EP0257319A1 - Method of producing protective coatings - Google Patents
Method of producing protective coatings Download PDFInfo
- Publication number
- EP0257319A1 EP0257319A1 EP87110805A EP87110805A EP0257319A1 EP 0257319 A1 EP0257319 A1 EP 0257319A1 EP 87110805 A EP87110805 A EP 87110805A EP 87110805 A EP87110805 A EP 87110805A EP 0257319 A1 EP0257319 A1 EP 0257319A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- suspension
- component
- temperature
- freeze
- solvent
- 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.)
- Granted
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
- C23C24/00—Coating starting from inorganic powder
Definitions
- the invention relates to a method for producing protective layers against thermal and / or chemical and / or mechanical stresses on components, in particular on complexly shaped components, such as turbine blades.
- Known protective layers or layered composites make use of the fact that it is possible with today's process technology to produce different properties in the surface of a component than those of the base material.
- Examples of such layers or composite materials with layers of this type are thermal insulation layers (pitting corrosion), wear protection layers (including tribological layers), rub-on and run-in coverings.
- the layers mentioned are predominantly applied by thermal spray processes.
- the object of the invention is to provide components or layered composite bodies with a protected surface, on parts already subjected to a shaping, in particular parts of complex shape, and to be able to cover them in a uniform layer thickness without great effort.
- the solution of the invention consists in a method for the deposition of layers in a physical way.
- a starting powder in a suspension is applied to a cooled component by immersion in the bath in the suspension and the component provided with the dip coating is subjected to freeze-drying.
- any desired layer thickness can be produced uniformly with the invention, and individual steps of the method can be repeated as often as desired, e.g. the production of the diving cover.
- a heat treatment and other treatments of the coated component can be carried out after the production of the coating, such as e.g. sealing sintering or sealing on the surface.
- a sintering or pressing program can also be combined for special requirements (hot isostatic pressing).
- Energy beam treatments of the surface, doping, infiltration of substances other than layer material and in a form other than powder can also be used within the scope of the present invention.
- a binder in particular an organic binder, can be dissolved in the suspension liquid, which brings about an increased green strength of the powder layer, in particular if a powder is used as the layer material, the mean grain size of which is above 25 ⁇ m. The organic binder is removed again at the beginning of the sintering process or in a separate heat treatment.
- the applications of the invention are not limited to the given exemplary embodiments, but generally in the case of layered materials or layered composite materials, the surfaces of which have a different property from the base material, ie the base of the component should.
- the invention is preferably used for protective layers, and here in particular for those which are subject to combined requirements.
- the main area of application is general mechanical engineering, components for vehicles of all kinds, but also stationary systems such as manufacturing systems, especially apparatus engineering.
- the base body of the composite body to be counted as the end product of the invention can be selected from almost any materials, such as metallic materials, metal compounds, intermetallic phases, ceramics, metal ceramics, metal glass, glass ceramics and / or combinations of the above materials with plastics.
- the devices which are necessary for carrying out the method according to the invention are of a simple and customary type, in particular as regards the containers required for the immersion method or the coolants for the component, such as refrigerators.
- the freeze dryers commonly used in food technology can be used for freeze drying, and the annealing and sintering ovens or presses or other post-treatment devices are also known per se.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
Es wird ein Verfahren zum Herstellen von Schutzschichten angegeben, und zwar u. a. gegen thermische und/oder chemische und/oder mechanische Beanspruchungen von Bauteilen, insbesondere auf kompliziert geformten Bauteilen wie Turbinenschaufeln, welches im wesentlichen folgende Verfahrensschritte beinhaltet: - Ein Pulver eines Ausgangsmaterials für die Schicht wird mit Lösungsmittel in eine Suspension gebracht. - Die Suspension wird auf einer Temperatur, knapp oberhalb des Gefrierpunktes des Lösungsmittels bereitgehalten. - Das zu beschichtende Bauteil wird auf einer Temperatur unterhalb des Gefrierpunktes des Lösungsmittels bereitgehalten. - Das Bauteil wird in die Suspension eingetaucht, und es friert eine Schicht des in der Suspension vorhandenen Ausgangspulvers fest, deren Dicke von der Temperatur des Bauteils und der Zeitdauer des Eintauchens des Bauteils in das Bad der Suspension abhängt. - Das mit der Schicht überzogene Bauteil wird einer Gefriertrocknung ausgesetzt und bis zum Abschluß des Gefriertrocknens nicht auf eine Temperatur oberhalb des Gefrierpunktes des Lösungsmittels erwärmt.A method for the production of protective layers is specified, i.a. a. against thermal and / or chemical and / or mechanical stresses on components, in particular on complexly shaped components such as turbine blades, which essentially comprises the following process steps: - A powder of a starting material for the layer is brought into a suspension with solvent. - The suspension is kept at a temperature just above the freezing point of the solvent. - The component to be coated is kept at a temperature below the freezing point of the solvent. - The component is immersed in the suspension and a layer of the starting powder present in the suspension freezes, the thickness of which depends on the temperature of the component and the duration of immersion of the component in the bath of the suspension. - The component coated with the layer is subjected to freeze-drying and is not heated to a temperature above the freezing point of the solvent until freeze-drying is complete.
Description
Die Erfindung betrifft ein Verfahren zum Herstellen von Schutzschichten gegen thermische und/oder chemische und/oder mechanische Beanspruchungen von Bauteilen, insbesondere auf kompliziert geformten Bauteilen, wie Turbinenschaufeln.The invention relates to a method for producing protective layers against thermal and / or chemical and / or mechanical stresses on components, in particular on complexly shaped components, such as turbine blades.
Stand der Technik: Bekannte Schutzschichten oder Schichtverbundwerkstoffe nutzen die Tatsache, daß es mit heutiger Verfahrenstechnologie möglich ist, in der Oberfläche eines Bauteils andere Eigenschaften zu erzeugen, als sie der Grundwerkstoff besitzt. Beispiele solcher Schichten bzw. Verbundwerkstoffe mit Schichten dieser Art sind Wärmedämmschichten (Pittingcorrosion), Verschleißschutzschichten (auch tribologische Schichten), Anstreif- und Einlaufbeläge. Die genannten Schichten werden in der Praxis überwiegend durch thermische Spritzverfahren aufgebracht.State of the art: Known protective layers or layered composites make use of the fact that it is possible with today's process technology to produce different properties in the surface of a component than those of the base material. Examples of such layers or composite materials with layers of this type are thermal insulation layers (pitting corrosion), wear protection layers (including tribological layers), rub-on and run-in coverings. In practice, the layers mentioned are predominantly applied by thermal spray processes.
Der Nachteil bekannter Verfahren besteht darin, daß bei kompliziert geformten Bauteilen nur mit großen Schwierigkeiten eine ausreichend gleichmäßige Schichtdicke auf das Bauteil aufgebracht werden kann. Zur - wenn auch nur teilweisen - Beseitigung dieser Schwierigkeiten ist ein erheblicher Aufwand erforderlich.The disadvantage of known methods is that a sufficiently uniform layer thickness can be applied to the component only with great difficulty in the case of complicatedly shaped components. Considerable effort is required to eliminate these difficulties, even if only partially.
Aufgabe der Erfindung ist es, Bauteile bzw. Schichtverbundkörper mit einer geschützten Oberfläche zu versehen, auf bereits einer Formgebung unterworfenen Teilen, insbesondere kompliziert geformten Teilen und diese dabei in gleichmäßiger Schichdicke, ohne großen Aufwand überziehen zu können.The object of the invention is to provide components or layered composite bodies with a protected surface, on parts already subjected to a shaping, in particular parts of complex shape, and to be able to cover them in a uniform layer thickness without great effort.
Die lösung der Erfindung besteht, allgemein gesprochen, in einem Verfahren zur Abscheidung von Schichten auf einem physikalischen Wege. Dabei wird ein Ausgangspulver in einer Suspension auf einem gekühlten Bauteil durch Eintauchen in das Bad in der Suspension aufgebracht und das mit dem Tauchüberzug versehene Bauteil einer Gefriertrocknung ausgesetzt.Generally speaking, the solution of the invention consists in a method for the deposition of layers in a physical way. Here, a starting powder in a suspension is applied to a cooled component by immersion in the bath in the suspension and the component provided with the dip coating is subjected to freeze-drying.
Ausgehend von einem Verfahren nach der eingangs genannten Gattung ist die gestellte Aufgabe insbesondere durch die im Kennzeichnungsteil des Patentanspruchs 1 angegebenen schrittweisen Verfahrensmerkmale erfindungsgemäß gelöst.Starting from a method according to the type mentioned at the outset, the object is achieved according to the invention in particular by the stepwise method features specified in the characterizing part of patent claim 1.
In vorteilhafter Weise kann mit der Erfindung praktisch jede gewünschte Schichtdicke gleichmäßig erzeugt werden, und dabei können einzelne Schritte des Verfahrens beliebig oft wiederholt werden, wie z.B. die Herstellung des Tauchüberzuges.Advantageously, practically any desired layer thickness can be produced uniformly with the invention, and individual steps of the method can be repeated as often as desired, e.g. the production of the diving cover.
Je nach gewünschtem Zweck der Schicht können anschließend an die Herstellung des Überzuges eine Wärmebehandlung und andere Behandlungen des überzogenen Bauteils durchgeführt werden, wie z.B. ein Dichtsintern oder Dichtpressen an der Oberfläche. Bei besonderen Anforderungen können auch ein Sinter- oder ein Preßprogramm kominiert werden (heißisostatisch Pressen). Auch Energiestrahlbehandlungen der Oberfläche, Dotieren, Infiltration von anderen Stoffen als Schichtwerkstoff und in anderer Form als Pulver können im Rahmen vorliegender Erfindung angewandt werden. Mit Vorteil kann in der Suspensionsflüssigkeit ein Bindemittel, insbesondere ein organisches Bindemittel, gelöst werden, das eine erhöhte Grünfestigkeit der Pulverschicht bewirkt, insbesondere dann, wenn als Schichtwerkstoff ein Pulver verwendet wird, dessen mittelere Korngröße oberhalb 25 µm liegt. Das organische Bindemittel wird dabei zu Beginn des Sintervorganges oder in einer separaten Wärmebehandlung wieder entfernt.Depending on the desired purpose of the layer, a heat treatment and other treatments of the coated component can be carried out after the production of the coating, such as e.g. sealing sintering or sealing on the surface. A sintering or pressing program can also be combined for special requirements (hot isostatic pressing). Energy beam treatments of the surface, doping, infiltration of substances other than layer material and in a form other than powder can also be used within the scope of the present invention. Advantageously, a binder, in particular an organic binder, can be dissolved in the suspension liquid, which brings about an increased green strength of the powder layer, in particular if a powder is used as the layer material, the mean grain size of which is above 25 μm. The organic binder is removed again at the beginning of the sintering process or in a separate heat treatment.
Weitere vorteilhafte Merkmale der Erfindung sind den übrigen Patentansprüchen sowie der Beschreibung von Ausführungsbeispielen zu entnehmen.Further advantageous features of the invention can be found in the remaining claims and the description of exemplary embodiments.
Die Anwendungen der Erfindung sind nicht auf die gegebenen Ausführungsbeispiele beschränkt, sondern allgemein bei Schichtwerkstoffen oder Schichtverbundwerkstoffen, deren Oberflächen eine vom Grundwerkstoff, d.h. der Basis des Bauteils, unterschiedliche Eigenschaft aufweisen sollen. Bevorzugt wird die Erfindung für Schutzschichten angewandt, und hier besonders für solche, die kombinierten Anforderungen unterworfen sind. Hauptanwendungsgebiet sind der allgemeine Maschinenbau, Bauteile für Fahrzeuge jeglicher Art, aber auch stationäre Anlagen wie Fabrikationsanlagen, insbesondere des Apparatebaus. Die Grundkörper des als Endprodukt der Erfindung zu zählenden Verbundkörpers können aus nahezu beliebigen Materialien ausgewählt werden, wie metallischen Werkstoffen, Metallverbindungen, intermetallischen Phasen, Keramik, Metallkeramik, Metallglas, Glaskeramik und/oder Kombinationen der o.g. Stoffe mit Kunststoffen. Als Schutzschichten können je nach Beanspruchungsart hierfür an sich bekannte Stoffe bzw. Werkstoffkombinationen ausgewählt werden. Die in den Beispielen angegebenen Prozentzahlen der Bestandteile für die Ausgangswerkstoffe bzw. Gemische bzw. Suspensionen können in weiten Grenzen verändert werden im Rahmen des eingangs erwähnten allgemeinen physikalischen Lösungsprinzips der Erfindung.The applications of the invention are not limited to the given exemplary embodiments, but generally in the case of layered materials or layered composite materials, the surfaces of which have a different property from the base material, ie the base of the component should. The invention is preferably used for protective layers, and here in particular for those which are subject to combined requirements. The main area of application is general mechanical engineering, components for vehicles of all kinds, but also stationary systems such as manufacturing systems, especially apparatus engineering. The base body of the composite body to be counted as the end product of the invention can be selected from almost any materials, such as metallic materials, metal compounds, intermetallic phases, ceramics, metal ceramics, metal glass, glass ceramics and / or combinations of the above materials with plastics. Depending on the type of stress, substances or combinations of materials known per se can be selected as protective layers. The percentages of the constituents for the starting materials or mixtures or suspensions given in the examples can be changed within wide limits within the framework of the general physical solution principle of the invention mentioned at the beginning.
Die Vorrichtungen, die zur durchführung des erfindungsgemäßen Verfahrens nötig sind, sind von einfacher und üblicher Art, insbesondere was die für das Tauchverfahren nötigen Behältnisse anbelangt oder die Kühlmittel für das Bauteil wie Kühlschränke. Für das Gefriertrocknen können die in der Lebensmitteltechnologie üblicherweise verwendeten Gefriertrockner angewandt werden und ebenso sind die Glüh- und Sinteröfen bzw. Pressen oder sonstigen Nachbehandlungseinrichtungen an sich bekannter Art.The devices which are necessary for carrying out the method according to the invention are of a simple and customary type, in particular as regards the containers required for the immersion method or the coolants for the component, such as refrigerators. The freeze dryers commonly used in food technology can be used for freeze drying, and the annealing and sintering ovens or presses or other post-treatment devices are also known per se.
-
1. Wärmedämmschicht für Turbinenleitschaufeln
- Suspension:
50 Vol % H₂O
50 Vol % Zr O₂-Pulver mit 5 % Y₂ O₃ teilstabilisiert,
mittlere Korngröße des Pulvers: 0,5 µm
Temperatur der Suspension: + 5 Grad Celsius
- Bauteil : Turbinenlaufschaufel
Temperatur - 20 Grad Celsius
- Eintauchen des Teiles: 10 s
- Gefriertrocknen (- 10 Grad Celcius, Vakuum 10⁻² mbar, 2 h)
- Sintern: 1200 Grad Celsius, 1 h im Vakuum1. Thermal insulation layer for turbine guide vanes
- suspension:
50 vol% H₂O
50 vol% Zr O₂ powder partially stabilized with 5% Y₂ O₃,
average grain size of the powder: 0.5 µm
Temperature of the suspension: + 5 degrees Celsius
- Component: turbine blade
Temperature - 20 degrees Celsius
- Immersion of the part: 10 s
- Freeze-drying (- 10 degrees Celcius, vacuum 10⁻² mbar, 2 h)
- Sintering: 1200 degrees Celsius, 1 h in vacuum -
2. Korrosionsschutzschicht für Turbinenleitschaufeln:
- Suspension:
54,5 Vol % H₂O
45 Vol % Co Cr Al Y - Pulver, mittlere Korngröße 30 µm
0,5 Vol % Polyvinylalkohol, Rest: Wasser
- Bauteil: Turbinenleitschaufeln,
Temperatur - 10 Grad Celsius
- Eintauchen des Bauteils : 5 s
- Bauteil erneut auf - 10 Grad Celsius kühlen
- Eintauchen: 5 s
- Gefriertrocknen (- 10 Grad Celsius, Vakuum 10⁻² mbar, 4 h)
- Ausbrennen des Polyvinylalkohols:
Warmbehandlung, kontinuierliches Aufheizen von Raumtemperatur auf 600 Grad Celsius in 24 h im Vakuum, Druck (p) < 10⁻² mbar
- Sintern der Schicht:
1150 Grad Celsius, 1/2 h, Vakuum, Druck (p) < 10⁻² mbar2. Corrosion protection layer for turbine guide vanes:
- suspension:
54.5 vol% H₂O
45 vol% Co Cr Al Y powder, average grain size 30 µm
0.5 vol% polyvinyl alcohol, rest: water
- component: turbine guide vanes,
Temperature - 10 degrees Celsius
- Immersion of the component: 5 s
- Cool the component again to - 10 degrees Celsius
- Immersion: 5 s
- Freeze drying (- 10 degrees Celsius, vacuum 10⁻² mbar, 4 h)
- Burning out the polyvinyl alcohol:
Heat treatment, continuous heating from room temperature to 600 degrees Celsius in 24 h in a vacuum, pressure (p) <10⁻² mbar
- Sintering the layer:
1150 degrees Celsius, 1/2 h, vacuum, pressure (p) <10⁻² mbar
Claims (10)
- Ein Pulver eines Ausgangsmaterials für die Schicht wird mit Lösungsmittel in eine Suspension gebracht.
- Die Suspension wird auf einer Temperatur, knapp oberhalb des Gefrierpunktes des Lösungsmittels bereitgehalten.
- Das zu beschichtende Bauteil wird auf einer Temperatur unterhalb des Gefrierpunktes des Lösungsmittels bereitgehalten.
- Das Bauteil wird in die Suspension eingetaucht, und es friert eine Schicht des in der Suspension vorhandenen Ausgangspulvers fest, deren Dicke von der Temperatur des Bauteils und der Zeitdauer des Eintauchens des Bauteils in das Bad der Suspension abhängt.
- Das mit der Schicht überzogene Bauteil wird einer Gefriertrocknung ausgesetzt und bis zum Abschluß des Gefriertrocknens nicht auf eine Temperatur oberhalb des Gefrierpunktes des Lösungsmittels erwärmt.1.Procedure for producing protective layers against thermal and / or chemical and / or mechanical stresses on components, in particular on complexly shaped components, such as turbine blades, characterized by the following steps:
- A powder of a starting material for the layer is brought into a suspension with solvent.
- The suspension is kept at a temperature just above the freezing point of the solvent.
- The component to be coated is kept at a temperature below the freezing point of the solvent.
- The component is immersed in the suspension and a layer of the starting powder present in the suspension freezes, the thickness of which depends on the temperature of the component and the duration of immersion of the component in the bath of the suspension.
- The component coated with the layer is subjected to freeze-drying and is not heated to a temperature above the freezing point of the solvent until freeze-drying is complete.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3628363 | 1986-08-21 | ||
DE19863628363 DE3628363A1 (en) | 1986-08-21 | 1986-08-21 | PROCESS FOR PRODUCING PROTECTIVE LAYERS |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0257319A1 true EP0257319A1 (en) | 1988-03-02 |
EP0257319B1 EP0257319B1 (en) | 1990-06-27 |
Family
ID=6307854
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87110805A Expired - Lifetime EP0257319B1 (en) | 1986-08-21 | 1987-07-25 | Method of producing protective coatings |
Country Status (4)
Country | Link |
---|---|
US (1) | US4902536A (en) |
EP (1) | EP0257319B1 (en) |
JP (1) | JPS6353278A (en) |
DE (2) | DE3628363A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3821819A1 (en) * | 1988-06-29 | 1990-02-08 | Nokia Unterhaltungselektronik | Process for producing a thin layer |
ES2009355A6 (en) * | 1988-10-17 | 1989-09-16 | Sintermetal Sa | Method to obtain coatings on mechanical parts by P/M techniques. |
JPH0765232B2 (en) * | 1989-10-12 | 1995-07-12 | 三菱レイヨン株式会社 | Amorphous alloy manufacturing method |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1126103A (en) * | 1954-06-17 | 1956-11-15 | Birmingham Small Arms Co Ltd | Heat resistant steel or alloy object |
FR1428311A (en) * | 1964-03-06 | 1966-02-11 | Siemens Planiawerke Ag | A method of manufacturing sheaths, as well as sheaths obtained by the present or similar process |
FR1502325A (en) * | 1965-11-26 | 1967-11-18 | Method and device for improving the surface condition of metal parts | |
US3475161A (en) * | 1967-03-14 | 1969-10-28 | Howmet Corp | Method of forming cemented carbide coatings on metal surfaces by employing volatile,organic liquid solvents and organic binders |
FR2179251A1 (en) * | 1972-04-07 | 1973-11-16 | Rca Corp | |
DE2718758A1 (en) * | 1977-04-27 | 1978-11-02 | Siemens Ag | Barium titanate ceramic tubes metallisation - by dipping into silver suspension ultrasonically vibrating and extracting from suspension at specified rates |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1271281A (en) * | 1968-07-31 | 1972-04-19 | Ethyl Corp | Coating of webs by freeze-drying and products therefrom |
US4328285A (en) * | 1980-07-21 | 1982-05-04 | General Electric Company | Method of coating a superalloy substrate, coating compositions, and composites obtained therefrom |
-
1986
- 1986-08-21 DE DE19863628363 patent/DE3628363A1/en not_active Withdrawn
-
1987
- 1987-07-25 EP EP87110805A patent/EP0257319B1/en not_active Expired - Lifetime
- 1987-07-25 DE DE8787110805T patent/DE3763430D1/en not_active Expired - Lifetime
- 1987-07-28 US US07/079,166 patent/US4902536A/en not_active Expired - Fee Related
- 1987-08-11 JP JP62201683A patent/JPS6353278A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1126103A (en) * | 1954-06-17 | 1956-11-15 | Birmingham Small Arms Co Ltd | Heat resistant steel or alloy object |
FR1428311A (en) * | 1964-03-06 | 1966-02-11 | Siemens Planiawerke Ag | A method of manufacturing sheaths, as well as sheaths obtained by the present or similar process |
FR1502325A (en) * | 1965-11-26 | 1967-11-18 | Method and device for improving the surface condition of metal parts | |
US3475161A (en) * | 1967-03-14 | 1969-10-28 | Howmet Corp | Method of forming cemented carbide coatings on metal surfaces by employing volatile,organic liquid solvents and organic binders |
FR2179251A1 (en) * | 1972-04-07 | 1973-11-16 | Rca Corp | |
DE2718758A1 (en) * | 1977-04-27 | 1978-11-02 | Siemens Ag | Barium titanate ceramic tubes metallisation - by dipping into silver suspension ultrasonically vibrating and extracting from suspension at specified rates |
Also Published As
Publication number | Publication date |
---|---|
EP0257319B1 (en) | 1990-06-27 |
US4902536A (en) | 1990-02-20 |
DE3763430D1 (en) | 1990-08-02 |
JPS6353278A (en) | 1988-03-07 |
DE3628363A1 (en) | 1988-02-25 |
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Owner name: DE DOMINICIS & MAYER S.R.L. |
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