5269296A (en) * | 1975-12-06 | 1977-06-08 | Agency Of Ind Science & Technol | Manufacture of superconductor wire |
JPH04141916A (ja) * | 1990-10-02 | 1992-05-15 | Furukawa Electric Co Ltd:The | Nb↓3Sn化合物超電導線材の製造方法 |
JP2003187654A (ja) * | 2001-12-14 | 2003-07-04 | Kobe Steel Ltd | Nb▲3▼Sn超電導線材の製造方法 |
Family Cites Families (1)
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JP4728024B2 (ja) * | 2005-03-24 | 2011-07-20 | 株式会社神戸製鋼所 | 粉末法Nb3Sn超電導線材の製造方法 |
-
2005
- 2005-05-17 WO PCT/JP2005/008970 patent/WO2005117032A1/ja not_active Application Discontinuation
- 2005-05-17 EP EP05744120A patent/EP1750287A1/en not_active Withdrawn
- 2005-05-17 US US11/596,470 patent/US7459030B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5269296A (en) * | 1975-12-06 | 1977-06-08 | Agency Of Ind Science & Technol | Manufacture of superconductor wire |
JPH04141916A (ja) * | 1990-10-02 | 1992-05-15 | Furukawa Electric Co Ltd:The | Nb↓3Sn化合物超電導線材の製造方法 |
JP2003187654A (ja) * | 2001-12-14 | 2003-07-04 | Kobe Steel Ltd | Nb▲3▼Sn超電導線材の製造方法 |
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Publication number | Publication date |
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US7459030B2 (en) | 2008-12-02 |
EP1750287A1 (en) | 2007-02-07 |
US20070175543A1 (en) | 2007-08-02 |
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