US20050016854A1 - Materials fabrication method and apparatus - Google Patents

Materials fabrication method and apparatus Download PDF

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US20050016854A1
US20050016854A1 US10/492,180 US49218004A US2005016854A1 US 20050016854 A1 US20050016854 A1 US 20050016854A1 US 49218004 A US49218004 A US 49218004A US 2005016854 A1 US2005016854 A1 US 2005016854A1
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infiltration
sample
metal
porous
alloy
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George Chen
Derek Fray
Bartiomiej Glowacki
Xiao-Yong Yan
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Cambridge University Technical Services Ltd CUTS
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Assigned to CAMBRIDGE UNIVERSITY TECHNICAL SERVICES LIMITED reassignment CAMBRIDGE UNIVERSITY TECHNICAL SERVICES LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEN, GEORGE ZHENG, FRAY, DEREK JOHN, GLOWACKI, BARTLOMIEJ ANDRZEJ, YAN, XIAO-YONG
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/402—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase

Definitions

  • microstructional requirements for such materials are very demanding and many approaches and many alloys or compounds have been developed to address the problems of improving materials performance, including mechanical and electrical performance for example, and ease and cost of fabrication.
  • Nb 3 Al which forms an A15 superconducting phase and, by way of illustration, methods for fabricating this material include the following.
  • the fabrication processes can be considered in three groups: low-temperature, high temperature and transformation processing.
  • an A15 Nb 3 Al strand is processed by first making the final-size strand, with the constituents subdivided, and then heat-treating it to form the A15 phase.
  • Low temperature ( ⁇ 1000 C) processes ensure that the grain size of Nb 3 Al does not become too coarse because the Nb/Al constituents directly react with diffusion to suppress Nb 3 Al grain growth. But, at low temperatures, there is a deviation from A15 stoichiometry, thus affecting high-field properties, especial J c . Low temperature processes include the following.
  • Clad chip extrusion (CCE)—A three-layered clad foil, of Al/Nb/Al, is cut into square chips, and then filled into a can in order to be extruded.
  • J c versus magnetic field curves are very similar for all of these processes. JR may have a slight advantage for producing long piece strands.
  • Nb 3 Al phase will not be completely stoichiometric.
  • high temperatures >1800 C
  • a diffusion reaction of Nb/Al composites with laser or electron-beam irradiation allows stoichiometric A15 phase formation.
  • Annealing at ⁇ 700 C improves long range order, and so better T c and H c2 .
  • high temperatures will cause very coarse grains in the conductor, thereby destroying low field properties.
  • the invention provides a method and an apparatus for fabricating materials as defined in the appended independent claims. Preferred or advantageous features of the invention are set out in dependent sub-claims.
  • the invention uses a process for extracting metals and alloys from solid compounds by direct electrochemical reduction, or electrodecomposition, in molten salt, known as the Fray-Farthing-Chen Cambridge process (FFC), as one of a series of steps to fabricate a material.
  • FFC Fray-Farthing-Chen Cambridge process
  • the FFC process is described in the present applicant's earlier International patent application PCT/GB99/01781 which is incorporated herein by reference.
  • the FFC process allows the treatment of a solid material, which may be a compound between a metal (or semi-metal) and a substance (such as an anionic species), or a solid solution of the substance in the metal, by electrodecomposition in a molten salt to remove the substance from the solid material. On completion of the process, the solid material has been converted to the metal.
  • the solid material comprises more than one metal, being for example a mixture of metal compounds, or a mixture of a metal and a metal compound, or comprises a solid solution of metal compounds, then on completion of the process an alloy or intermetallic compound of the metals is formed.
  • the product of the FFC process is typically porous and, in the method of the present invention, is then infiltrated with an element, metal or alloy, typically as a liquid, to form a material which can be used or further processed to fabricate a product.
  • the invention may be particularly efficacious for fabricating superconductors.
  • the FFC process is performed on a preform comprising a mixture of powdered Nb 2 O 5 and TiO 2 , a porous sample of NbTi alloy is produced. This can then be infiltrated with molten Al to form a material which can be further processed, for example by deformation and heat treatment, to form a high-performance superconductor, advantageously at lower cost than for conventional methods.
  • the FFC process is performed on a preform comprising a mixture of powdered Nb and Sn oxides. A Nb 3 Sn superconductor can then be fabricated.
  • the invention may advantageously provide a method having four steps as follows for fabricating Nb-based superconductors:
  • the method of the invention envisages any suitable starting material or materials and not only Nb and Al.
  • the invention relates particularly to steps 1 and 2 of the list above and that steps 3 and 4 may be replaced by any appropriate superconductor fabrication techniques.
  • the invention is not limited to the field of superconductor fabrication but relates primarily to the technique of infiltrating a porous material formed by the FFC process.
  • the FFC process is very flexible and can produce a wide range of metals, semi-metals, alloys and intermetallic compounds, including materials which are difficult to fabricate in other ways.
  • the additional novel step of infiltrating a product of the FFC process, which is typically porous, with a metal or other material may advantageously allow the fabrication of a wide variety of novel and useful materials compositions and microstructures.
  • the infiltration step may be carried out ex-situ or, preferably, in-situ.
  • the FFC process can produce a porous alloy or intermetallic immersed in a molten salt.
  • the molten salt is contained in a bath which also contains the molten material for infiltration.
  • the infiltration material will usually be denser than the salt, in which case the salt will float on the infiltration material.
  • the porous sample can then move directly from the salt into the infiltration material, which can displace the molten salt and infiltrate the porous sample.
  • the porous sample can move directly from the salt to the infiltration material, advantageously avoiding contact with any other substances.
  • the porous sample may be immersed in the infiltration material by moving the interface between the salt and the infiltration medium rather than by moving the porous sample.
  • the bath containing the salt may be flooded with infiltration material to displace the salt, or where the bath contains both salt and infiltration material, the bath may be moved, rather than the porous sample.
  • the molten infiltration material In ex-situ infiltration the molten infiltration material is held in a separate bath from the molten salt and the porous sample moves from one bath to the other for infiltration. If this is done in an oxidising atmosphere, disadvantageous oxidation of the porous sample may occur. An inert atmosphere may be used to alleviate this problem but nevertheless contamination of the porous sample may be more likely than with the in-situ method.
  • the porous sample is withdrawn from the molten salt and allowed to cool, preferably in an inert atmosphere or in vacuum above the molten salt. As the sample is withdrawn, much or all of the salt within pores in the sample is retained and then solidifies. The sample is then transferred to a pool of molten infiltration material, where it is immersed and the salt melts and is displaced by the infiltration material to infiltrate the sample.
  • This implementation has the advantage that the solidified salt in the pores of the sample during transfer to the immersion material helps to protect the sample surface from contamination or oxidation.
  • the infiltration material wets the FFC product better than the molten salt, it may advantageously substantially entirely displace the salt from the porous FFC product.
  • molten salts wet metals relatively poorly and so, where the FFC product is metallic and the infiltration material is also metallic, the infiltration material will tend to wet the FFC product more strongly than the molten salt.
  • One method for this is to pump the molten salt out of the porous sample after or as it is immersed in the infiltration material.
  • a second method which may be combined with the first, is to vibrate or agitate the porous sample or the infiltration material, for example by using an ultrasonic transducer.
  • FIG. 1 illustrates an electrolytic cell for carrying out the FFC process
  • FIG. 2 illustrates the infiltration and subsequent steps in a first method embodying the invention
  • FIG. 3 is a micrograph of a sample of porous Nb alloy following the FFC process
  • FIG. 4 is a micrograph of a sample of Nb alloy following infiltration
  • FIG. 5 is a micrograph of a Nb—Al—Ge(X) wire following mechanical reduction and diffusion treatment
  • FIG. 6 is a plot of AC susceptibility against temperature for Nb and NbTi rods embodying the invention.
  • FIG. 7 is a plot of AC susceptibility against temperature for reduced Nb 2 O 5 —SnO 2 rods embodying the invention.
  • FIG. 8 illustrates a cell for in-situ infiltration according to an embodiment of the invention.
  • FIG. 9 illustrates a second stage in the in-situ infiltration method using the cell of FIG. 8 ;
  • FIG. 10 is an element distribution plot for an infiltrated pellet of niobium oxide.
  • the electrochemical reduction route of the FFC process may advantageously be a much easier, quicker and cheaper way to extract many metals and alloys than established metallurgical routes.
  • a schematic of such a process is presented in FIG. 1 .
  • FIG. 1 shows an apparatus for making the binary alloy NbTi. It comprises a cell 2 containing molten CaCl 2 4. A graphite anode 6 and a rod-shaped preform 8 of mixed Nb 2 O 5 and TiO 2 are immersed in the salt. The preform is supported on and electronically connected to a Kanthal wire 10 . The preform is made by mixing powdered Nb 2 O 5 and TiO 2 in the desired proportion, slip casting and optionally partially sintering the mixture.
  • a polymer binder may be added to improve the slip-casting process and the polymer then burned off.
  • a prefabricated polymer matrix may be used to make the preform. In this case the polymer matrix is infiltrated with metal oxide powders and then the polymer is burned off.
  • the final product of the FFC process in the embodiment is a porous, rod-shaped, metallic sponge of NbTi alloy, as shown in FIG. 3 .
  • Rapid oxidation of the Nb-based porous rod normally takes place after its removal from the chloride bath and may have a detrimental effect on its surface quality and any subsequent processing. Therefore a different approach is proposed to provide better infiltration conditions, using either in-situ or ex-situ infiltration as described below.
  • the degree of porosity of the final percolative network of the Nb-based alloy sponge depends on the density of the oxide preform and on the initial preparation technique of the prefabricated oxide. For example, preforms which are sintered show a significant shrinkage (increased density) and greatly increased strength in comparison with those prepared by slip casting only.
  • the metallic product of the electrochemical reduction (for NbTi or other materials) is soft and porous, without structural defects or secondary phases, it can not be regarded as a high critical current density, J c , superconducting material.
  • the invention may thus advantageously provide new techniques that allow manufacture of complex compositional superconducting alloy rods by ex-situ and in-situ infiltration processes.
  • FIG. 2 A schematic representation of an embodiment of the process following the fabrication of the FFC process alloy sponge is shown in FIG. 2 , which shows the steps of infiltration 50 , here in a Sn/Ga/Al infiltrant bath 52 , cladding 54 , mechanical reduction 56 and diffusion processing 58 in a furnace 60 .
  • FIG. 2 relates to (Nb, X) 3 (Sn, Al, Z) wire processing, using porous (Nb,X) rod fabricated using the FFC process, for example.
  • a NbTi alloy was formed by direct electrochemical reduction to form an alloy sponge, or rod-shaped sample. Its microstructure is shown in cross-section in FIG. 3 .
  • the Nb-based alloy rod is immersed in a bath of molten Sn or Al-based alloy maintained at a temperature above melting. Lower temperatures are preferred in order to prevent the extensive, very often rapid, formation of brittle intermediate phases which could impair the ductility of the composite infiltrated material.
  • the microstructure of the infiltrated alloy sponge is shown in FIG. 4 .
  • the final products of reducing Nb-oxide-based oxide mixtures in the FFC process typically have pore sizes in the range of 2-20 ⁇ m
  • special care should be taken to ensure that the Nb-based sponge surface is as clean and pure as possible to enable complete infiltration of the porous rod, efficient wetting by the infiltrating metal or alloy such as Sn, Al etc. and finally minimisation of superconductor filament damage caused by the formation of hard Nb 2 O 5 (or even of more complex insulating compounds) on the sponge surface during removal of the metallic Nb-based rod from the chloride bath.
  • the oxygen content in the Nb can reach 2%- 3 at. %, which is about the solubility limit at the extrusion temperature used later in processing.
  • Oxygen adsorbed at the surface of the particles in the sponge may also diffuse into the Nb, increasing its microhardness to 3500 MNm ⁇ 2 .
  • the plastic deformation of the composite may then not be uniform because of severe solution hardening of the Nb, mainly due to interstitial oxygen.
  • a successful co-deformation of Nb and Sn particles requires sufficient reduction of the oxygen content in the Nb. If the oxygen content in the Nb is reduced to 0.1 at % the microhardness of the Nb matrix drops to ⁇ 1200 MNm ⁇ 2 , which is about the value of the surrounding Cu matrix in which the Nb material is typically subsequently encased and which is used for cryostability.
  • ex-situ infiltration can be used to fabricate superconductors but care needs to be taken to avoid deleterious oxide formation, which may require additional processing steps and add to the complexity of the method.
  • a variant of ex-situ infiltration aims to address these concerns.
  • the porous metal or alloy sponge is withdrawn from the molten salt using a control and positioning system until it is held in an inert atmosphere or in vacuo above or near the salt bath. If wetting of the metal by the salt is sufficient, the pores in the sponge remain filled with molten salt, and the sponge can be cooled to solidify the salt. The sponge surface is thus protected against contamination or oxidation by the presence of the solid salt and can be transferred to an infiltration bath without damage. On immersion in the infiltration bath, the salt melts and is displaced by the immersion material.
  • FIGS. 8 and 9 illustrate the technique of in-situ infiltration.
  • a cell 20 contains molten salt 22 floating above a molten metal alloy 24 held in an extended lower portion 26 of the cell.
  • a NbTi based superconductor to carry out the FFC process, a Nb 201 /TiO 2 preform 28 and a graphite anode 30 are immersed in the molten salt, which is CaCl 2 .
  • the preform is supported on a tubular Kanthal support 32 .
  • various methods may be used to encourage the full metal infiltration of the porous Nb-based rod.
  • One of these is to pump out or suck out the molten CaCl 2 from the rod. This can be achieved by pumping the salt through the tubular Kanthal support shown in FIGS. 8 and 9 .
  • sucking will be very effective and any excess of the molten metal within the core of the sample or in the Kanthal support can be easily removed after infiltration and replaced with internal cryogenically stabilising composite such as Cu with a protective Ta diffusion barrier.
  • an ultrasonic device mechanically coupled to the rod or its support, or to the bath of infiltration material, may also be used to accelerate the infiltration process.
  • rods After the infiltration process, rods would be machined to the desired shape and inserted in subsequent tubes 62 to serve as a diffusion barrier and for electrical and thermal stabilisation. This is the cladding step 54 of FIG. 2 . Although an elevated temperature during the infiltration stage may produce some A15 phase, it may be desired to subject the infiltrated rod or tape to a substantial reduction in thickness by cold rolling 56 prior to the final diffusion formation 58 of the intermetallic A15 layers in the conductor.
  • microstructure control An important aspect of superconductor fabrication is microstructure control.
  • Use of the FFC process as a step in fabrication enables an element of control through control of the particle size of the powder used to make the preform, densification of the preform through sintering, and the temperature and other electrolysis parameters at which the electrodecomposition is performed.
  • the temperature of the furnace was lowered to 690° C.
  • the cathode was then immediately lowered into the molten aluminium underneath the molten salt.
  • the cathode was removed from the crucible, cooled first in the upper region of the Inconel reactor, and then removed from the reactor and further cooled in air. It was seen that the pellet was completely covered in aluminium.
  • the pellet was broken into two halves, and the cross section examined by SEM (scanning electron microscopy) and EDX (energy-dispersive x-ray analysis). It was observed that the pellet contained two different phases.
  • the outer layer of the pellet was about 400 micrometres in thickness and relatively dense, but the central part was porous.
  • EDX analysis revealed that, as shown in FIG. 10 , the outer layer was composed mainly of niobium and aluminium with about 20 at % oxygen, but the central part was of niobium and calcium with 58 at % oxygen (Nb 2 O 5 contains 71 at % oxygen). The calcium content was also much lower in the outer layer than in the central part.
US10/492,180 2001-10-10 2002-10-10 Materials fabrication method and apparatus Abandoned US20050016854A1 (en)

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GBGB0124303.9A GB0124303D0 (en) 2001-10-10 2001-10-10 Material fabrication method and apparatus
GB0124303.9 2001-10-10
PCT/GB2002/004603 WO2003031665A2 (en) 2001-10-10 2002-10-10 Superconductor materials fabrication method using electrolytic reduction and infiltration

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US20080304975A1 (en) * 2007-06-05 2008-12-11 Rolls-Royce Plc Method for producing abrasive tips for gas turbine blades
US20100150730A1 (en) * 2008-12-15 2010-06-17 Rolls-Royce Plc Component having an abrasive layer and a method of applying an abrasive layer on a component
CN105903473A (zh) * 2016-04-17 2016-08-31 北京化工大学 一种水滑石前驱体法制备M-Sn金属间化合物的方法及其应用
US20220118512A1 (en) * 2019-02-08 2022-04-21 Taniobis Gmbh Powders based on niobium-tin compounds for producing superconductive components

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US20080169204A1 (en) * 2006-10-25 2008-07-17 Rolls-Royce Plc Method and apparatus for treating a component of a gas turbine engine
US8168046B2 (en) * 2006-10-25 2012-05-01 Rolls-Royce Plc Method and apparatus for treating a component of a gas turbine engine
US20080304975A1 (en) * 2007-06-05 2008-12-11 Rolls-Royce Plc Method for producing abrasive tips for gas turbine blades
US8266801B2 (en) 2007-06-05 2012-09-18 Rolls-Royce Plc Method for producing abrasive tips for gas turbine blades
US20100150730A1 (en) * 2008-12-15 2010-06-17 Rolls-Royce Plc Component having an abrasive layer and a method of applying an abrasive layer on a component
CN105903473A (zh) * 2016-04-17 2016-08-31 北京化工大学 一种水滑石前驱体法制备M-Sn金属间化合物的方法及其应用
US20220118512A1 (en) * 2019-02-08 2022-04-21 Taniobis Gmbh Powders based on niobium-tin compounds for producing superconductive components

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EP1440175A2 (en) 2004-07-28
WO2003031665A3 (en) 2003-05-22
WO2003031665A2 (en) 2003-04-17
BR0213217A (pt) 2004-12-21
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