EP0016961B1 - Procédé de fabrication d'un matériau composite à base de fibres supraconductrices par métallurgie des poudres - Google Patents

Procédé de fabrication d'un matériau composite à base de fibres supraconductrices par métallurgie des poudres Download PDF

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Publication number
EP0016961B1
EP0016961B1 EP80100955A EP80100955A EP0016961B1 EP 0016961 B1 EP0016961 B1 EP 0016961B1 EP 80100955 A EP80100955 A EP 80100955A EP 80100955 A EP80100955 A EP 80100955A EP 0016961 B1 EP0016961 B1 EP 0016961B1
Authority
EP
European Patent Office
Prior art keywords
powder
oxygen
component
components
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80100955A
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German (de)
English (en)
Other versions
EP0016961A1 (fr
Inventor
Hans Wilhelm Prof. Dr. Bergmann
Rüdiger Dr. Bormann
Herbert C. Prof.Dr. Freyhardt
Barry Leslie Prof. Dr. Mordike
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BORMANN RUDIGER DR
Mordike Barry L Profdr
Original Assignee
BORMANN RUDIGER DR
Mordike Barry L Profdr
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BORMANN RUDIGER DR, Mordike Barry L Profdr filed Critical BORMANN RUDIGER DR
Publication of EP0016961A1 publication Critical patent/EP0016961A1/fr
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Expired legal-status Critical Current

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Classifications

    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
    • 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
    • C22C1/0425—Copper-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • 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
    • Y10S505/80—Material per se process of making same
    • Y10S505/801—Composition
    • Y10S505/807—Powder
    • 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
    • Y10S505/80—Material per se process of making same
    • Y10S505/815—Process of making per se
    • Y10S505/823—Powder metallurgy

Definitions

  • the invention relates to a process for the powder metallurgical production of a superconducting fiber composite material deformed in at least one dimension from at least two starting powder components, at least one of which is contaminated in volume or on the surface with oxygen or an oxygen compound, and wherein at least one starting powder component is a body-centered cubic component Metal, especially niobium or vanadium, is used.
  • two starting powder components preferably two metal powders
  • two metal powders are mixed, compacted, extruded and drawn out to form wires.
  • This fiber composite is deformed in two dimensions. If the composite material is deformed in only one dimension, the powder particles are drawn out into unrelated bands.
  • the two starting powder components are generally mixed, compacted, sintered and then subsequently subjected to the shaping process in which the powder grains are drawn out into long fibers.
  • the reaction with atmospheric oxygen and / or during the production process of the powder interstitially dissolves the volume and / or binds it to the surface as a corresponding oxide.
  • the interstitially dissolved oxygen increases both the hardness of the powder of the starting powder component and the critical temperature of the ductile-brittle transition.
  • the invention has for its object to develop the method of the type described above so that a ductile superconducting fiber composite material can be produced.
  • the ductility of the starting powder components should be matched to one another in a simple manner.
  • this is achieved in that one or more comparatively less noble additional components with a comparatively greater enthalpy of binding for the oxygen in powder form or as an alloy additive are added to the starting powder components and the oxygen is bound to this additional component by an internal solids reduction.
  • the invention thus turns away from the prior art, according to whichever attempts were made to get the oxygen out of the composite material or to prevent the diffusion of further oxygen during the individual processing steps as far as possible.
  • the invention binds the interstitially dissolved oxygen and / or the oxygen adsorbed on the surface to the additional component by an internal reduction in solids.
  • the oxygen then remains in the composite material. Since the oxygen is no longer interstitially dissolved, as an oxide of the additional component it can no longer have a disadvantageous effect on the ductility of the starting powder components, in particular those with the body-centered cubic lattice.
  • the additional component which has a comparatively higher enthalpy of binding to the oxygen, enables successful and complete purification of the starting powder component (s) from oxygen.
  • the reduction in solids is generally carried out at elevated temperature, this process taking place during the annealing treatment during sintering as an internal reduction in solids. A renewed reaction of the cleaned starting powder components with atmospheric oxygen is avoided.
  • the amount of the additional component is added in a small proportion, the proportion advantageously being so small that the composite material is only insignificantly dispersion-cured.
  • the reduction in solids is carried out in the volume of the mixture of starting powder components and the additional component.
  • the method according to the invention primarily impresses with the simplicity of producing a superconducting fiber composite material, in particular with high density (extremely) thin fibers and a high strength associated therewith. In particular, this applies to materials that, due to their high affinity for oxygen, have so far not been able to be converted into a fiber structure by deformation.
  • Lanthanum, a lanthanide, calcium, beryllium, magnesium, lithium, hafnium, titanium, zirconium and / or aluminum can be used as one or more additional components. Particularly good results are achieved if copper and the cubic body-centered niobium are used as the starting powder components and 0.5 to 2.0% by weight aluminum powder is used as the additional component. Excellent properties were achieved if copper and the cubic body-centered vanadium were used as the starting powder components and 2 to 10% by weight of copper-calcium powder as the additional component.
  • a niobium-copper fiber composite material is produced.
  • Commercial niobium powder (grain size ⁇ 20 ⁇ m) and copper powder as starting powder components are mixed in a weight ratio of 1: 4 with the addition of 0.5 to 2.0% by weight aluminum powder (grain size ⁇ 10 ⁇ m) and at approx. 1050 ° C. extruded.
  • the aluminum reacts with the powder metallurgically introduced oxygen to form Al z 0 3 , whereby the microhardness H v of the niobium powder is reduced from 3500 to 1000 to 1200 N / mm 2 .
  • Excess aluminum dissolves substitutionally in the copper. This balances the hardness and ductility of the niobium and copper.
  • the composite material can then be cold-formed (rolling, hammering, wire drawing) into a band-shaped or a fiber structure.
  • fiber thicknesses of less than 100 nm are achieved. A breakage of the fibers during the deformation is not observed.
  • magnesium powder or calcium alloy powder can also be used.
  • a vanadium-copper fiber composite material is to be produced.
  • vanadium powder (grain size ⁇ ZO, um) is mixed with copper powder in a ratio of 1: 2 and 2 to 10% by weight of copper-calcium powder is added. It is then extruded at 1000 ° C, the oxygen content in Vanadium is reduced from approximately 3 at% to less than 0.1 at%. Unoxidized calcium is excreted as CugCa. The subsequent deformation of the structure then leads to a vanadium-copper fiber composite wire.
  • Aluminum and / or magnesium powder can also be used here as an additional component.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Claims (6)

1. Procédé de fabrication par métallurgie des poudres d'un matériau composite à base de fibres supraconductrices déformé au moins suivant une dimension, à partir d'au moins deux constituants pulvérulents de départ, dont l'un au moins est pollué dans le volume ou à la surface par de l'oxygène ou par un composé oxygéné, un métal cubique centré, notamment du niobium ou du vanadium, étant utilisé comme au moins l'un des constituants pulvérulents de départ, caractérisé en ce qu'il consiste à ajouter aux constituants pulvérulents de départ un ou plusieurs constituants d'addition comparativement non nobles, ayant une enthalpie de liaison pour l'oxygène comparativement plus grande, et se présentant sous la forme d'une poudre ou comme additif d'alliage à l'un ou à plusieurs des constituants pulvérulents de départ, et à fixer l'oxygène sur ce constituant d'addition par une réduction interne en phase solide.
2. Procédé suivant la revendication 1, caractérisé en ce qu'il consiste à ajouter le constituant d'addition quantitativement en une proportion moindre.
3. Procédé suivant la revendication 1 et 2, caractérisé en ce qu'il consiste à effectuer la réduction en phase solide dans le volume du mélange des constituants pulvérulents de départ et du constituant d'addition.
4. Procédé suivant les revendications 1 à 3, caractérisé en ce qu'il consiste à utiliser, comme l'un ou comme plusieurs des constituants d'addition, du lanthane, un lanthanide, du calcium, du béryllium, du magnésium, du lithium, de l'hafnium, du titane, du zirconium et/ou de l'aluminium.
5. Procédé suivant les revendications 1 à 3, caractérisé en ce qu'il consiste à utiliser, en plus du niobium cubique centré, comme autre constituant de départ, du cuivre, ainsi que comme constituant d'addition, de 0,5 à 2,0% en poids de poudre d'aluminium.
6. Procédé suivant les revendications 1 à 3, caractérisé en ce qu'il consiste à utiliser, en plus du vanadium cubique centré, comme autre constituant de départ, du cuivre, ainsi que comme constituant d'addition, de 2 à 10% en poids de poudre de cuivre et de calcium.
EP80100955A 1979-03-09 1980-02-26 Procédé de fabrication d'un matériau composite à base de fibres supraconductrices par métallurgie des poudres Expired EP0016961B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2909290A DE2909290C2 (de) 1979-03-09 1979-03-09 Verfahren zur pulvermetallurgischen Herstellung eines supraleitenden Faserverbundmaterials
DE2909290 1979-03-09

Publications (2)

Publication Number Publication Date
EP0016961A1 EP0016961A1 (fr) 1980-10-15
EP0016961B1 true EP0016961B1 (fr) 1984-02-08

Family

ID=6064945

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80100955A Expired EP0016961B1 (fr) 1979-03-09 1980-02-26 Procédé de fabrication d'un matériau composite à base de fibres supraconductrices par métallurgie des poudres

Country Status (3)

Country Link
US (1) US4336065A (fr)
EP (1) EP0016961B1 (fr)
DE (1) DE2909290C2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3531770A1 (de) * 1985-09-06 1987-03-19 Kernforschungsz Karlsruhe Multifilament-supraleiterdraehte, bestehend aus mit kupfer oder mit kupfer-legierung umgebenen filamenten aus nb(pfeil abwaerts)3(pfeil abwaerts)sn oder v(pfeil abwaerts)3(pfeil abwaerts)ga mit zusaetzen sowie verfahren zu deren herstellung
DE3531769A1 (de) * 1985-09-06 1987-03-19 Kernforschungsz Karlsruhe Verfahren zur herstellung von multifilament-supraleiterdraehten aus nb(pfeil abwaerts)3(pfeil abwaerts)sn- oder v(pfeil abwaerts)3(pfeil abwaerts)ga-filamenten, eingebettet in einer cu- oder cu-legierungs-matrix, welche metallische zusatzelemente enthalten, mit vorbestimmten supraleitenden eigenschaften
US4952554A (en) * 1987-04-01 1990-08-28 At&T Bell Laboratories Apparatus and systems comprising a clad superconductive oxide body, and method for producing such body
US5264293A (en) * 1992-01-02 1993-11-23 General Electric Company Composite structure with NbTiHf alloy matrix and niobium base metal
US5277990A (en) * 1992-01-02 1994-01-11 General Electric Company Composite structure with NbTiAl and high Hf alloy matrix and niobium base metal reinforcement
US5226947A (en) * 1992-02-17 1993-07-13 Wisconsin Alumni Research Foundation Niobium-titanium superconductors produced by powder metallurgy having artificial flux pinning centers
US5304427A (en) * 1992-07-02 1994-04-19 General Electric Company Composite structure with NBTIA1CRHF alloy matrix and niobium base metal reinforcement

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3070440A (en) * 1960-04-27 1962-12-25 Grant Production of dispersion hardened metals
GB1152481A (en) * 1966-03-07 1969-05-21 Ass Elect Ind Copper Alloy Material
FR1473618A (fr) * 1966-03-30 1967-03-17 Sherritt Gordon Mines Ltd Procédé de fabrication d'alliages de nickel et de chrome renforcés par une dispersion d'oxyde réfractaire
US3552954A (en) * 1968-09-20 1971-01-05 Handy & Harman Method of making internally oxidized dispersion hardened copper product
US3807968A (en) * 1969-09-03 1974-04-30 Copper Range Co Products involving copper composition materials and assemblages
US3779714A (en) * 1972-01-13 1973-12-18 Scm Corp Dispersion strengthening of metals by internal oxidation
DE2346179A1 (de) * 1973-09-13 1975-06-26 Siemens Ag Verbundmetall als kontaktwerkstoff fuer vakuumschalter
DE2357733A1 (de) * 1973-11-20 1975-05-22 United States Borax Chem Verfahren zur herstellung von formteilen aus faserverstaerkten, duktilen metallen oder legierungen hiervon
DE2360129A1 (de) * 1973-12-03 1975-06-12 Battelle Institut E V Verfahren zur pulvermetallurgischen herstellung duktiler, supraleitender legierungen auf der basis von metallen mit hoher leitfaehigkeit fuer elektrizitaet und waerme
DE2412022A1 (de) * 1974-03-13 1975-09-25 Krupp Gmbh Verfahren zur herstellung hochwarmfester, dispersionsgehaerteter, aushaertbarer legierungen

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HANDBOOK of Chemistry and Physics, 60th Edition, D-67, D-70, D-72 *
Zeitschrift für Metallkunde, Band 65, Mai 1974, Heft 5, Seiten 395 and 396 *

Also Published As

Publication number Publication date
EP0016961A1 (fr) 1980-10-15
DE2909290A1 (de) 1980-09-11
DE2909290C2 (de) 1984-08-09
US4336065A (en) 1982-06-22

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