WO1990012409A1 - Procede de traitement d'un fil a supraconducteur d'oxide et objet ainsi realise - Google Patents
Procede de traitement d'un fil a supraconducteur d'oxide et objet ainsi realise Download PDFInfo
- Publication number
- WO1990012409A1 WO1990012409A1 PCT/JP1990/000421 JP9000421W WO9012409A1 WO 1990012409 A1 WO1990012409 A1 WO 1990012409A1 JP 9000421 W JP9000421 W JP 9000421W WO 9012409 A1 WO9012409 A1 WO 9012409A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide superconducting
- superconducting wire
- base material
- long base
- product
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000002887 superconductor Substances 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- -1 niggel Substances 0.000 claims 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- 229910001182 Mo alloy Inorganic materials 0.000 claims 1
- 229910001257 Nb alloy Inorganic materials 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 9
- 238000004804 winding Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 4
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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
- H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
- H01B12/06—Films or wires on bases or cores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F6/00—Superconducting magnets; Superconducting coils
- H01F6/06—Coils, e.g. winding, insulating, terminating or casing arrangements therefor
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Definitions
- the present invention relates to a method of handling an oxide superconducting wire and a product such as a coil using the oxide superconducting wire.
- oxide superconducting materials for applications such as coils and cables, for example, technology is needed to make them longer. Also, long ones must have some flexibility.
- a method of elongating the oxide superconducting material that can satisfy the above-mentioned requirements, that is, a method of obtaining an oxide superconducting wire having a certain degree of flexibility, for example, a method in which a long base material having flexibility is provided
- a method for forming an oxide superconducting layer is known.
- a vapor phase thin film forming method such as vapor deposition, sputtering, and CVD can be applied.
- Oxide superconducting materials are generally vulnerable to strain, especially tensile strain. For example, when tensile strain is applied, there is a disadvantage that the superconducting properties such as critical temperature and current density are significantly deteriorated.
- the tensile strain if this exceeds a predetermined magnitude, even if such tensile strain is removed, However, the superconducting properties obtained before the application of tensile strain could not be obtained anymore. On the other hand, when the tensile strain did not exceed the predetermined value, it was possible to reproduce the superconducting characteristics obtained before applying the tensile strain by removing the tensile strain. .
- the oxide superconducting layer when an oxide superconducting layer is formed on a flexible elongate base material to obtain an oxide superconducting wire, the oxide superconducting layer needs to pass through at least a heating step. Formed. Therefore, the long base material used for forming the oxide superconducting layer thereon can withstand such a heating step and undesired reaction or diffusion with the oxide superconducting layer in this heating step. Materials that do not cause any problems must be composed. For this reason, for example, YZZ (yttria-stabilized zirconia) is advantageously used as the long base material. In addition to YSZ, there are several other materials that are suitable as materials for long substrates for forming oxide superconductors within ⁇ _.
- the oxide superconducting layer in which the oxide superconducting layer is formed on the long base material as described above is, for example, in a preparation stage for subjecting it to the next ⁇ ) process such as enamel coating, or in a stage of shipping the same. Requires a process of winding on a bobbin, and when trying to obtain a product using an oxide superconducting wire, for example, in the case of a coil, this is wound into a coil! ) In the case of a cable, this can be A process of spirally winding the surface of the long body is required. In handling such an oxide superconducting wire, it is necessary to bend the oxide superconducting wire in any case.
- an object of the present invention is to provide an oxide superconducting wire that includes a process of bending an oxide superconducting wire, and to prevent the deterioration of the superconducting characteristics of the oxide superconducting layer as described above. Is to provide a method of handling superconducting wires.
- Another object of the present invention is to provide a product in which an oxide superconducting wire is used in such a state that deterioration of superconducting characteristics of an oxide superconducting layer contained therein can be prevented as much as possible. Disclosure of the invention
- the present invention is directed to a method for handling an oxide superconducting wire formed on a flexible long base material at least through a heating step and having an oxide superconducting layer. It was made based on seeing.
- the oxide superconducting material generally has a disadvantage that it is vulnerable to strain.
- oxidation occurs on a certain kind of flexible long substrate.
- the oxide superconducting layer is bent in a certain direction after obtaining the oxide superconducting wire formed at least through the heating step, despite the fact that the oxide superconducting layer is inevitably strained,
- the superconducting characteristics hardly deteriorated, or rather, that the superconducting characteristics improved.
- this was caused by the difference between the thermal expansion coefficient of the long base material and the thermal expansion coefficient of the oxide superconducting layer material. That is, at present, most flexible long substrates suitable for forming an oxide superconducting wire for obtaining an oxide superconducting wire have a higher thermal expansion coefficient than that of the oxide superconducting layer. It has a small coefficient of thermal expansion.
- oxide superconducting layer 2 when oxide superconducting layer 2 is formed on long base material 1, it is subjected to a heating step at a temperature of, for example, 400 to 100,000. After the desired oxide superconducting layer 2 is formed, the oxide superconducting layer 2 is cooled together with the long base material 1. During this cooling, the long base material 1 shrinks as indicated by the arrow symbol 3, while the oxide superconducting layer 2 shrinks as indicated by the arrow symbol 4. At this time, the arrow symbol 3 is shown shorter than the arrow symbol 4 to indicate that the thermal expansion coefficient of the long base material 1 is smaller than the thermal expansion coefficient of the oxide superconducting layer 2. Therefore, after cooling, the oxide superconductor 2 is given a tensile strain based on such a difference in the coefficient of thermal expansion, as indicated by an arrow 5.
- the present invention provides a thermal expansion It is intended for an oxide superconducting wire whose coefficient is smaller than the thermal expansion coefficient of the material of the oxide superconducting layer 2.
- the oxide superconducting layer in order to solve the above-mentioned technical problem, in handling the oxide superconducting wire, the oxide superconducting layer is positioned inside and the long base material is positioned outside the bending center with respect to the bending center.
- the oxide superconducting wire is bent. Referring again to FIG. 1, according to the characteristic handling method described above, the tensile strain indicated by the arrow symbol 5 previously given to the oxide superconducting layer 2 is relaxed. Become like
- a tape-shaped substrate is preferably used as the long base material.
- Examples of the material of the long base material that can satisfy the above-described conditions of the thermal expansion coefficient include, for example, zirconia, alumina, glass, titanium, zirconium, tungsten, platinum, chrome, nickel, and niobium. , Molybdenum, iron, stainless steel mesh and nickel alloy.
- the present invention also provides a product using the above-described oxide superconducting wire.
- the oxide superconducting wire is bent so that the oxide superconducting layer is located inside and the force and the long base material are located outside the bending center.
- Examples of the above-mentioned products include a coil using an oxide superconducting wire, a bobbin around which an oxide superconducting wire is wound, and a cable formed by spirally winding an oxide superconducting wire on the surface of a long body. There is.
- the oxide superconducting wire is handled so that the tensile strain inevitably remaining in the oxide superconducting layer contained therein is released, so that the superconducting characteristics of the oxide superconducting layer are deteriorated. Is prevented. According to the present invention, not only the deterioration of the superconducting property is simply prevented but also the improvement of the superconducting property can be expected in some cases. Further, as described above, when the oxide superconducting wire is bent, the tensile strain previously given to the oxide superconducting layer is not only relieved, but also a compressive strain may be generated. It has been found that a large compressive strain does not adversely affect the superconducting properties as much as a bow-strain, and may possibly further improve the superconducting properties.
- the long base material if a tape-shaped material is used as the long base material, it becomes easier to bend the oxide superconducting wire in a desired direction.
- the superconducting characteristics of the oxide superconducting wire should be used to the utmost. Can be.
- FIG. 1 is an explanatory diagram showing the influence of the coefficient of thermal expansion in the manufacturing process of an oxide superconductor that triggered the invention.
- FIG. 2 is an explanatory view schematically showing an apparatus used in Embodiment 1 of the present invention.
- FIG. 3 is a front view showing a bobbin arranged in the winding chamber 8 shown in FIG.
- FIG. 4 is an enlarged sectional view showing a state in which oxide superconducting wire 11 is wound around core 10 of bobbin 9 shown in FIG.
- FIG. 5 is a front view showing a part of the coil 18 obtained according to the second embodiment of the present invention.
- FIG. 6 is a cross-sectional view showing an enlarged part of the oxide superconducting wire 14 included in the coil 18 shown in FIG.
- a Y-Ba-Cu-0 superconductor is deposited on a long tape-shaped base material (5 mm wide, 0.1 mm thick) made of stabilized zirconia and lzm Films were formed with a thickness.
- the film forming conditions are as follows.
- composition Y, Ba 2 Cu 3 3 3 ⁇
- the moving speed of the long base material is set to 4 c hours. Meanwhile, in the heat treatment room 7, the heat treatment of the obtained oxide superconducting wire was performed at 900 for 10 minutes. Subsequently, in the winding chamber 8, as shown in FIGS. 3 and 4, the oxide superconducting wire 11 was wound on the winding core 10 of the bobbin 9 by 5 hours. At this time, as shown in FIG. 4, the film was wound so that the oxide superconducting layer 12 was positioned inside and the long base material 13 was positioned outside. The core 10 had a diameter of 30 min.
- oxide superconducting wire 1 1 taken Pobin 9 wound where, immersed in liquid nitrogen, and measuring the critical current, rarely 0 5 A
- Example 1 when the oxide superconducting wire 11 was wound around the core 10 of the bobbin 9, the same conditions as in Example 1 were used except that the oxide superconducting layer 12 was positioned outside.
- the critical current of the oxide superconducting wire 11 wound on bobbin 9 was measured under the same conditions, it was only 2 A.
- An oxide superconducting wire was obtained using the same long substrate and the same film forming conditions as in Example 1. Using this oxide superconducting wire, a superconducting coil was produced as follows.
- the oxide superconducting wire 14 As shown in Fig. 5, start winding the oxide superconducting wire 14 on the circumference having a radius of 30 mm from the center 15 of the coil 18 and wind it up to five layers, and then wind the coil 18 Produced. This and As shown in FIG. 6, the oxide superconducting wire 14 was wound so that the oxide superconducting layer 16 was positioned inside and the long base material 17 was positioned outside.
- Example 2 a coil was manufactured under the same conditions as in Example 2 except that the oxide superconductor 16 was wound so as to be on the outside, and the critical current was measured under the same conditions, and only a value of 8 A was obtained. It wasn't.
- Example 3 The oxide superconducting wire obtained in Example 1 was cut into an appropriate length without winding, and the critical current in liquid nitrogen was measured in a linear state. was obtained ⁇ Example 3
- the film forming conditions are as follows.
- Target composition Y, B a 2 C u 3 0 7 —
- the critical current density was 90% or more. Showed a decrease.
- the oxide superconducting wire when handled according to the present invention, the tensile strain of the oxide superconducting layer contained in the oxide superconducting wire is released, and the oxide superconducting layer is not deteriorated without deteriorating the superconducting characteristics of the oxide superconducting layer. Since the wire can be bent, the present invention can be advantageously applied in the manufacture of products such as coils, cables, or intermediate products such as bobbins, where the oxide superconducting wire must be bent. I can do it.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69015524T DE69015524T2 (de) | 1989-03-31 | 1990-03-29 | Verfahren zur herstellung eines supraleitenden drahtes auf oxidbasis. |
EP90905662A EP0417329B1 (en) | 1989-03-31 | 1990-03-29 | Method of producing an oxide superconducting wire |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1/82556 | 1989-03-31 | ||
JP8255689 | 1989-03-31 | ||
JP1179423A JP2986107B2 (ja) | 1989-03-31 | 1989-07-12 | 酸化物超電導線の製造方法および酸化物超電導線を用いた製品の製造方法 |
JP1/179423 | 1989-07-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990012409A1 true WO1990012409A1 (fr) | 1990-10-18 |
Family
ID=26423581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1990/000421 WO1990012409A1 (fr) | 1989-03-31 | 1990-03-29 | Procede de traitement d'un fil a supraconducteur d'oxide et objet ainsi realise |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0417329B1 (ja) |
CA (1) | CA2030559C (ja) |
DE (1) | DE69015524T2 (ja) |
WO (1) | WO1990012409A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003050826A1 (fr) * | 2001-12-10 | 2003-06-19 | Mitsubishi Denki Kabushiki Kaisha | Materiau de base metallique pour film epais supraconducteur renfermant un oxyde et procede de preparation associe |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3501828B2 (ja) | 1993-10-21 | 2004-03-02 | 住友電気工業株式会社 | 酸化物超電導導体の製造方法 |
DE102004048646B4 (de) * | 2004-10-04 | 2006-08-10 | Siemens Ag | Supraleitende Strombegrenzereinrichtung vom resistiven Typ mit bandförmiger Hoch-Tc-Supraleiterbahn |
DE102010040272B4 (de) * | 2010-09-06 | 2018-04-19 | Siemens Aktiengesellschaft | Hochtemperatur-Supraleiter (HTS)-Spule |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6459713A (en) * | 1987-08-28 | 1989-03-07 | Matsushita Electric Ind Co Ltd | Superconductor wire |
JPS6459728A (en) * | 1987-08-28 | 1989-03-07 | Matsushita Electric Ind Co Ltd | Manufacture of superconducting wire |
JPS6459714A (en) * | 1987-08-28 | 1989-03-07 | Matsushita Electric Ind Co Ltd | Superconductive wire |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63274017A (ja) * | 1987-04-30 | 1988-11-11 | Tdk Corp | 超電導線材 |
JPS6452327A (en) * | 1987-08-22 | 1989-02-28 | Sumitomo Electric Industries | Superconductive material |
US4994435A (en) * | 1987-10-16 | 1991-02-19 | The Furukawa Electric Co., Ltd. | Laminated layers of a substrate, noble metal, and interlayer underneath an oxide superconductor |
DE3829227A1 (de) * | 1988-08-29 | 1990-03-01 | Kabelmetal Electro Gmbh | Supraleitendes langgestrecktes gut aus einem beschichteten gewellten metallrohr |
-
1990
- 1990-03-29 DE DE69015524T patent/DE69015524T2/de not_active Expired - Lifetime
- 1990-03-29 CA CA002030559A patent/CA2030559C/en not_active Expired - Fee Related
- 1990-03-29 EP EP90905662A patent/EP0417329B1/en not_active Expired - Lifetime
- 1990-03-29 WO PCT/JP1990/000421 patent/WO1990012409A1/ja active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6459713A (en) * | 1987-08-28 | 1989-03-07 | Matsushita Electric Ind Co Ltd | Superconductor wire |
JPS6459728A (en) * | 1987-08-28 | 1989-03-07 | Matsushita Electric Ind Co Ltd | Manufacture of superconducting wire |
JPS6459714A (en) * | 1987-08-28 | 1989-03-07 | Matsushita Electric Ind Co Ltd | Superconductive wire |
Non-Patent Citations (1)
Title |
---|
See also references of EP0417329A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003050826A1 (fr) * | 2001-12-10 | 2003-06-19 | Mitsubishi Denki Kabushiki Kaisha | Materiau de base metallique pour film epais supraconducteur renfermant un oxyde et procede de preparation associe |
Also Published As
Publication number | Publication date |
---|---|
DE69015524D1 (de) | 1995-02-09 |
CA2030559C (en) | 1995-01-31 |
DE69015524T2 (de) | 1995-08-10 |
EP0417329A4 (en) | 1992-04-29 |
EP0417329B1 (en) | 1994-12-28 |
CA2030559A1 (en) | 1990-10-01 |
EP0417329A1 (en) | 1991-03-20 |
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