EP1625598B1 - Verfahren zur herstellung einer elektrisch isolierenden und mechanisch strukturierenden mantelung auf einem elektrischen leiter - Google Patents

Verfahren zur herstellung einer elektrisch isolierenden und mechanisch strukturierenden mantelung auf einem elektrischen leiter Download PDF

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Publication number
EP1625598B1
EP1625598B1 EP04767829A EP04767829A EP1625598B1 EP 1625598 B1 EP1625598 B1 EP 1625598B1 EP 04767829 A EP04767829 A EP 04767829A EP 04767829 A EP04767829 A EP 04767829A EP 1625598 B1 EP1625598 B1 EP 1625598B1
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European Patent Office
Prior art keywords
conductor
ceramic
precursor
heat treatment
forming
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EP04767829A
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English (en)
French (fr)
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EP1625598A1 (de
Inventor
Alexandre Puigsegur
Françoise RONDEAUX
Eric Prouzet
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Commissariat A L'energie Atomique En Centre Nation
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Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique CEA
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    • 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
    • H01B13/06—Insulating conductors or cables
    • H01B13/16—Insulating conductors or cables by passing through or dipping in a liquid bath; by spraying
    • 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
    • H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment

Definitions

  • the present invention relates to a method of manufacturing an electrically insulating and mechanically structuring sheath on an electrical conductor.
  • the invention makes it possible to obtain an electrically isolated conductor that can be used over a wide range of temperatures and more particularly at very low temperatures, less than or equal to 4.2K, corresponding to the operating range of the superconducting magnets used for generate strong magnetic fields.
  • the invention thus applies in particular to the manufacture of such superconducting magnets.
  • Superconductive electromagnets are already known, made from Nb 3 Sn type alloys. Such alloys are capable of producing intense magnetic fields of up to 24 Tesla, which gives them a definite advantage over the NbTi-type alloys usually employed in such electromagnets.
  • Nb 3 Sn make it difficult to implement because, unlike NbTi which is a very ductile and easily extrudable alloy, it is difficult to manufacture multi-filament Nb 3 Sn compounds.
  • Nb 3 Sn is a polycrystalline intermetallic material which, to be formed, must undergo a long heat treatment of up to 3 weeks at temperatures of 600 ° C to 720 ° C under an inert atmosphere. Once treated, it becomes brittle and its superconducting properties are very sensitive to any mechanical deformation.
  • the implementation of the electrical insulation of the cable is particularly difficult because, for this insulation, it is difficult to use a conventional material of organic type. Indeed, such a material is not resistant to a heat treatment during which the temperature exceeds 600 ° C.
  • This document discloses a method of manufacturing an electrically insulating and mechanically structuring sheath on an electrical conductor and proposes the use of a gelled solution, containing an organic binder, for the deposition of a ceramic precursor or directly on the conductor to isolate either on a ribbon serving to surround this conductor.
  • This document describes a method for coating superconductors with an electrical insulator.
  • this process also uses a sol-gel solution requiring oxides and organic solvents, i.e. isopropanol and acetyl-acetone, to form the ceramic precursor.
  • the present invention aims to overcome the above disadvantages.
  • the suspension for forming the ceramic precursor is not a gel but a fluid solution without any organic element.
  • the method which is the subject of the invention leads to a simplification of the compositions used for its implementation and to a clear separation of the phases of elaboration of the isolated conductor, as will be seen later.
  • the clay is selected from the group of smectites and in this group, montmorillonite is preferably selected.
  • the solution comprises, in weight percent, 35% to 50% water, 8% to 15% clay and 35% to 55% glass frit.
  • the conductor is a precursor of a superconductor, in particular Nb 3 Sn, and an overall heat treatment of this conductor provided with the coating is carried out. global heat treatment being able to form the superconductor and the ceramic.
  • the conductor is either a non-superconducting metal or a superconducting metal and a heat treatment of this conductor provided with the coating is carried out, this heat treatment being able to form the ceramic.
  • the step of forming the coating comprises a step of depositing the ceramic precursor on a fiber ribbon and then a step of arranging the ribbon provided with the ceramic precursor around the conductor.
  • the ceramic precursor there is a coating of the ribbon by the ceramic precursor and the fibers may be made of a material selected from type E glass, type C glass, type R glass, type S2 glass pure silica, an alumina and an aluminosilicate.
  • the fiber ribbon is previously desensitized, for example thermally or chemically.
  • the conductor provided with the coating is shaped before the heat treatment step capable of forming the ceramic.
  • the conductor can for example wind this conductor (provided with the coating), before the heat treatment step capable of forming the ceramic.
  • the electrical insulation technique proposed in the present invention makes it possible to deposit a ceramic cladding on an unreacted conductive cable (made of a Nb 3 Sn precursor), before forming a superconducting magnet coil.
  • the ceramic cladding will react simultaneously during the thermal cycle necessary for the formation of Nb 3 Sn superconductor and will thus contribute to the electrical insulation and mechanical cohesion of the coil (structuring function).
  • the phases of preparation of the ceramic precursor, preparation of the ceramic sheath (for example by coating a ribbon of glass fibers) and sheathing of the conductive cable (covering) are distinct.
  • the solution used in the invention for the formation of this precursor has no organic component, especially binder type, to prevent the formation of carbon residues that are known to be harmful to good electrical insulation.
  • This solution is preferably a ternary mixture of a montmorillonite-type clay, glass frit and water which form a ceramic suspension.
  • the montmorillonite used is produced by Arvel SA under the trade name Expans.
  • This clay makes it possible to give the necessary plasticity to the impregnated tape that will be used during the wrapping of the conductive cable (made of a precursor of the Nb 3 Sn alloy). In addition, it allows bending radii of about 2mm for the cladding tape.
  • the glass frit used is manufactured by Johnson & Mattey, under the reference 2495F. Its melting point is 538 ° C.
  • the glass frit is a fuse element that contributes to the cohesion of the ceramic insulation after the heat treatment.
  • the water makes it possible to adjust the viscosity of the suspension.
  • the clay and the glass frit are heated at 100 ° C for 12 hours in an oven to remove any traces of moisture. Then two powders of clay and glass frit are ground separately until a particle size of less than 20 .mu.m is obtained. The glass frit is then mixed with water with a magnetic stirrer.
  • the clay is then incorporated by successive additions, which facilitates the mixing of the whole, then the suspension obtained is again treated with the aid of the ultrasonic gun to obtain a homogeneous mixture.
  • This suspension is then stirred. To do this, in the example described, it is placed on a roller stirrer for 12 hours, in a polyethylene bottle containing twenty or so porcelain balls of diameter 20 mm. Thanks to this stirring technique, a good homogenization of the solution is obtained and the suspension is given a fluid appearance.
  • the reduced viscosity of the mixture is necessary for a good impregnation of the fiberglass ribbon which will be used for the cladding of the conductor.
  • a volume of about 600 milliliters of mixture is constituted for each preparation.
  • the ceramic sheath is made of a glass fiber ribbon which is impregnated with the ceramic suspension described above.
  • the fibers of this ribbon may be type E, C, R or S2 glass. These fibers may equally well be pure silica, alumina or aluminosilicate.
  • the ribbon Before being impregnated, the ribbon undergoes heat treatment - it is maintained at 350 ° C for 12 hours - to eliminate the organic size of the fibers of which it is made.
  • This size is indeed detrimental to good fiber coating by the ceramic suspension and is a source of carbon elements, which can reduce the insulating properties of the ceramic.
  • the coating of the glass fiber ribbon with the ceramic solution is carried out by means of an impregnation bench which is diagrammatically shown in FIG.
  • the desensitized ribbon in the form of a roller 2, is attached to a brake system 4 which allows unrolling the ribbon while keeping a constant tension.
  • Pulleys 6 guide the ribbon through the various components of the impregnation bench. The direction of movement is indicated by the arrow F.
  • the ribbon passes into an impregnating tank 8 containing the ceramic suspension 10. This is kept under stirring, thanks to a magnetic stirrer 12, during the impregnation phase of the ribbon, in order to preserve the homogeneity of the latter and avoid sedimentation problems.
  • the ribbon 2 passes through a scraper system 14 which limits the thickness of the ceramic deposit 16 formed on the ribbon (due to its passage through the ceramic suspension).
  • a drying column 18, heated to 150 ° C, allows complete evaporation of water from the ceramic solution deposited on the ribbon.
  • the sheath, ceramic precursor is completely dry. She is packaged in the form of a roller 20, thanks to a motor 22 which maintains a constant running speed of 20cm per minute.
  • the Rutherford cables are approximately trapezoidal in cross-section and consist of 36 conductive strands which are twisted together and finally made of Nb 3 Sn in the example.
  • These strands are distributed so as to form a flat two-layer conductor, the cross section of which has the following approximate dimensions: 1.3 mm for the short side, 1.6 mm for the long side and 15.1 mm for the width .
  • the ceramic cladding consisting of the glass fiber ribbon impregnated with the ceramic precursor, is wrapped around the Rutherford conductor cable (formed of the Nb 3 Sn precursor), in two layers offset by half a width, as it is see figure 2.
  • references 24, 26, 28 and 30 respectively represent the cable (before the treatment intended to form Nb 3 Sn), the strands of the cable, the first layer of the ribbon and the second layer of the ribbon.
  • the edge of one turn of ribbon is against the edge of the adjacent turn.
  • the first layer 28 is placed first on the cable and the second layer 30 ensures the continuity of the electrical insulation, as seen in Figure 2.
  • this cable After covering the conductor cable by means of the two ceramic cladding layers 28 and 30, this cable is formed into coils according to means known in the state of the art. Then the coils thus obtained from the conductive cable, consisting of the precursor covered with the ceramic sheath, are subjected to a heat treatment under a neutral gas such as argon.
  • a neutral gas such as argon
  • This treatment comprises a slow rise in temperature, at a speed close to 6 ° C. per hour, up to the temperature of 660 ° C., then a plateau at 660 ° C. for 240 hours, then a slow cooling down to the temperature ambient temperature (20 ° C to 23 ° C) in the furnace chamber.
  • This treatment allows the reaction of the precursor cable and obtaining a Nb 3 Sn superconducting material having the desired properties.
  • the glass frit used in the example of the invention has a melting point of 540 ° C. It therefore melts during the heat treatment necessary for the formation of the Nb 3 Sn superconductor (during which the temperature is maintained at 660 ° C.) and thus provides, after cooling to ambient temperature, the electrical insulation and the mechanical cohesion necessary for the applications of the invention, such as the formation of superconducting coils.
  • each coil is cooled to the temperature of liquid helium (4.2K at atmospheric pressure) or that of superfluid helium (temperature below 2.1K under reduced pressure) to superconducting the alloy Nb 3 Sn component conductor which is formed the winding cable.
  • any other clay from the group of smectites can be used.
  • Figure 3 corresponds to a first composition
  • Figure 4 to a second composition, different from the first.
  • Each of these flow curves represents the variations of the stress ⁇ (expressed in Pa) as a function of the shear rate ⁇ (expressed in s -1 ).
  • the low speed movement of the glass ribbon in the ceramic suspension creates low shear rates.
  • the experimental conditions are such that the rheological behavior corresponds to the beginning of the flow curves.
  • composition of the two suspensions is given in Table I below.
  • the clay used for the two suspensions is montmorillonite marketed by Arvel SA under the name Expans.
  • Table 1 Clay % by mass
  • Glass frit % by mass
  • Water % by mass
  • Suspension 1 11.5 46 42.5

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Processes Specially Adapted For Manufacturing Cables (AREA)
  • Insulating Bodies (AREA)
  • Manufacturing Of Electric Cables (AREA)

Claims (12)

  1. Verfahren zur Herstellung einer elektrisch isolierenden und mechanisch strukturierenden Mantelung eines elektrischen Leiters (2), insbesondere eines Leiters aus nicht-supraleitendem Metall, eines Leiters aus supraleitendem Metall oder eines Leiters aus Supraleitervorläufer, wobei dieses Verfahren die folgenden Schritte umfasst:
    - Bildung eines Keramikvorläufers (10) in Form einer flüssigen Lösung, wobei dieser Keramikvorläufer (10) eine Flüssigkeit ist, die durch eine Lösung gebildet wird, die Wasser, Glasfritte und einen Ton, suspendiert in Wasser, umfasst,
    - Bildung eines Überzugs des Leiters mit diesem Keramikvorläufer, und
    - thermische Behandlung dieses Überzugs, wobei diese thermische Behandlung fähig ist, die Keramik aus dem Keramikvorläufer zu bilden,
    wobei dieses Verfahren dadurch gekennzeichnet ist, dass in dem Schritt zur Bildung eines Keramikvorläufers die genannte Flüssigkeit kein organisches Element umfasst.
  2. Verfahren nach Anspruch 1, bei dem der Ton aus der Gruppe der Smektide gewählt wird.
  3. Verfahren nach Anspruch 2, bei dem der Ton ein Montmorillonit ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem die Lösung in Massenanteilen 35% bis 50% Wasser, 8% bis 15% Ton und 35% bis 55% Glasfritte enthält.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem der Leiter (2) Vorläufer eines Supraleiter ist, insbesondere Nb3Sn, und man eine globale thermische Behandlung dieses mit dem Überzug versehenen Leiters durchführt, wobei diese globale thermische Behandlung fähig ist, den Supraleiter und die Keramik zu bilden.
  6. Verfahren nach einem der Ansprüche 1 bis 4, bei dem der Leiter (2) aus nicht-supraleitendem Metall oder aus supraleitendem Metall ist und man eine thermische Behandlung dieses mit dem Überzug versehenen Leiters durchführt, wobei diese thermische Behandlung fähig ist, den Supraleiter und die Keramik zu bilden.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem der Schritt zur Bildung der Mantelung einen Schritt zum Überziehen eines Faserbands mit dem Keramikvorläufer und dann einen Schritt zum Anordnen des mit dem Keramikvorläufer versehenen Bands um den Leiter herum umfasst.
  8. Verfahren nach Anspruch 7, bei dem die Fasern aus einem Material gemacht sind, das ausgewählt wird unter Glas des Typs E, Glas des Typs C, Glas des Typs R, Glas des Typs S2, reinem Siliciumdioxid, einem Aluminiumoxid und einem Aluminiumsilikat.
  9. Verfahren nach einem der Ansprüche 7 und 8, bei dem das Faserband vorher entsensimiert (désensimé) wird.
  10. Verfahren nach Anspruch 9, bei dem das Faserband vorher auf thermische oder chemische Weise antsensimiert (désensimé) wird.
  11. Verfahren nach einem der Ansprüche 1 bis 10, bei dem man den mit dem Überzug versehenen Leiter (2) vor dem zur thermischen Behandlung der Keramik befähigten Schritt ausbildet.
  12. Verfahren nach Anspruch 11, bei dem man den mit dem Überzug versehenen Leiter (2) vor dem zur thermischen Behandlung der Keramik befähigten Schritt aufspult.
EP04767829A 2003-05-19 2004-05-18 Verfahren zur herstellung einer elektrisch isolierenden und mechanisch strukturierenden mantelung auf einem elektrischen leiter Expired - Lifetime EP1625598B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0350158A FR2855313A1 (fr) 2003-05-19 2003-05-19 Procede de fabrication d'une gaine electriquement isolante et mecaniquement structurante sur un conducteur electrique.
PCT/FR2004/050200 WO2004105058A1 (fr) 2003-05-19 2004-05-18 Procede de fabrication d'une gaine electriquement isolante et mecaniquement structurante sur un conducteur electrique.

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EP1625598A1 EP1625598A1 (de) 2006-02-15
EP1625598B1 true EP1625598B1 (de) 2006-10-18

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US (1) US20070042910A1 (de)
EP (1) EP1625598B1 (de)
JP (1) JP2007510257A (de)
CN (1) CN1791949A (de)
AT (1) ATE343212T1 (de)
DE (1) DE602004002867T2 (de)
ES (1) ES2273285T3 (de)
FR (1) FR2855313A1 (de)
WO (1) WO2004105058A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005047938B4 (de) 2005-10-06 2022-01-27 Bruker Biospin Gmbh Supraleitendes Magnetspulensystem mit Quenchschutz
KR100945195B1 (ko) * 2008-08-27 2010-03-03 한국전기연구원 러더퍼드 케이블을 이용한 전류리드
DE102014207373A1 (de) * 2014-04-17 2015-10-22 Siemens Aktiengesellschaft Verfahren zur Herstellung einer elektrischen Spulenwicklung mit einem zweifach zusammenhängenden Bandleiter
CN109509590A (zh) * 2018-12-24 2019-03-22 上海申远高温线有限公司 一种硅橡胶电缆湿法涂滑石粉的专用装置
CN114446536A (zh) * 2022-02-24 2022-05-06 福建师范大学 一种改进的制备Nb3Al超导长线材的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3298936A (en) * 1961-04-17 1967-01-17 North American Aviation Inc Method of providing high temperature protective coatings
US3352009A (en) * 1962-12-05 1967-11-14 Secon Metals Corp Process of producing high temperature resistant insulated wire, such wire and coils made therefrom
US4342814A (en) * 1978-12-12 1982-08-03 The Fujikura Cable Works, Ltd. Heat-resistant electrically insulated wires and a method for preparing the same
DE3168609D1 (en) * 1980-07-15 1985-03-14 Imi Kynoch Ltd Flexible insulation for filamentary intermetallic superconductor wire
US5246729A (en) * 1986-06-30 1993-09-21 United States Of America As Represented By The Secretary Of The Air Force Method of coating superconductors with inorganic insulation
US5587226A (en) * 1993-01-28 1996-12-24 Regents, University Of California Porcelain-coated antenna for radio-frequency driven plasma source
AU5057096A (en) * 1995-04-24 1996-11-07 Rohm And Haas Company Method for forming extruded parts from inorganic material
US6344287B1 (en) * 1997-04-14 2002-02-05 Florida State University High temperature compatible insulation for superconductors and method of applying insulation to superconductors
FR2827699B1 (fr) * 2001-07-20 2007-04-13 Commissariat Energie Atomique Procede de fabrication d'une gaine electriquement isolante et mecaniquement structurante sur un conducteur electrique

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Publication number Publication date
EP1625598A1 (de) 2006-02-15
US20070042910A1 (en) 2007-02-22
FR2855313A1 (fr) 2004-11-26
WO2004105058A1 (fr) 2004-12-02
DE602004002867T2 (de) 2007-05-10
CN1791949A (zh) 2006-06-21
JP2007510257A (ja) 2007-04-19
ES2273285T3 (es) 2007-05-01
DE602004002867D1 (de) 2006-11-30
ATE343212T1 (de) 2006-11-15

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