EP1051760A1 - Methods for producing percursor material for the production of high-temperature superconducting wires - Google Patents
Methods for producing percursor material for the production of high-temperature superconducting wiresInfo
- Publication number
- EP1051760A1 EP1051760A1 EP99908831A EP99908831A EP1051760A1 EP 1051760 A1 EP1051760 A1 EP 1051760A1 EP 99908831 A EP99908831 A EP 99908831A EP 99908831 A EP99908831 A EP 99908831A EP 1051760 A1 EP1051760 A1 EP 1051760A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- temperature
- melt
- precursor
- melting
- mixture
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 76
- 239000000155 melt Substances 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 238000002844 melting Methods 0.000 claims abstract description 50
- 230000008018 melting Effects 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002887 superconductor Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 54
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 33
- 239000004332 silver Substances 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 241000446313 Lamella Species 0.000 claims description 4
- -1 alkaline earth metal sulfate Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000010292 electrical insulation Methods 0.000 claims description 3
- 230000005496 eutectics Effects 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052729 chemical element Inorganic materials 0.000 claims 4
- 229910000510 noble metal Inorganic materials 0.000 claims 2
- 229910014454 Ca-Cu Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 7
- 239000000843 powder Substances 0.000 description 37
- 238000005253 cladding Methods 0.000 description 24
- 239000011575 calcium Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 16
- 239000002356 single layer Substances 0.000 description 14
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000005496 tempering Methods 0.000 description 9
- 239000011241 protective layer Substances 0.000 description 8
- 239000011810 insulating material Substances 0.000 description 7
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 238000010671 solid-state reaction Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 208000002352 blister Diseases 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000007669 thermal treatment Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ARCZIIMKMCECQB-UHFFFAOYSA-N [O].[Cu].[Sr].[Ca].[Pb].[Bi] Chemical class [O].[Cu].[Sr].[Ca].[Pb].[Bi] ARCZIIMKMCECQB-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
- H10N60/0772—Processes including the use of non-gaseous precursors
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/04—Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Definitions
- OPIT Oxide Powder In Tube
- a preliminary product the so-called precursor material
- a metallic tube which usually has a high proportion of silver.
- This is hammered out and drawn into a monofilament wire, then bundled into a multifilament, pulled out again and usually rolled afterwards.
- the actual reaction to the high-temperature superconducting material takes place in the last process steps of wire production as a solid-state reaction at temperatures preferably between 650 ° C and 850 ° C under a defined atmosphere.
- the quality of the precursor material is largely determined by the degree of reaction and thus by the reaction time in the wire for conversion into the desired target phase. In addition, the quality of the precursor material determines the properties of the superconducting wire such.
- the aim of the production of the precursor material is to pre-react and optimize the high-temperature superconductive material to such an extent that the actual strip / wire production takes place particularly shortly, cheaply and with the best superconducting properties, particularly with regard to the thermal treatment.
- wire and tape manufacture or wire and tape in summary only spoken of wires and their manufacture.
- the precursor powder is made from partially precalcined in a variety of ways
- Metal oxides such as. B. by a solid-state reaction, wet chemical, for. B. by co-precipitation, or by spray pyrolysis.
- Another method is the grinding of melted parts.
- reaction e.g. calcining, tempering
- work-up steps e.g. drying, grinding
- the precursor material is used almost exclusively as a powder or as a rod pressed from powder.
- extremely fine grinding with average grain sizes of d 5 o ⁇ 5 ⁇ m results in good mechanical ductility of the wires in the process steps of drawing and rolling
- grinding results in very good homogeneity achieved which is a particular challenge given the large number of components.
- carbonates and hydroxides in particular of the alkaline earth metals, are very thermally stable compounds.
- Wire with a multilayer structure can be produced in one work step if the precursor material is already present in the spaces between concentrically arranged silver tubes.
- tubes have to be pressed out of the precursor powder according to the pressing technique previously used. This is particularly problematic because the dimensional accuracy of the individual components, the homogeneity of the
- concentrically nested tubes are an interesting starting geometry for producing superconducting wires.
- Annealing temperatures neither destroy the shell, which mostly contains silver, nor diffuse through the layer, which mostly contains silver.
- Silver shells in the superconducting material are also foreign elements in high concentrations, which deteriorate or destroy the superconducting properties in the superconducting or superconducting material, not desired in the insulation. For this reason, various attempts have been made to achieve an insulating material with a highly contaminated two or three-layer connection. At concentrations of foreign ions such as Al, Ti, B etc. above 1000 ppmw, a complete loss of the superconducting properties is observed. In order to achieve such an insulating material, again, as in the case of the conductor concept with concentric tubes, first an inner silver tube must be filled with superconductor precursor material and then the space between the inner and outer tube with insulating material. For this too, either pipes made of powder have to be pressed or the powder has to be pressed directly into the cavities, which causes extremely inhomogeneous pressing and is associated with great difficulties. 6
- DE-A-196 13 163 describes a method in which powder is first poured into a cladding tube and this powder is then heated and melted in the cladding tube, whereby a high, homogeneous degree of filling is to be achieved. Difficulties can arise during practical implementation from both a chemical and a physical point of view:
- the cladding tube which mostly consists of silver, is heated to temperatures above the melting temperature of the molten filler material in the range of approx. 860 - 900 ° C depending on the desired superconductor material together with the superconductive material to be melted, then the previously fine-grained, homogeneous cladding tube material recrystallizes and, due to the formation of large grains, offers starting points for tearing open the cladding tube during cold forming into wire or tape.
- Silver has a relatively low melting point of only 962 ° C (Handbook of Chemistry and Physics, CRC Press, Boca Raton, Florida, 70 th Ed. 1900), while many of the silver-rich alloys used in practice a somewhat above lying of 962 ° C
- the object is achieved with a method for producing a high-temperature superconductor precursor material for use in strip or wire production, in which a mixture of oxides or / and their precursors is prepared, in which this mixture is heated so high that one at temperature there is good mixing and pourable melt, in which individual phases may still be in the solid state, this melt being introduced into a shell and solidifying there on cooling, and which is characterized in that the melt solidifies so quickly that here essentially no reaction layer made of the material of the shell with which the melt is formed, that the solidified melting body is heated in a temper firing to a temperature at which a conversion of the melting body material into a precursor material containing at least one high-temperature superconducting and / or high-temperature superconducting P hare of at least 10 wt .-% occurs and that no grinding is carried out after melting the mixture.
- the object is further achieved with a method for producing a high-temperature superconductor precursor material for use in strip or wire production, in which a mixture of oxides and / or their precursors is prepared, in which this mixture is heated to such an extent that one at
- this melt being introduced into a shell and solidifying there on cooling, which is characterized in that the melt is heated to such an extent that no segregation of the melt is formed for the superconducting material that the solidified melting body is heated in a temper firing to a temperature at which a conversion of the melting body material into a precursor material with a content of at least one high-temperature superconducting and / or high-temperature superconducting phase of at least 10% by weight occurs and that no grinding occurs after the mixture has melted is made.
- Remedy for segregation of the two superconductor components in the melt can be achieved by further heating the melt above 1000 ° C or by rapidly quenching the melt to freeze the structure before segregation.
- the cladding tube made of a silver-rich alloy with the melt; the silver can be dissolved in the melt and excreted as silver oxide.
- the cladding tube which usually has a wall thickness of around 1 mm thickness, a reaction layer which mostly contains mixed oxides containing silver can be recognized; a cladding tube attacked in this way can no longer be used for wire or strip production.
- the sleeve tube together with the superconductive or superconducting material can usually still be used if the reaction layer is thinner than 10 ⁇ m, preferably thinner than 5 ⁇ m.
- the process according to the invention is characterized in particular by the complete avoidance of grinding processes after melting and thus by the avoidance of extremely air-sensitive powders as an intermediate product, since the material is not filled in in the form of powder or compressed powder, but rather in the form of a melt in the majority covers containing silver.
- a mixture of the metal oxides such. B. Bi 2 0 3 , PbO, SrO, CaO, CuO or their precursor materials according to the desired atomic ratio for the superconducting bismuth (lead) strontium calcium copper oxides at temperatures above 1000 ° C, preferably above 1050 ° C , melted.
- Preferably all cations are in the form of oxides in the batch.
- a stoichiometric or approximately stoichiometric ratio of the oxides with respect to the nominal composition of the two- or three-layer compound in the mixture is preferably set.
- bismuth can be substituted up to 50 mol% by lead, antimony and / or yttrium;
- a high-melting compound in particular of alkaline earth metal sulfates, preferably SrS0, BaS0 or / and (Ba, Sr) S0 4 , can be added to improve the crystallinity.
- alkaline earth metal sulfates preferably SrS0, BaS0 or / and (Ba, Sr) S0 4
- the melting preferably takes place in platinum crucibles, in platinum-lined crucibles or in crucibles made of another suitable material such as, for. B. Ba umzirkonat in ovens such. B. in muffle furnaces.
- the melt can during the melting process by mechanical, preferably platinum-coated
- the oxide melt should only be used with inert materials such as e.g. Platinum, related precious metals or their alloys come into contact. So be
- the crucible After melting, which does not have to take place completely, particularly when adding optional high-melting compounds such as alkaline earth metal sulfates, the crucible is removed from the furnace, and the pourable melt is preferably poured directly into pipes or pipe-like casings or via communicating systems, without delay, poured or sucked.
- the term “shell” is intended to mean all pipes, pipe systems and similar designs which are suitable, together with the precursor material and possibly with an insulating material, to give an essentially rod-shaped molded body which is referred to in this application as a rod.
- the sleeves used are either at room temperature or are on
- Temperatures preferably up to 750 ° C, in particular up to 700 ° C, particularly preferably to 200 ° C to 500 ° C, preheated.
- the temperature difference between the melt and the preheated cladding tube should preferably be used 11
- this protective layer is usually 50 to 250 ⁇ m, especially depending on the temperature difference between the melt and the cladding tube. This layer now protects the shell from the further poured liquid and aggressive
- this layer insulates the casing against the still molten melt inside, thus reducing the maximum temperature of the casing.
- This phenomenon means that the casing is not heated above its softening point, but the maximum temperatures are ⁇ 800 ° C. Therefore, there are no problems such as tearing open the silver sheath in the actual wire production process when the melt reacts with the silver-containing alloy or when the sheath tube is heated to excessively high temperatures, in particular at temperatures of more than 850 ° C.
- the cooling rate of the melt can be achieved by pouring the melt into the
- Cooling outside the furnace usually results in a cooling rate of the order of 20 to 100 K / s.
- care must be taken that the gases contained in the melt and in the casings can escape as completely as possible and that as few and only very small cavities or pores are formed.
- care must always be taken to ensure that the protective layer formed on the inner surface of the casing is not melted again. If the process is good, after cooling,
- the melting or / and casting of the melt is preferably carried out in air, but can also be carried out under in order to further reduce impurities
- Protective gas particularly preferably under nitrogen, argon or synthetic air, 12 done.
- the degassing of the melt can be facilitated if necessary.
- the sleeves preferably have a diameter of 5 to 20 mm or a wall thickness of 0.5 to 5 mm and can preferably be made of pure silver (> 99
- Wt .-%) or a silver alloy which may have in particular contents of Mg, Au, Pd or / and Cu ⁇ 10 wt .-%, and have any cross-section, in particular a round or angular, and be welded on one side.
- the shells serve primarily to delineate the outer shape and to delineate the superconductive or, if appropriate, also the insulating material areas.
- the tube elements and fins serve in particular to align the superconductive or superconducting crystallites in preferred directions and as a ductile sheathing of the brittle ceramic material during hammering, drawing, rolling, etc. for producing the superconducting wire.
- the sleeves can also have atypical cross-sections and shapes for conventional pipes and, for example, have a U-shaped curve, in particular one side of the sleeves can preferably be developed obliquely, for example in order to be particularly adapted to the casting process and the escape of the gases.
- the wall thickness of the tube elements and fins should preferably be chosen to be small, but in such a way that a sufficient separating layer between the adjacent material layers is still retained during the further wire production.
- Such multi-hole covers are preferably provided with thin chamber walls; they can be made by extrusion processes or by joining several
- Shells are preferably accessible at both ends so that the melt can penetrate from one side and allow the gases to escape on the other side.
- the envelopes can also have branches of the individual channels, for example in order to allow gases to escape even better.
- the sleeves preferably have essentially the same length
- the slats do not necessarily have to separate the chambers from each other, but can also protrude into a free space like wings.
- a laterally closed envelope it is also possible to use pipes of more complicated construction, in which individual chambers can be open to the outside, or particularly advantageously wound foils, in particular spirally wound foils, which can be open, partially contacted or closed in the longitudinal direction on the outer edge; these wound foils have the advantage of a better distribution of the melt and, insofar as they are not gas-tight in the longitudinal direction on the outer edge, the more diverse ways of filling the
- the wrapped foils can also be combined with lamellas and / or tubular elements.
- the more complex sleeves can also consist of at least one tube element and at least one set of fins, of several tube elements lying one inside the other without or with fins or additionally of further channels.
- the number of tube elements lying one inside the other is preferably 2 to 25, particularly preferably 3 to 10, that of the fins preferably 1 to 12, particularly preferably 2 to 8, without counting a lamella leading through several tube elements or a tube element leading through several fins.
- the sleeves of the invention with a more complicated structure of several
- Pipe elements or / and lamellae have the great advantage that bundling into multifilaments can be dispensed with, in particular when there are a large number of tube elements or lamellae, and process steps in wire production can also be saved, since they are electrically conductive with superconductive and possibly also in individual chambers insulating material filled casing can be regarded from the start as a "multifilament".
- Such precursor rods 14 are electrically conductive with superconductive and possibly also in individual chambers insulating material filled casing can be regarded from the start as a "multifilament".
- wrapped foils are also addressed under the generic term "envelope".
- the solidified melt shows depending on its composition and content
- the precursor material thus has a bulk density that is at least 20%, often at least 50% higher than conventional precursor material that was produced via a powder route.
- the main crystalline component of the precursor material according to the invention is preferably the single-layer compound with the nominal composition Bi 2 (Sr, Ca) 2 CuO x ;
- alkaline earth metal cuprates, copper (l) oxide and, in the case of lead oxide, alkaline earth metal plumbates often occur in the starting mixture.
- the amorphous fraction depending on the cooling rate of the melt, is preferably between 10 and 90% by weight, in particular between 20 and 80% by weight. The lower the cooling rate, the higher the crystalline content.
- the impurities are less than 500 ppmw carbon, preferably less than 300 ppmw carbon, and less than 300 ppmw hydrogen, preferably less than 150 ppmw hydrogen in the solidified melting bodies.
- the strontium oxide to be used can be briefly annealed at temperatures> 1250 ° C before use in the batch, whereby the C content drops below 100 ppmw.
- the intermediate product, the solidified melt, is significantly less sensitive to air than the fine powders used in the usual precursor material production 15
- intermediate products can advantageously be carried out under protective gas and / or under a reduced pressure.
- the solidified melt is usually characterized in that, in contrast to the oxide mixture used, there is a clear copper (I) content, which is synonymous with an oxygen deficit. If one considers the stable oxidation levels Bi (III), Sr (II), Ca (II), Cu (II), Pb (II) in the cations used, the oxygen content of the two-layer compound should be about 8 per formula unit, in In the case of the lead-free three-layer connection of about 10 per formula unit. In the solidified melt, this oxygen content is usually reduced by more than 5 mol%.
- oxygen In the final tempering step, oxygen must be taken up and diffuse into the wire, in particular from the outside, in order to produce superconducting materials from superconductive materials and to adjust the oxygen content with the optimal superconducting properties for the connection. In the case of an excess of oxygen, as is often the case with
- Precursor powder or in the case of bars pressed from powders this must be removed through the casing during tempering, which can lead to the formation of bubbles if oxygen is released spontaneously.
- the casting mold for the precursor material melt can contain several, for example, concentrically nested or machined tubular elements.
- the melt can now either in one casting or in several separate casting processes into the cavities of the shells, in particular between the pipe elements or, if appropriate,
- At least two casting processes which can be carried out separately, but also at the same time, are necessary if different melts are to be filled into the different chambers. This is necessary in order to achieve electrical insulation of the super-conductive "monofiaments" from one another in the "multifilament conductor" here, for example, the single-layer connection - but only for
- the solidified melt Due to the high density, the solidified melt has a significantly poorer forming behavior in wire production than comparable OPIT silver tubes according to the prior art.This is why another thermal treatment before forming, the so-called annealing, is advantageously carried out, during which part Conversion of the preliminary product to a preliminary product with a phase stock with a higher proportion of the significantly more ductile two-layer connection takes place, which can then be formed cheaply during wire production
- the annealing reaction is preferably carried out in a muffle furnace or tube furnace under flowing nitrogen, oxygen, air or a nitrogen / oxygen gas mixture, if appropriate also under reduced gas pressure.
- the temperatures here are preferably between 600 ° C. and 900 ° C., particularly preferably between 700 ° C. and 840 ° C, the reaction time is in particular 0.2 to 50 hours, preferably 0.5 to 20 hours.
- the reaction can be 10 to 100% by weight of the
- Two-layer connection is carried out, preferably 50 to 90% by weight 17
- phase occurs primarily as the single-layer connection, alkaline earth metal cuprates and copper (I) oxide.
- portions of the three-layer connection and alkaline earth metal plumbate can additionally appear; with the exception of the one and two-layer connection, the proportions of all others occurring
- Phases usually below 20% by weight, preferably below 10% by weight.
- a further variant of the method according to the invention is to first pour the melt into split molds, i.e. molds to be opened, or into molds, dishes or crucibles made of a heat-resistant material, preferably of copper or a copper-rich alloy, which in particular are at room temperature or at temperatures up to 500 ° C.
- the melting takes place in the same way as for casting in casings.
- the melting bars are first annealed, preferably under the same conditions as mentioned above.
- a mechanical post-processing such. B. done by milling, turning or sawing, so that the melt body bars obtained can be inserted with a precise fit before further processing into wire in sleeves.
- the melting bodies show a significantly increased reactivity.
- the reaction times for generating a defined proportion of two-layer connection are 18th
- Gas composition have no influence on the melting body during tempering.
- Figures 1 a and 1 b schematically represent a multifilament wire (1) and a concentrically constructed wire (2) according to the prior art. These wires contain several chambers (3), the walls (4) and (5) of which consist of a silver-rich matrix or a silver-rich casing material. The chambers are filled with a high-temperature superconductor material (6).
- Figure 2a shows a multifilament wire (7) with several chambers (8) according to the prior art, the walls (9) of which consist of a silver-rich matrix.
- the inside of the chambers contains a high-temperature superconductor material (10), first of all of a silver-rich shell (9a) and then of an insulated one
- FIG. 2b shows a wire (12) constructed according to the invention with a plurality of chambers (13) made of concentrically constructed layers of silver-rich chamber walls (14) and a high-temperature superconductor material (15) 19
- the thickness of the glass-like protective layer on the inside of the cladding tube was approximately 100 ⁇ m.
- melt was poured into a round Ag tube with an inner diameter of 10 mm and a wall thickness of 1 mm.
- X-ray powder images crystalline fraction (X-pert, Philips): 62 ( ⁇ 5)% by weight two-layer compound,
- the thickness of the glass-like protective layer on the inside of the cladding tube was approximately 150 ⁇ m.
- melt was preheated to 350 ° C.
- ICP-AES analysis ICP-Plasma 400 and AAS 1100B, from Perkin-Elmer
- Bi 47 1% by weight
- Cu 14.4% by weight corresponds to: Bii.ggSn.ssCao. gC ⁇ Ox 22
- composition ICP-AES analysis (ICP-Plasma 400 and AAS
- Cu 19.2% by weight corresponds to: Bi 1 , 68Pbo, 33Sr 1 , 84 Ca 1 , 7 3CU 3 O ⁇
- Example 6 As in Example 6, but the melt was poured into a copper mold preheated to 350 ° C. with an internal dimension of 20 ⁇ 100 ⁇ 100 mm 3
- T a composition of ICP-AES analysis (ICP-Plasma 400 and AAS 1100B, from Perkin-Elmer) Bi 35.2% by weight, Pb 6.8% by weight, Sr 16.4% by weight, Ca 7.3% by weight -%, Cu 19.1% by weight
- Impurities C 400 ppmw (Couiomat 702, Ströhlein) H 70 ppmw (CHNS 932; Leco) Pt 370 ppmw (ICP-AES)
- precursor material A melt in a silver tube (precursor material A; according to the invention) or in a mold according to Example 2 and subsequent sawing to melt rods (precursor material B; according to the invention).
- powder was obtained by grinding the fusible rods of precursor material B in an air jet mill directly after the casting (precursor material C; comparative example). Isostatic rods were pressed from this powder (Precursormate ⁇ al D; comparative example) with a diameter of 10 mm and a length of 100 mm.
- Table 1 shows the surprisingly high proportions of two-layer compound in comparison with the powdery precursor materials C and D in the case of solidified ones
- Precursor materials A and B already have a high proportion of two-layer compound at these short annealing times.
- Example 6 but first three Ag tube elements with a round cross-section of 8, 13 and 18 mm inside diameter and 1 mm wall thickness were put into each other and soldered at the lower end with centering rings so that there were even distances between the individual tubes. Then 400 g of a mixture as in Example 6 were melted and poured into the interstices and then further treated as in Example 6.
- Phase composition Phase composition; amorphous fraction below 10% by volume; no reaction of the precursor material with the tube walls.
- the thickness of the glass-like protective layer on the inside of the cladding tube was approx. 80 ⁇ m for the inner tube, approx. 120 ⁇ m for the middle tube and approx. 220 ⁇ m for the outer tube.
- Other analysis data as in example 6.
- iSr-i ⁇ Ca L osC ⁇ Ox (Bi 47.0% by weight, Sr 18.8% by weight, Ca 4.7% by weight; Cu 14.2% by weight) was placed in a platinum crucible at a temperature of Melted 1100 ° C within 30 minutes in a muffle furnace and poured into the inner Ag tube element. Then 200 g of a mixture of the composition Bh.ggSn. sCuOx, melted in a platinum crucible at a temperature of 1000 ° C within 30 minutes in a muffle furnace and poured into the cavity between the inner and outer Ag tube element. The tube was then annealed in a muffle furnace in air at 710 ° C for 20 hours.
- the preliminary product thus obtained was characterized as follows:
- composition ICP-AES analysis (ICP-Plasma 400 and AAS
- Cu 14.3 wt -% corresponds: Bi 2 0 ⁇ Sr 1 ⁇ 8 GCA 1, o 4 Cu 2 O ⁇ outer tubular member:
- Bi 55.7% by weight; Sr 22.8% by weight; Cu 8.5% by weight corresponds to: Bi-i.g Sr-i.gsCuOx b.
- Impurities C 400 ppmw (Couiomat 702; Ströhlein)
- the thickness of the glass-like protective layer on the inside of the cladding tubes was approximately 80 ⁇ m for the inner tube and approximately 150 ⁇ m for the outer tube.
- Example 6 The procedure was as in Example 6, but instead of a (not gas-tight) muffle furnace, a very well sealed tube furnace with Inconel steel tube was used. In addition, synthetic, C0 2 -free air was used as the atmosphere. The composition was identical to that in Example 6. The following were determined: b. Impurities: C 120 ppmw (Couiomat 702; Ströhlein)
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Abstract
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE19803447A DE19803447A1 (en) | 1998-01-30 | 1998-01-30 | Process for the production of precursor material for the production of high-temperature superconductor wires |
DE19803447 | 1998-01-30 | ||
PCT/EP1999/000566 WO1999039392A1 (en) | 1998-01-30 | 1999-01-28 | Methods for producing percursor material for the production of high-temperature superconducting wires |
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EP1051760A1 true EP1051760A1 (en) | 2000-11-15 |
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EP99908831A Withdrawn EP1051760A1 (en) | 1998-01-30 | 1999-01-28 | Methods for producing percursor material for the production of high-temperature superconducting wires |
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EP (1) | EP1051760A1 (en) |
JP (1) | JP2002502099A (en) |
KR (1) | KR20010040471A (en) |
CN (1) | CN1289457A (en) |
AU (1) | AU2830599A (en) |
CA (1) | CA2318113A1 (en) |
DE (1) | DE19803447A1 (en) |
WO (1) | WO1999039392A1 (en) |
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CN113436811A (en) * | 2021-07-01 | 2021-09-24 | 广东金源宇电线电缆有限公司 | Cable anti-oxidation wrapping device and method |
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AU777934B2 (en) * | 1999-11-08 | 2004-11-04 | Hiroshi Maeda | High-temperature oxide superconductor wire and method for preparing the same |
DE10013060A1 (en) * | 2000-03-19 | 2001-10-04 | Selic Heinz Anton | Method of removing fault-zones in high-temperature super conductor (HTSL) cable, involves utilizing the shock wave action of ignited explosive material |
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JP2558695B2 (en) * | 1987-05-25 | 1996-11-27 | 株式会社東芝 | Method for manufacturing oxide superconducting wire |
DE3822685A1 (en) * | 1988-07-05 | 1990-01-11 | Asea Brown Boveri | Electrical conductor in wire or cable form, consisting of at least two strands in the form of a sheathed wire or a multifilament conductor or a coaxial cable based on a ceramic high-temperature superconductor |
EP0442210B1 (en) * | 1990-02-13 | 1996-03-06 | Kabushiki Kaisha Toshiba | Bi oxide superconductors |
JP3074753B2 (en) * | 1990-03-26 | 2000-08-07 | 住友電気工業株式会社 | Method for producing bismuth-based oxide superconductor |
DE4124823A1 (en) * | 1991-07-26 | 1993-01-28 | Hoechst Ag | HIGH TEMPERATURE SUPER LADDER AND METHOD FOR THE PRODUCTION THEREOF |
DE19613163A1 (en) * | 1996-04-02 | 1997-10-09 | Cryoelectra Ges Fuer Kryoelekt | Producing superconducting elements e.g. wires and strips |
-
1998
- 1998-01-30 DE DE19803447A patent/DE19803447A1/en not_active Ceased
-
1999
- 1999-01-28 CN CN99802455A patent/CN1289457A/en active Pending
- 1999-01-28 WO PCT/EP1999/000566 patent/WO1999039392A1/en not_active Application Discontinuation
- 1999-01-28 KR KR1020007008326A patent/KR20010040471A/en not_active Application Discontinuation
- 1999-01-28 AU AU28305/99A patent/AU2830599A/en not_active Abandoned
- 1999-01-28 EP EP99908831A patent/EP1051760A1/en not_active Withdrawn
- 1999-01-28 CA CA002318113A patent/CA2318113A1/en not_active Abandoned
- 1999-01-28 JP JP2000529757A patent/JP2002502099A/en not_active Withdrawn
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---|---|---|---|---|
CN113436811A (en) * | 2021-07-01 | 2021-09-24 | 广东金源宇电线电缆有限公司 | Cable anti-oxidation wrapping device and method |
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Publication number | Publication date |
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DE19803447A1 (en) | 1999-09-16 |
JP2002502099A (en) | 2002-01-22 |
CN1289457A (en) | 2001-03-28 |
CA2318113A1 (en) | 1999-08-05 |
WO1999039392A1 (en) | 1999-08-05 |
AU2830599A (en) | 1999-08-16 |
KR20010040471A (en) | 2001-05-15 |
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