WO1998043253A1 - Coating of a superconductor - Google Patents

Coating of a superconductor Download PDF

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Publication number
WO1998043253A1
WO1998043253A1 PCT/DK1998/000120 DK9800120W WO9843253A1 WO 1998043253 A1 WO1998043253 A1 WO 1998043253A1 DK 9800120 W DK9800120 W DK 9800120W WO 9843253 A1 WO9843253 A1 WO 9843253A1
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WO
WIPO (PCT)
Prior art keywords
tube
superconducting
metal
metal oxide
coating
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.)
Ceased
Application number
PCT/DK1998/000120
Other languages
Danish (da)
French (fr)
Inventor
Zhenghe Han
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.)
Nordic Superconductor Technologies AS
Original Assignee
Nordic Superconductor Technologies AS
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
Priority to EP98907923A priority Critical patent/EP0970483B1/en
Priority to SK1182-99A priority patent/SK118299A3/en
Priority to AT98907923T priority patent/ATE241205T1/en
Priority to CA002284782A priority patent/CA2284782A1/en
Priority to DE69814842T priority patent/DE69814842T2/en
Priority to NZ337593A priority patent/NZ337593A/en
Priority to JP54091498A priority patent/JP2001516495A/en
Priority to AU66127/98A priority patent/AU727072B2/en
Priority to US09/380,115 priority patent/US6223418B1/en
Application filed by Nordic Superconductor Technologies AS filed Critical Nordic Superconductor Technologies AS
Publication of WO1998043253A1 publication Critical patent/WO1998043253A1/en
Priority to NO994666A priority patent/NO994666D0/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/04—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing coils
    • H01F41/048—Superconductive coils
    • 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
    • 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

  • a method of manufacturing a superconducting length of wire is a method of manufacturing a superconducting length of wire.
  • the present invention relates to a method of manufacturing a superconducting length of wire, comprising at least insertion of a superconducting base material into a tube of metal and subsequent packing or coiling of the metal- lie tube in such a manner that a first part of the outer surface of the tube contacts a second part of the surface of the tube, following which the metal tube filled with the superconducting base material is heated to a temperature close to the melting point temperature of the metal tube so as to form the superconducting phase of the base material.
  • the superconducting material is formed by e.g. a powder material which, after the insertion into the metal tube, does not per se cause the length of wire to become supercon- ducting, but which is activated after the subsequent heat treatment so that the length of wire becomes superconducting.
  • a known solution to this problem is one wherein a ceramic tape is used in the coiling of the length of wire not heat treated yet, said tape being coiled together with the length of wire so that no areas on the length of wire contact other areas on the length of wire during coiling. Subsequent unwinding of the heat treated length of wire may hereby be performed without any risk of the supercon ⁇ ducting length of wire adhering to itself.
  • EP A2 44 144 discloses a method wherein the superconduct ⁇ ing length of wire is provided with an insulating layer consisting of a silicate and another component capable of reacting with said silicate to form a ceramic layer by heating to temperatures above 500 °C, following which the layer is dried and heat treated at the above-mentioned temperature to form the insulating ceramic article.
  • JP 09082146-A it is moreover known from JP 09082146-A to manufacture a superconducting length of wire with a coating of nickel oxide or zirconium oxide by placing the tube of silver filled with the superconducting base material in an outer tube of nickel or zirconium, following which the two tubes are drawn to a reduced diameter for a substantially round wire which is subsequently rolled and heat-treated so as to form the superconducting phase in the supercon- ducting base material, said outer tube forming a layer of nickel oxide or zirconium oxide.
  • the resulting tube may very well be wound into e.g. a coil without the outer coatings adhering to each other in an optional heat treatment, but the process clearly requires a relatively accurate process control to ensure that the outer layer of metal oxide has a reasonable uniform thickness, particularly if an outer layer of a very small thickness is desired.
  • a problem of this prior art is thus that the ceramic tape is difficult to handle, or that its thickness causes a coil containing a given length of conductor to be rela- tively large.
  • the object of the present invention is to provide a method of manufacturing a superconducting length of wire of the type stated in the opening para- graph, which does not necessitate the use of a ceramic tape to separate the individual layers of the conductor not heat treated yet in the packing or coiling of it, thereby achieving a method which lends itself for heat treatment of superconducting lengths of wire in a compact coiled or otherwise packed state, following which the superconducting length of wire may be unwound again and be used in a production process.
  • the tube of metal before being packed or coiled, is provided with a liquid coating on at least the first and second parts of the outer surface of the tube, said coating comprising a substantially liquid component which evaporates or burns completely at the temperature at which the su- perconducting phase in the superconducting material is formed, and a powder material suspended in the liquid component and having a melting temperature which is higher than the melting temperature of the metallic tube.
  • the coating applied to the length of wire comprises a ceramic material, in particu ⁇ lar a metal oxide preferably selected from the group: A1 2 0 3 , CR 2 0 3 , Cu x O y , Ni x O y , Zn x O y , Zr x O y , Ta x O y .
  • the coating may advantageously be formed by the application of a metal oxide powder. It may be applied particularly simply as a paint consisting of a liquid medium in which the metal oxide powder is sus- pended.
  • the metal oxide powder is suspended in an amount ensuring that the individual metal oxide particles, when applied to the first and second outer surfaces of the metal tube, are disposed in a density such that metal oxide particles on the first outer surface of the metal tube do not touch the second outer surface of the metal tube, and vice versa.
  • the liquid medium for the suspension of the metal oxide powder may expediently comprise a solvent, such as acetone, alcohol or toluene, admixed with an amount of polymer, such as polyvinyl butyral (PVB) , and polyvinyl butyral is advantageously added in an amount of between 0.1 and 10 per cent by weight, preferably between 1 and 4 per cent by weight, as this provides suitable ad- hesion properties for the liquid medium and the suspended metal oxide powder.
  • a solvent such as acetone, alcohol or toluene
  • polymer such as polyvinyl butyral (PVB)
  • PVB polyvinyl butyral
  • zirconium oxide may preferably be used as the metal oxide powder, but other ceramic powders and particularly metal oxides may be used.
  • Fig. 1 is a basic view which shows a coiled conductor containing superconducting material.
  • Fig. 2 is a basic view which shows a cross-section through the conductor shown in fig. 1 in a first embodiment.
  • Fig. 3 is a basic view which shows a cross-section through the conductor of fig. 1 in a second embodiment.
  • Fig. 1 thus shows a conductor containing superconducting material. As will be seen, the conductor is wound around a core with a view to heat treatment.
  • the wound conductor 1 may be manufactured according to a generally known method by filling a tube 2 with superconducting material 7 and then stretching, drawing or otherwise machining it in order to reduce the cross-sectional dimensions of the tube 2.
  • this manufactur- ing process may comprise a rolling process or other process which provides a conductor in the form of a tape having a desired thickness.
  • Such manufacturing processes are generally known from the literature and will therefore not be described in detail here.
  • the product is a conductor containing a superconducting base material, which subsequently requires a heat treatment to form the superconducting phase in the base material .
  • the conductor Owing to the handling of the conductor, the conductor is coiled or packed into e.g. a coil 1, as shown in fig. 1, and then the heat treatment may be initiated.
  • Fig. 2 thus shows a first embodiment of the invention in which the tube 2 itself contains a superconducting base material, but the surfaces 3 and 4 of the tube are covered by a coating 5 of ceramic material selected from the group of materials having the basic formula M x O, where M is a metal, such as Cu, Ni, Al, Zn, Zr, Sr, Mn, Ta, etc., and where 0 is oxygen.
  • M is a metal, such as Cu, Ni, Al, Zn, Zr, Sr, Mn, Ta, etc., and where 0 is oxygen.
  • the coating 5 may be provided by e.g. applying a paint which comprises the de- sired ceramic material suspended in a liquid, such as a solvent in the form of acetone, alcohol or toluene, ad- mixed with an amount of polymer, such as polyvinyl butyral (PVB) .
  • a paint which comprises the de- sired ceramic material suspended in a liquid, such as a solvent in the form of acetone, alcohol or toluene, ad- mixed with an amount of polymer, such as polyvinyl butyral (PVB) .
  • the ceramic coating 5 may be applied as a powder, or it may be formed by simple oxidation of the material of the tube 2.
  • Fig. 3 shows a second embodiment of the invention in which the tube 2 is filled with rows of filament tubes 6, which are in turn filled with a superconducting base material 7.
  • the conductor shown in fig. 3 is provided with a ceramic coating 5, but here, in contrast to the embodiment shown in fig. 2, the coating is applied so that it covers the entire circumference of the tube 2.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a method of manufacturing a superconducting length of wire, comprising at least insertion of a superconducting base material into a tube of metal, packing or coiling of the metallic tube in such a manner that a first part of the outer surface of the tube contacts a second part of the surface of the tube, heating of the tube filled with the superconducting base material to a temperature close to the melting temperature of the metal tube so as to form the superconducting phase in the base material. In the method, the tube of metal, before being packed or coiled, is provided with a coating on at least the first and second parts of the outer surface of the tube, said coating comprising a material having a melting temperature which is higher than the melting temperature of the metallic tube.

Description

COATING OF A SUPERCONDUCTOR
A method of manufacturing a superconducting length of wire.
The present invention relates to a method of manufacturing a superconducting length of wire, comprising at least insertion of a superconducting base material into a tube of metal and subsequent packing or coiling of the metal- lie tube in such a manner that a first part of the outer surface of the tube contacts a second part of the surface of the tube, following which the metal tube filled with the superconducting base material is heated to a temperature close to the melting point temperature of the metal tube so as to form the superconducting phase of the base material.
This method is normal in the manufacture of superconducting lengths of wire, there being hereby formed a tube having suitable mechanical properties in which the super¬ conducting material is enclosed. In this connection, the superconducting material is formed by e.g. a powder material which, after the insertion into the metal tube, does not per se cause the length of wire to become supercon- ducting, but which is activated after the subsequent heat treatment so that the length of wire becomes superconducting.
However, a problem of the above-mentioned heat treatment is that for practical reasons the conductor not heat treated yet is packed or more expediently coiled so that the length of wire is easier to handle. As a consequence, the subsequent heat treatment of the packed or coiled length of wire may make it impossible to unpack or unwind the length of wire, because the length of wire adheres to itself in the regions where the first area on the length of wire contacts the second area.
A known solution to this problem is one wherein a ceramic tape is used in the coiling of the length of wire not heat treated yet, said tape being coiled together with the length of wire so that no areas on the length of wire contact other areas on the length of wire during coiling. Subsequent unwinding of the heat treated length of wire may hereby be performed without any risk of the supercon¬ ducting length of wire adhering to itself.
EP A2 44 144 discloses a method wherein the superconduct¬ ing length of wire is provided with an insulating layer consisting of a silicate and another component capable of reacting with said silicate to form a ceramic layer by heating to temperatures above 500 °C, following which the layer is dried and heat treated at the above-mentioned temperature to form the insulating ceramic article.
Since the insulating layer will form an insulating sur¬ face which is sticky at said temperatures, this method does not lend itself for heat treatment of superconduct¬ ing lengths of wire which have e.g. been coiled into a coil and which are subsequently to be unwound from said coil and then used in a production.
It is moreover known from JP 09082146-A to manufacture a superconducting length of wire with a coating of nickel oxide or zirconium oxide by placing the tube of silver filled with the superconducting base material in an outer tube of nickel or zirconium, following which the two tubes are drawn to a reduced diameter for a substantially round wire which is subsequently rolled and heat-treated so as to form the superconducting phase in the supercon- ducting base material, said outer tube forming a layer of nickel oxide or zirconium oxide.
The resulting tube may very well be wound into e.g. a coil without the outer coatings adhering to each other in an optional heat treatment, but the process clearly requires a relatively accurate process control to ensure that the outer layer of metal oxide has a reasonable uniform thickness, particularly if an outer layer of a very small thickness is desired.
A problem of this prior art is thus that the ceramic tape is difficult to handle, or that its thickness causes a coil containing a given length of conductor to be rela- tively large.
Accordingly, the object of the present invention is to provide a method of manufacturing a superconducting length of wire of the type stated in the opening para- graph, which does not necessitate the use of a ceramic tape to separate the individual layers of the conductor not heat treated yet in the packing or coiling of it, thereby achieving a method which lends itself for heat treatment of superconducting lengths of wire in a compact coiled or otherwise packed state, following which the superconducting length of wire may be unwound again and be used in a production process.
This is achieved according to the invention in that the tube of metal, before being packed or coiled, is provided with a liquid coating on at least the first and second parts of the outer surface of the tube, said coating comprising a substantially liquid component which evaporates or burns completely at the temperature at which the su- perconducting phase in the superconducting material is formed, and a powder material suspended in the liquid component and having a melting temperature which is higher than the melting temperature of the metallic tube.
This allows formation of a very thin layer of material on the conductor not heat treated yet, said layer ensuring that, during coiling or packing, the first outer area on the metal tube does not contact the second outer area on the meal tube in the heat treatment, while e.g. a coil of a given length of the conductor is not very bulky.
In a preferred embodiment, the coating applied to the length of wire comprises a ceramic material, in particu¬ lar a metal oxide preferably selected from the group: A1203, CR203, CuxOy, NixOy, ZnxOy, ZrxOy, TaxOy.
Alternatively, the coating may advantageously be formed by the application of a metal oxide powder. It may be applied particularly simply as a paint consisting of a liquid medium in which the metal oxide powder is sus- pended.
It is expedient in this connection if the metal oxide powder is suspended in an amount ensuring that the individual metal oxide particles, when applied to the first and second outer surfaces of the metal tube, are disposed in a density such that metal oxide particles on the first outer surface of the metal tube do not touch the second outer surface of the metal tube, and vice versa.
In addition, the liquid medium for the suspension of the metal oxide powder may expediently comprise a solvent, such as acetone, alcohol or toluene, admixed with an amount of polymer, such as polyvinyl butyral (PVB) , and polyvinyl butyral is advantageously added in an amount of between 0.1 and 10 per cent by weight, preferably between 1 and 4 per cent by weight, as this provides suitable ad- hesion properties for the liquid medium and the suspended metal oxide powder.
Tests have shown that zirconium oxide may preferably be used as the metal oxide powder, but other ceramic powders and particularly metal oxides may be used.
The invention will be described more fully below with reference to the drawing, in which:
Fig. 1 is a basic view which shows a coiled conductor containing superconducting material.
Fig. 2 is a basic view which shows a cross-section through the conductor shown in fig. 1 in a first embodiment.
Fig. 3 is a basic view which shows a cross-section through the conductor of fig. 1 in a second embodiment.
Fig. 1 thus shows a conductor containing superconducting material. As will be seen, the conductor is wound around a core with a view to heat treatment.
The wound conductor 1 may be manufactured according to a generally known method by filling a tube 2 with superconducting material 7 and then stretching, drawing or otherwise machining it in order to reduce the cross-sectional dimensions of the tube 2. In particular, this manufactur- ing process may comprise a rolling process or other process which provides a conductor in the form of a tape having a desired thickness. Such manufacturing processes are generally known from the literature and will therefore not be described in detail here. The product, however, is a conductor containing a superconducting base material, which subsequently requires a heat treatment to form the superconducting phase in the base material .
Owing to the handling of the conductor, the conductor is coiled or packed into e.g. a coil 1, as shown in fig. 1, and then the heat treatment may be initiated.
This heat treatment frequently requires the use of temperatures close to the melting temperature of the tube 2, so that, if the coiled conductor 1 has surfaces 3, 4 touching each other, as shown, then it is likely that the surface of the tube 3 will fuse or melt together with the other surface 4 on the conductor.
This is remedied according to the invention, as shown in figs. 2 and 3, by providing the tube 2 with an outer coating 5 before the tube is coiled into a coil or is otherwise packed with a view to the subsequent heat treatment, said coating 5 having a melting temperature which is higher than the melting temperature of the material of which the tube 2 is made.
Fig. 2 thus shows a first embodiment of the invention in which the tube 2 itself contains a superconducting base material, but the surfaces 3 and 4 of the tube are covered by a coating 5 of ceramic material selected from the group of materials having the basic formula MxO, where M is a metal, such as Cu, Ni, Al, Zn, Zr, Sr, Mn, Ta, etc., and where 0 is oxygen.
In embodiments of the method, the coating 5 may be provided by e.g. applying a paint which comprises the de- sired ceramic material suspended in a liquid, such as a solvent in the form of acetone, alcohol or toluene, ad- mixed with an amount of polymer, such as polyvinyl butyral (PVB) .
Alternatively, the ceramic coating 5 may be applied as a powder, or it may be formed by simple oxidation of the material of the tube 2.
Fig. 3 shows a second embodiment of the invention in which the tube 2 is filled with rows of filament tubes 6, which are in turn filled with a superconducting base material 7. In the same manner as shown in fig. 2, the conductor shown in fig. 3 is provided with a ceramic coating 5, but here, in contrast to the embodiment shown in fig. 2, the coating is applied so that it covers the entire circumference of the tube 2.
Clearly, in view of the basic idea of the present invention, a skilled person will be able to devise other embodiments of conductors which are provided with a coating to protect against fusing of the coiled conductor. Thus, the present invention may be applied in connection with conductors having other cross-sections than e.g. those shown in figs. 2 and 3, both as regards the outer cross- sectional dimensions and the internal structure of the tube.

Claims

P a t e n t C l a i m s
1. A method of manufacturing a superconducting length of wire, comprising at least
insertion of a superconducting base material into a tube of metal,
packing or coiling of the metallic tube in such a manner that a first part of the outer surface of the tube contacts a second part of the surface of the tube,
heating of the tube filled with the superconducting base material to a temperature close to the melting temperature of the metal tube so as to form the superconducting phase in the base material,
c h a r a c t e r i z e d in that
the tube of metal, before being packed or coiled, is provided with a liquid coating on at least the first and second parts of the outer surface of the tube, said coating comprising a substantially liquid component which evaporates or burns completely at the temperature at which the superconducting phase in the superconducting material is formed, and a powder material suspended in the liquid component and having a melting temperature which is higher than the melting temperature of the e- tallic tube.
2. A method according to claim 1, c h a r a c t e r i z e d in that the powder material is formed by a metal oxide.
3. A method according to claim 2, c h a r a c t e r - i z e d in that the metal oxide powder is suspended in an amount ensuring that the individual metal oxide particles, when applied to the first and second outer surfaces of the metal tube, are disposed in a density such that the metal oxide particles on the first outer surface of the metal tube do not touch the second outer surface of the metal tube, and vice versa.
4. A method according to claim 2, c h a r a c t e r - i z e d in that the liquid medium comprises a solvent, such as acetone, alcohol or toluene, admixed with an amount of polymer, such as polyvinyl butyral (PVB) .
5. A method according to claim 4, c h a r a c t e r - i z e d in that polyvinyl butyral is used as the polymer in an amount of between 0.1 and 10 per cent by weight, preferably between 1 and 4 per cent by weight.
6. A method according to claim 2, 3, 4 or 5, c h a r - a c t e r i z e d in that at least zirconium oxide is used as the metal oxide powder.
PCT/DK1998/000120 1997-03-25 1998-03-25 Coating of a superconductor Ceased WO1998043253A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AU66127/98A AU727072B2 (en) 1997-03-25 1998-03-25 Coating of a superconductor
SK1182-99A SK118299A3 (en) 1997-03-25 1998-03-25 Coating of a superconductor
AT98907923T ATE241205T1 (en) 1997-03-25 1998-03-25 SUPERCONDUCTOR COATING
CA002284782A CA2284782A1 (en) 1997-03-25 1998-03-25 Coating of a superconductor
DE69814842T DE69814842T2 (en) 1997-03-25 1998-03-25 SUPERCONDUCTOR COATING
EP98907923A EP0970483B1 (en) 1997-03-25 1998-03-25 Coating of a superconductor
JP54091498A JP2001516495A (en) 1997-03-25 1998-03-25 Superconductor coating
NZ337593A NZ337593A (en) 1997-03-25 1998-03-25 Superconductor inserted into metal tube coated with metal oxide suspension prior to coiling and heating
US09/380,115 US6223418B1 (en) 1997-03-25 1998-03-25 Coating of a superconductor
NO994666A NO994666D0 (en) 1997-03-25 1999-09-24 Coating of a superconductor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK0340/97 1997-03-25
DK34097 1997-03-25

Publications (1)

Publication Number Publication Date
WO1998043253A1 true WO1998043253A1 (en) 1998-10-01

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PCT/DK1998/000120 Ceased WO1998043253A1 (en) 1997-03-25 1998-03-25 Coating of a superconductor

Country Status (14)

Country Link
US (1) US6223418B1 (en)
EP (1) EP0970483B1 (en)
JP (1) JP2001516495A (en)
KR (1) KR20000076104A (en)
CN (1) CN1126118C (en)
AT (1) ATE241205T1 (en)
AU (1) AU727072B2 (en)
CA (1) CA2284782A1 (en)
DE (1) DE69814842T2 (en)
NO (1) NO994666D0 (en)
NZ (1) NZ337593A (en)
RU (1) RU2183875C2 (en)
SK (1) SK118299A3 (en)
WO (1) WO1998043253A1 (en)

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Publication number Publication date
NO994666L (en) 1999-09-24
AU6612798A (en) 1998-10-20
JP2001516495A (en) 2001-09-25
ATE241205T1 (en) 2003-06-15
DE69814842T2 (en) 2004-02-26
NZ337593A (en) 2000-04-28
AU727072B2 (en) 2000-11-30
US6223418B1 (en) 2001-05-01
EP0970483A1 (en) 2000-01-12
CN1251201A (en) 2000-04-19
SK118299A3 (en) 2000-12-11
CA2284782A1 (en) 1998-10-01
KR20000076104A (en) 2000-12-26
NO994666D0 (en) 1999-09-24
DE69814842D1 (en) 2003-06-26
EP0970483B1 (en) 2003-05-21
RU2183875C2 (en) 2002-06-20
CN1126118C (en) 2003-10-29

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