WO1989008332A1 - Procede et dispositif pour le depot de couches d'un materiau supraconducteur a haute temperature sur des substrats - Google Patents

Procede et dispositif pour le depot de couches d'un materiau supraconducteur a haute temperature sur des substrats Download PDF

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Publication number
WO1989008332A1
WO1989008332A1 PCT/DE1989/000103 DE8900103W WO8908332A1 WO 1989008332 A1 WO1989008332 A1 WO 1989008332A1 DE 8900103 W DE8900103 W DE 8900103W WO 8908332 A1 WO8908332 A1 WO 8908332A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
spraying
oxygen
nozzle
chamber
Prior art date
Application number
PCT/DE1989/000103
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Gunzelmann
Fritz Eberlein
Werner Herkert
Reiner Müller
Original Assignee
Siemens Aktiengesellschaft
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 claimed from DE3806174A external-priority patent/DE3806174A1/de
Priority claimed from DE3806176A external-priority patent/DE3806176A1/de
Application filed by Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Publication of WO1989008332A1 publication Critical patent/WO1989008332A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C23C4/11—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • 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
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H10N60/0492—Processes for depositing or forming copper oxide superconductor layers by thermal spraying, e.g. plasma deposition

Definitions

  • the invention relates to a method for applying layers of high-temperature superconducting material (HTSL) to substrates, in which a closed cover layer is applied to the arbitrarily shaped substrate by thermal spraying of ceramic powder with superconducting properties as the starting material.
  • HTSL high-temperature superconducting material
  • the invention also relates to associated devices for carrying out this method, with a spraying device with a nozzle for spraying the powdery starting material onto the substrate.
  • thermal spray processes are one of the options.
  • HTSL high-temperature materials
  • proposals have already been made to be sprayed on as closed cover layers with a thickness of> 20 ⁇ m onto any substrates or workpieces with complex surfaces.
  • plasma spraying or also high-speed flame spraying are suitable as thermal spraying methods. It is a matter of producing such closed layers which do not detach from the substrate when the components produced in this way are subsequently used as intended and which, in particular, ensure adequate current carrying capacity.
  • an oxygen annealing treatment is carried out after coating, for example at 900 ° C. for about 20 hours. This is the only way to regenerate the superconducting properties that are lost during the production of the thick layers by the spraying process due to the oxygen release of the layer material.
  • Subsequent oxygen annealing treatment poses problems: especially in the case of large-area components, the furnace size necessary for the substrates or their warpage must be taken into account.
  • substrates can be specified which only allow low annealing temperatures, for example plastics, printed circuit boards or aluminum.
  • the annealing process can lead to crack formation or detachment of the layer, so that the coated component is defective or at least does not guarantee sufficient current carrying capacity.
  • the object of the invention is therefore to improve the process of the type mentioned in the introduction in such a way that a subsequent oxygen annealing treatment is no longer necessary.
  • the necessary devices are to be created for this.
  • the object is achieved in that the thermal spraying takes place under an oxygen atmosphere with an adjustable oxygen partial pressure.
  • an oxygen-temperature treatment of the substrate be carried out, for which purpose the substrate C is brought at least through the spray jet to a temperature> 600 *. If necessary, the substrate is additionally heated.
  • the method according to the invention can advantageously be used both in the plasma spraying process and in the high-speed flame spraying process (so-called hypersonic process).
  • the spray nozzle with a protective gas tube is in a first embodiment Front part extended, which encloses the entire space between the opening of the spray nozzle and the substrate and can be acted upon with oxygen.
  • Front part extended which encloses the entire space between the opening of the spray nozzle and the substrate and can be acted upon with oxygen.
  • HTSL spray layers can be produced on the basis of the four-component systems yttrium-barium-copper-oxygen or lanthanum-strontium-copper-oxygen which have superconducting properties after the thermal spraying without oxygen annealing treatment Jump temperature T from 80 K to 90 K. This can only be achieved if, during the spraying process, alternatively using the plasma or the high-speed flame spraying process, there is a defined excess of oxygen which specifically counteracts the depletion of oxygen.
  • HTSL spray layers based on the bismuth-strontium-calcium-copper-oxygen or thallium-barium-calcium-copper-oxygen five-component systems, which are less critical with regard to the oxygen setting, can be applied.
  • the latter HTSL materials have transition temperatures T between 80 and 125 K.
  • the bismuth superconductors can stabilize the equilibrium phases with a higher transition temperature or increase the transition temperatures themselves.
  • FIGS. 3 to 5 show a protective gas tube as an attachment for the known spray nozzles in three views
  • FIG. 6 shows a chamber for receiving a complete coating system consisting of a spraying device, substrate and further aids,
  • FIG 7 shows a partial section of the chamber of FIG 6 with a
  • Heating device for the substrate is
  • the substrate is denoted by 1 and the spray layers produced on the substrate 1 by the different spraying methods are denoted by 2 or 3.
  • FIG. 1 shows a spraying device 10 for plasma spraying from a housing 11 in which a cathode 12 and an anodically connected copper nozzle 13 (anode) are arranged. There are supply lines for the powder inlet 14, for the plasma gas 15 and for water as a coolant 18.
  • a high voltage is applied between cathode 12 and anode 13 via an electrical generator 19, so that an arc is ignited.
  • the supply of the plasma gas 15 creates a plasma flame 16 at the opening of the spray nozzle 13, through which a conical spray jet 17 of the powder supplied laterally via the powder inlet 14 is formed.
  • a large-area spray layer 2 can thus be formed on the substrate 1.
  • a hypersonic spraying device 20 consists of a housing 21 with a proximal spray nozzle 23 and a distal powder inlet 24. Oxygen and fuel gas are supplied laterally via separate inlets 25 and 26, which are mixed in the nozzle 23 in a suitable mixing ratio for combustion reach. This applies to the supplied powder, which is accelerated to supersonic speed in a spray jet 27.
  • the complete housing 21 ' is cooled via cooling lines 28.
  • the focused spray jet 27 during hypersonic spraying allows spray layers 3 which are closely localized to be applied to the substrate 1. This spraying method is particularly advantageous for complicated geometries.
  • the protective gas tube 30 shown in FIGS. 3 to 5 is designed as a front part that can be placed on the spraying device 10 or 20.
  • the protective gas tube 30 consists of a tubular housing 31, for example made of brass, which is water-cooled over the entire circumference of the tube and whose inner contour is adapted to the formation of the spray jet.
  • the protective gas tube 30 can be cylindrical or flared towards the substrate 1.
  • the tubular housing 31 has a connection head 32 into which the sprayer 10 or 20 is inserted and fixed.
  • a U-shaped recess 33 is provided, which is open at the top and on the side, so that in particular the spray nozzle 23 according to FIG. 2 can be inserted tightly with the lateral outlet 28 for cooling water.
  • the spray nozzle 23 can be fixed by means of a screw 34 running through the recess 33.
  • connection head 32 there is a cooling water inlet 35 and an oxygen connection 36 on two surfaces lying perpendicular to one another, which can be connected to external lines. Specifically, the oxygen reaches the interior of the protective gas tube 30 from the connection 36 via a distributor nozzle 37, the size of the partial pressure of the oxygen being able to be precisely specified by means of external setting and control means.
  • an expanding concentric end part 38 is attached opposite the connection head 32, which carries a cooling water outlet 39.
  • An annular disk 40 is attached around the opening of the end part 38, which ensures a uniform distribution of the oxygen on the substrate surface. The annular disk 40 leaves the part of the substrate 1 to be coated free.
  • the disk 40 is only shown on one side in FIG. 4. It has the contour of the substrate surface and can in particular be adapted to the shape of the component to be produced if workpieces of a more complicated design are to be coated.
  • the chamber 60 shows a chamber 60 with a pump connection 61 and a gas connection 62.
  • the chamber 60 accommodates the entire device for spraying with a spraying device 10 for plasma spraying according to FIG. 1 or a spraying device 20 for hypersonic spraying according to FIG. 2 and the workpiece to be coated as substrate 1.
  • There is a handling device 65 which guides the nozzle 13 or 23 of the spraying device 10 or 20 in a suitable manner, controllable from the outside.
  • the chamber 60 according to FIG. 6 is first evacuated via the pump connection 61 before the coating process and then pressurized with oxygen predetermined partial pressure via the gas connection 62. The actual spraying process then takes place in the chamber 60, which is completely filled with oxygen.
  • a heating device 64 is assigned to a substrate 1 in a chamber 60 according to FIG.
  • the heating device 64 serves for the additional heating of the substrate in addition to the energy supply by the spray jet and advantageously works inductively or as resistance heating. Instead, a fuel gas flame can be used, the handling of which is simple.
  • the heating device 64 is used expediently, in particular in the case of larger workpieces, since the thermal energy of the spray jet is then generally not sufficient to uniformly heat the workpiece to a temperature of over 600.degree.
  • the alternatively described devices according to FIGS. 3 to 5 or FIGS. 6 and 7 can each be designed optionally for piasma spraying or also for hypersonic spraying.
  • the previously known HTSL materials can thus be sprayed onto substrates of any geometry in layers of a predetermined thickness. In this case, the oxygen depletion of the HTSL material is counteracted “in situ” immediately during spraying, so that the superconducting properties remain intact, without the need for afterglow in an oxygen atmosphere.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

Le dépôt d'un matériau supraconducteur à haute température sur des pièces peut s'effectuer par pulvérisation thermique, sur des substrats de forme quelconque, d'une poudre céramique faisant office de substance de base et ayant des propriétés supracondutrices, de manière à obtenir une couche de protection fermée. Jusqu'à présent, les pièces recouvertes d'une couche de protection devaient ensuite être frittées sous une atmosphère d'oxygène pour régénérer les propriétés supraconductrices. Avec le procédé objet de l'invention, la pulvérisation thermique sous atmosphère d'oxygène s'effectue avec une pression partielle d'oxygène réglable. En outre, dans un premier mode d'exécution, la buse (13, 23), nécessaire à l'application, qui équipe le pulvérisateur (10, 20) peut être prolongée par une conduite de gaz protecteur (30) qui entoure totalement l'espace situé entre l'orifice de la buse (13, 23) du pulvérisateur (10, 20) et le substrat (1) et qui peut être alimentée avec de l'oxygène (O2). Dans un deuxième mode d'exécution, on peut avoir une grande chambre (60) dans laquelle on peut disposer le pulvérisateur (10, 20), le substrat (1) et d'autres adjuvants pour l'enduction sous atmosphère d'oxygène.
PCT/DE1989/000103 1988-02-26 1989-02-23 Procede et dispositif pour le depot de couches d'un materiau supraconducteur a haute temperature sur des substrats WO1989008332A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP3806174.0 1988-02-26
DEP3806176.7 1988-02-26
DE3806174A DE3806174A1 (de) 1988-02-26 1988-02-26 Verfahren und vorrichtung zum aufbringen von schichten aus hochtemperatur-supraleitendem material auf substrate
DE3806176A DE3806176A1 (de) 1988-02-26 1988-02-26 Verfahren und vorrichtung zum aufbringen von schichten aus hochtemperatur-supraleitendem material auf substrate

Publications (1)

Publication Number Publication Date
WO1989008332A1 true WO1989008332A1 (fr) 1989-09-08

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1989/000103 WO1989008332A1 (fr) 1988-02-26 1989-02-23 Procede et dispositif pour le depot de couches d'un materiau supraconducteur a haute temperature sur des substrats

Country Status (2)

Country Link
EP (1) EP0401259A1 (fr)
WO (1) WO1989008332A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0456600A1 (fr) * 1990-05-11 1991-11-13 Plasma-Invent Ag Procédé pour le dépôt de couches minces d'un matériau céramique composite supra-conducteur
EP0507520A2 (fr) * 1991-03-28 1992-10-07 Ngk Insulators, Ltd. Méthode pour fabriquer des couches minces électriquement conductrices en céramique
DE29609637U1 (de) * 1996-05-30 1997-10-02 Siemens AG, 80333 München Vorrichtung zur Plasma-Kurzzeitverdampfung von Substanzen
DE102004059716B3 (de) * 2004-12-08 2006-04-06 Siemens Ag Verfahren zum Kaltgasspritzen
CN103451592A (zh) * 2013-08-28 2013-12-18 周星心 一种机车油压式减振器活塞杆的表面处理方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0288711A2 (fr) * 1987-04-28 1988-11-02 International Business Machines Corporation Revêtement rapide et sur une grande surface, en supraconducteurs à température critique élevée

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0288711A2 (fr) * 1987-04-28 1988-11-02 International Business Machines Corporation Revêtement rapide et sur une grande surface, en supraconducteurs à température critique élevée

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Advancee Ceramic Materials-Ceramic Super-Conductors, Band 2, Nr. 3B, Juli 1987, (Westerville, Ohio, US), W.T. Elam et al.: "Plasma sprayed high Tc superconductors"; Seiten 411-419 *
New Scientist, Nr. 1595, Januar 1988, (London, GB), "Breakthrough in thin-film superconductors", Seite 42 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0456600A1 (fr) * 1990-05-11 1991-11-13 Plasma-Invent Ag Procédé pour le dépôt de couches minces d'un matériau céramique composite supra-conducteur
EP0507520A2 (fr) * 1991-03-28 1992-10-07 Ngk Insulators, Ltd. Méthode pour fabriquer des couches minces électriquement conductrices en céramique
EP0507520A3 (en) * 1991-03-28 1993-10-13 Ngk Insulators, Ltd. Method of producing electrically conductive ceramic film
US5418081A (en) * 1991-03-28 1995-05-23 Ngk Insulators, Ltd. Method of producing electrically conductive ceramic film for interconnectors of solid oxide fuel cells
DE29609637U1 (de) * 1996-05-30 1997-10-02 Siemens AG, 80333 München Vorrichtung zur Plasma-Kurzzeitverdampfung von Substanzen
DE102004059716B3 (de) * 2004-12-08 2006-04-06 Siemens Ag Verfahren zum Kaltgasspritzen
US8012601B2 (en) 2004-12-08 2011-09-06 Siemens Aktiengesellschaft Cold gas spraying method
CN103451592A (zh) * 2013-08-28 2013-12-18 周星心 一种机车油压式减振器活塞杆的表面处理方法
CN103451592B (zh) * 2013-08-28 2017-02-08 周星心 一种机车油压式减振器活塞杆的表面处理方法

Also Published As

Publication number Publication date
EP0401259A1 (fr) 1990-12-12

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