EP0368082B1 - Oxygenated molybdenum metal powder and process for its preparation - Google Patents
Oxygenated molybdenum metal powder and process for its preparation Download PDFInfo
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- EP0368082B1 EP0368082B1 EP89119866A EP89119866A EP0368082B1 EP 0368082 B1 EP0368082 B1 EP 0368082B1 EP 89119866 A EP89119866 A EP 89119866A EP 89119866 A EP89119866 A EP 89119866A EP 0368082 B1 EP0368082 B1 EP 0368082B1
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- metal powder
- molybdenum metal
- molybdenum
- carbon dioxide
- oxygen
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- 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
- C23C4/06—Metallic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12181—Composite powder [e.g., coated, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
Definitions
- the present invention relates to molybdenum metal powder with a shell made of oxides of molybdenum and methods for its production.
- Molybdenum metal powders with a defined oxygen content are used in plasma spraying in order to achieve particularly hard spray coatings.
- Flame spraying with an ethine / oxygen mixture is preferably carried out using molybdenum wire as the melting material.
- the metal droplets are partially oxidized during flame spraying.
- a method for producing oxygen-containing molybdenum powder by an oxidizing plasma treatment is known from US Pat. No. 4,146,388.
- EP-A 233 574 describes three processes for producing oxygen-containing molybdenum wettable powders. These are the treatment of molybdenum metal with dilute hydrogen peroxide solution, the thermal treatment of molybdenum metal powder with water vapor under an inert gas atmosphere and the production of agglomerated oxygen-containing molybdenum metal powder using molybdenum oxides.
- a disadvantage of the molybdenum powders thus produced is that their oxygen content is not precisely defined.
- these molybdenum metal powders are often inhomogeneous.
- these molybdenum metal powders often have a MoO3 content, which has a disadvantageous effect on the spray behavior of the powder.
- the object of the present compound is to provide a molybdenum metal powder with a defined oxygen content which does not have the disadvantages described.
- the molybdenum metal powder according to the invention has an oxygen content of 1 to 18, preferably 2 to 12,% by weight.
- the oxygen is in a defined form as MoO2 and is in particular on the surface as a homogeneous layer. This oxide layer adheres firmly to the metallic core, so that the molybdenum metal powder according to the invention has very special structural properties.
- the powder grains consist of a molybdenum metal core and a uniform, closed MoO2 layer.
- the average diameter of the molybdenum metal powder individual grains is 5 to 90 microns and the thickness of the MoO2 shell 0.1 to 20 microns.
- the surface of the partially oxidized molybdenum metal powder according to the invention shows a typical MoO2 color.
- SEM scanning electron microscope
- the present invention also relates to a method for producing the molybdenum metal powder according to the invention. Surprisingly, this can be carried out in a very controllable oxidation of the molybdenum metal powder under a carbon dioxide atmosphere at unexpectedly low temperatures.
- the subject of this invention is thus a process for the production of molybdenum metal powder with a defined oxygen content, whereby molybdenum metal powder is partially oxidized by thermal treatment in a carbon dioxide atmosphere at temperatures below 1200 ° C.
- the partial oxidation is preferably carried out at temperatures from 700 to 1200 ° C.
- the oxygen uptake in the molybdenum metal powder is carried out by the process according to the invention exclusively with the formation of MoO2, which can be demonstrated by X-ray diffraction. An equivalent amount of carbon monoxide is released in the reaction.
- the weight increase in the starting powder is limited to 12% by weight.
- the increase in the particle diameter of the individual molybdenum metal particles corresponds to the oxygen uptake and the associated change in density.
- the oxygen loading of the molybdenum metal powder is inversely proportional to its surface. Preselected oxygen levels can be set with great accuracy using the parameters mentioned.
- the oxygen content of the molybdenum metal powder is set by the choice of the reaction time and / or the reaction temperature and / or the carbon dioxide concentration in the gas atmosphere. This is illustrated in FIGS. 1 to 3.
- Fig. 2 shows the dependence of the oxygen uptake of a molybdenum metal powder on the carbon dioxide volume flow and the time of constant temperature, measured by the CO2 / CO content in the exhaust gas.
- a grain coarsening occurs due to the oxygen absorption of the molybdenum metal powder, the density of the powder decreases.
- This invention therefore also relates to the use of the molybdenum metal powder according to one or more of claims 1 to 6 as molybdenum wettable powder.
- 800 g of a molybdenum metal powder with a grain size of> 5 ⁇ m and ⁇ 45 ⁇ m are gassed in a tube furnace with 20 l / h of carbon dioxide and heated to 900 ° C.
- the oxygen content of the metal powder is 3.6% by weight, after 2 hours reaction time 4.6% by weight, after 3 hours reaction time 5.5% by weight.
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Coating By Spraying Or Casting (AREA)
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Abstract
Description
Die vorliegende Erfindung betrifft Molybdänmetallpulver mit einer Hülle aus Oxiden des Molybdäns sowie Verfahren zu dessen Herstellung.The present invention relates to molybdenum metal powder with a shell made of oxides of molybdenum and methods for its production.
Molybdänmetallpulver mit einem definierten Sauerstoffgehalt werden beim Plasmaspritzen eingesetzt, um besonders harte Spritzschichten zu erzielen Beim Flammspritzen mit Ethin-Sauerstoffgemisch wird vorzugsweise Molybdän-Draht als Abschmelzmaterial eingesetzt. Hierbei werden die Metalltröpfchen während des Flammspritzens partiell oxidiert.
(Gmelin Handbuch der anorganischen Chemie, Molybdän, Ergänzungsband Teil A1, 1977, Seiten 182ff.)Molybdenum metal powders with a defined oxygen content are used in plasma spraying in order to achieve particularly hard spray coatings. Flame spraying with an ethine / oxygen mixture is preferably carried out using molybdenum wire as the melting material. The metal droplets are partially oxidized during flame spraying.
(Gmelin Handbook of Inorganic Chemistry, Molybdenum, Supplement Volume A1, 1977, pages 182ff.)
Verfahren zur Herstellung entsprechender sauerstoffhaltiger Molybdänmetallpulver sind zwar bekannt, jedoch hat sich für Molybdän das Plasmaspritzen gegenüber dem Flammspritzen bisher aus verschiedenen Gründen noch nicht durchsetzen können, da die Bereitstellung entsprechender Pulver nicht technisch gewährleistet ist.Processes for producing corresponding oxygen-containing molybdenum metal powders are known, but have For various reasons, plasma spraying has not yet been able to establish itself over flame spraying for molybdenum, since the provision of corresponding powders is not technically guaranteed.
Aus der US-A 4.146.388 ist ein Verfahren zur Herstellung sauerstoffhaltiger Molybdänpulver durch eine oxidierende Plasma-Behandlung bekannt. In der EP-A 233 574 werden drei Verfahren zur Herstellung sauerstoffhaltiger Molybdän-Spritzpulver beschrieben. Dies sind die Behandlung von Molybdänmetall mit verdünnter Wasserstoffperoxidlösung, die thermische Behandlung von Molybdänmetallpulver mit Wasserdampf unter Inertgasatmosphäre und die Herstellung agglomerierter sauerstoffhaltiger Molybdänmetallpulver unter Verwendung von Molybdänoxiden. Nachteilig an den so hergestellten Molybdänpulvern ist ihr nicht genau definierter Sauerstoffgehalt. Außerdem sind diese Molybdänmetallpulver häufig inhomogen. Weiterhin weisen diese Molybdänmetallpulver häufig einen MoO₃-Gehalt auf, der sich nachteilig auf das Spritzverhalten der Pulver auswirkt.A method for producing oxygen-containing molybdenum powder by an oxidizing plasma treatment is known from US Pat. No. 4,146,388. EP-A 233 574 describes three processes for producing oxygen-containing molybdenum wettable powders. These are the treatment of molybdenum metal with dilute hydrogen peroxide solution, the thermal treatment of molybdenum metal powder with water vapor under an inert gas atmosphere and the production of agglomerated oxygen-containing molybdenum metal powder using molybdenum oxides. A disadvantage of the molybdenum powders thus produced is that their oxygen content is not precisely defined. In addition, these molybdenum metal powders are often inhomogeneous. Furthermore, these molybdenum metal powders often have a MoO₃ content, which has a disadvantageous effect on the spray behavior of the powder.
Aufgabe der vorliegenden Verbindung ist es, ein Molybdänmetallpulver mit definiertem Sauerstoffgehalt bereitzustellen, welches die beschriebenen Nachteile nicht aufweist.The object of the present compound is to provide a molybdenum metal powder with a defined oxygen content which does not have the disadvantages described.
Überraschenderweise wurde nun gefunden, daß diese Anforderungen erfüllt werden durch ein Molybdänmetallpulver mit einer Hülle aus Oxiden des Molybdäns, wobei die oxidische Hülle aus MoO₂ besteht. In einer bevorzugten Ausführungsform weist das erfindungsgemäße Molybdänmetallpulver einen Sauerstoffgehalt von 1 bis 18, bevorzugt 2 bis 12 Gew.-%, auf. Der Sauerstoff liegt dabei in definierter Form als MoO₂ vor und befindet sich insbesondere an der Oberfläche als homogene Schicht. Diese Oxidschicht haftet fest am metallischen Kern, so daß das erfindungsgemäße Molybdänmetallpulver ganz besondere Struktur-Eigenschaften aufweist.Surprisingly, it has now been found that these requirements are met by a molybdenum metal powder with a shell made of oxides of molybdenum, the oxide shell consisting of MoO₂. In a preferred embodiment, the molybdenum metal powder according to the invention has an oxygen content of 1 to 18, preferably 2 to 12,% by weight. The oxygen is in a defined form as MoO₂ and is in particular on the surface as a homogeneous layer. This oxide layer adheres firmly to the metallic core, so that the molybdenum metal powder according to the invention has very special structural properties.
Die Pulverkörner bestehen aus einem Molybdänmetallkern und einer gleichmäßigen, geschlossenen MoO₂-Schicht. Bevorzugt beträgt der mittlere Durchmesser der Molybdänmetallpulver-Einzelkörner 5 bis 90 µm und die Dicke der MoO₂-Hülle 0,1 bis 20 µm.The powder grains consist of a molybdenum metal core and a uniform, closed MoO₂ layer. Preferably, the average diameter of the molybdenum metal powder individual grains is 5 to 90 microns and the thickness of the MoO₂ shell 0.1 to 20 microns.
Die Oberfläche des erfindungsgemäßen partiell oxidierten Molybdänmetallpulvers zeigt eine typische MoO₂-Färbung. Rasterelektronenmikroskopische (REM)-Aufnahmen zeigen im Gegensatz zur glatten Pulveroberfläche des Ausgangsmaterials einen zernarbten, geschlossenen Oxidbelag.The surface of the partially oxidized molybdenum metal powder according to the invention shows a typical MoO₂ color. In contrast to the smooth powder surface of the starting material, scanning electron microscope (SEM) images show a grained, closed oxide coating.
Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung des erfindungsgemäßen Molybdänmetallpulvers. Überraschenderweise läßt sich dieses in einer sehr gut kontrollierbaren Oxidation des Molybdänmetallpulvers unter einer Kohlendioxid-Atmosphäre bei unerwartet tiefen Temperaturen durchführen.The present invention also relates to a method for producing the molybdenum metal powder according to the invention. Surprisingly, this can be carried out in a very controllable oxidation of the molybdenum metal powder under a carbon dioxide atmosphere at unexpectedly low temperatures.
Gegenstand dieser Erfindung ist somit ein Verfahren zur Herstellung von Molybdänmetallpulver mit definiertem Sauerstoffgehalt, wobei Molybdänmetallpulver durch thermische Behandlung in einer Kohlendioxid-Atmosphäre bei Temperaturen unterhalb 1200°C partiell oxidiert wird. Bevorzugt erfolgt die partielle Oxidation bei Temperaturen von 700 bis 1200°C.The subject of this invention is thus a process for the production of molybdenum metal powder with a defined oxygen content, whereby molybdenum metal powder is partially oxidized by thermal treatment in a carbon dioxide atmosphere at temperatures below 1200 ° C. The partial oxidation is preferably carried out at temperatures from 700 to 1200 ° C.
Die Sauerstoffaufnahme im Molybdänmetallpulver erfolgt nach dem erfindungsgemäßen Verfahren ausschließlich unter Bildung von MoO₂, was durch Röntgenbeugung nachgewiesen werden kann. Bei der Reaktion wird eine äquivalente Menge an Kohlenmonoxid freigesetzt.The oxygen uptake in the molybdenum metal powder is carried out by the process according to the invention exclusively with the formation of MoO₂, which can be demonstrated by X-ray diffraction. An equivalent amount of carbon monoxide is released in the reaction.
Bei der erfindungsgemäßen Oxidationsbehandlung wird die Gewichtszunahme des Ausgangspulvers auf 12 Gew.-% begrenzt. Der Anstieg des Partikeldurchmessers der einzelnen Molybdänmetallpartikel entspricht dabei der Sauerstoffaufnahme und der damit verbundenen Dichteänderung.In the oxidation treatment according to the invention, the weight increase in the starting powder is limited to 12% by weight. The increase in the particle diameter of the individual molybdenum metal particles corresponds to the oxygen uptake and the associated change in density.
Mit steigendem Kohlendioxid-Angebot und steigender Temperatur nimmt die Geschwindigkeit der Sauerstoffaufnahme zu. Unter gleichem Kohlendioxid-Angebot und bei gleicher Reaktionstemperatur verhält sich die Sauerstoffbeladung des Molybdänmetallpulvers umgekehrt proportional zu seiner Oberfläche. Über die erwähnten Parameter sind vorgewählte Sauerstoffgehalte mit großer Genauigkeit einzustellen. In einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird somit der Sauerstoffgehalt des Molybdänmetallpulvers durch die Wahl der Reaktionszeit und/oder der Reaktionstemperatur und/oder der Kohlendioxid-Konzentration in der Gasatmosphäre eingestellt. Dies wird in den Fig. 1 bis 3 veranschaulicht.With increasing carbon dioxide supply and increasing temperature, the rate of oxygen uptake increases. With the same carbon dioxide supply and at the same reaction temperature, the oxygen loading of the molybdenum metal powder is inversely proportional to its surface. Preselected oxygen levels can be set with great accuracy using the parameters mentioned. In a particularly preferred embodiment of the method according to the invention thus the oxygen content of the molybdenum metal powder is set by the choice of the reaction time and / or the reaction temperature and / or the carbon dioxide concentration in the gas atmosphere. This is illustrated in FIGS. 1 to 3.
Fig. 1 zeigt die Sauerstoff-Aufnahme eines Molybdänmetallpulvers in Abhängigkeit von Temperatur und Zeit bei konstantem Kohlendioxid-Volumenstrom.1 shows the oxygen uptake of a molybdenum metal powder as a function of temperature and time with a constant carbon dioxide volume flow.
Fig. 2 zeigt die Abhängigkeit der Sauerstoff-Aufnahme eines Molybdänmetallpulvers vom Kohlendioxid-Volumenstrom und der Zeit konstanter Temperatur, gemessen am CO₂/CO-Gehalt im Abgas.Fig. 2 shows the dependence of the oxygen uptake of a molybdenum metal powder on the carbon dioxide volume flow and the time of constant temperature, measured by the CO₂ / CO content in the exhaust gas.
Fig. 3 zeigt die Abhängigkeit der Sauerstoff-Aufnahme von Molybdänmetallpulvern verschiedener Körnungen von der spezifischen Oberfläche der Pulver bei gleichem Kohlendioxid-Volumenstrom, gleicher Temperatur und Reaktionszeit.3 shows the dependence of the oxygen uptake of molybdenum metal powders of different grain sizes on the specific surface of the powders with the same carbon dioxide volume flow, the same temperature and reaction time.
Durch die Sauerstoffaufnahme des Molybdänmetallpulvers tritt eine Kornvergröberung ein, die Dichte des Pulvers nimmt ab.A grain coarsening occurs due to the oxygen absorption of the molybdenum metal powder, the density of the powder decreases.
Bei der Anwendung der erfindungsgemäßen Molybdänmetallpulver in Spritzversuchen zeigte sich eine deutliche Verbesserung der Härteeigenschaften der Auftragsschichten, wenn man anstelle von bekannten oxidhaltigen Molybdän-Spritzpulvern oder auch Molybdän-Spritzdraht das erfindungsgemäß sauerstoffdotierte Molybdänmetallpulver verwendet.When the molybdenum metal powders according to the invention were used in spray tests, there was a significant improvement in the hardness properties of the application layers, if instead of known oxide-containing molybdenum wettable powders or molybdenum spray wire that uses the oxygen-doped molybdenum metal powder according to the invention.
Gegenstand dieser Erfindung ist somit auch die Verwendung des Molybdänmetallpulvers gemäß einem oder mehrerer der Ansprüche 1 bis 6 als Molybdän-Spritzpulver.This invention therefore also relates to the use of the molybdenum metal powder according to one or more of
Im folgenden wird die Erfindung beispielhaft erläutert, ohne daß dadurch eine Einschränkung zu sehen ist.In the following, the invention is explained by way of example, without any limitation being thereby seen.
800 g eines Molybdän-Metallpulvers der Körnung >5 µm und <45 µm werden in einem Röhrenofen mit 20 l/h Kohlendioxid begast und auf 900°C aufgeheizt.800 g of a molybdenum metal powder with a grain size of> 5 µm and <45 µm are gassed in a tube furnace with 20 l / h of carbon dioxide and heated to 900 ° C.
Nach 1 Stunde Reaktionszeit beträgt der Sauerstoffgehalt des Metallpulvers 3,6 Gew.-%, nach 2 Stunden Reaktionszeit 4,6 Gew.-%, nach 3 Stunden Reaktionszeit 5,5 Gew-%.After a reaction time of 1 hour, the oxygen content of the metal powder is 3.6% by weight, after 2 hours reaction time 4.6% by weight, after 3 hours reaction time 5.5% by weight.
Nachfolgend einige ausgewählte Daten des zu 3,6 % oxidierten Molybdänmetallpulvers und seines Ausgangsmaterials:
Claims (7)
- Molybdenum metal powder having a shell of oxides of molybdenum, characterised in that the oxidic shell consists of MoO₂.
- Molybdenum metal powder according to Claim 1, characterised in that the oxygen content of the molybdenum metal powder is from 1 to 18% by weight, preferably from 2 to 12% by weight.
- Molybdenum metal powder according to one of the Claims 1 or 2, characterised in that the average diameter of the individual grains of the molybdenum metal powder is from 5 to 90 µm and the thickness of the MoO₂ shell is from 0.1 to 20 µm.
- A process for the preparation of molybdenum metal powder according to one or more of Claims 1 to 3, characterised in that molybdenum metal powder is oxidized by heat treatment in a carbon dioxide atmosphere at temperatures below 1200°C.
- Process according to Claim 4, characterised in that the partial oxidation is carried out at temperatures of from 700 to 1200°C.
- Process according to one of the Claims 4 or 5, characterised in that the oxygen content of the molybdenum metal powder is adjusted by the choice of reaction time and/or reaction temperature and/or carbon dioxide concentration in the gas atmosphere.
- Use of the molybdenum metal powder according to one or more of Claims 1 to 6 as molybdenum spraying powder.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT89119866T ATE90242T1 (en) | 1988-11-08 | 1989-10-26 | OXYGENATED MOLYBDENUM METAL POWDER AND PROCESS FOR PRODUCTION THEREOF. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE3837782A DE3837782A1 (en) | 1988-11-08 | 1988-11-08 | OXYGENOUS MOLYBDAEN METAL POWDER AND METHOD FOR THE PRODUCTION THEREOF |
DE3837782 | 1988-11-08 |
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EP0368082A2 EP0368082A2 (en) | 1990-05-16 |
EP0368082A3 EP0368082A3 (en) | 1990-07-25 |
EP0368082B1 true EP0368082B1 (en) | 1993-06-09 |
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EP89119866A Expired - Lifetime EP0368082B1 (en) | 1988-11-08 | 1989-10-26 | Oxygenated molybdenum metal powder and process for its preparation |
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US (2) | US4976779A (en) |
EP (1) | EP0368082B1 (en) |
JP (1) | JPH02185902A (en) |
AT (1) | ATE90242T1 (en) |
DE (2) | DE3837782A1 (en) |
ES (1) | ES2040964T3 (en) |
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US5302450A (en) * | 1993-07-06 | 1994-04-12 | Ford Motor Company | Metal encapsulated solid lubricant coating system |
US5776264A (en) * | 1996-04-12 | 1998-07-07 | Rutgers University | Method for producing amorphous based metals |
US6127654A (en) * | 1997-08-01 | 2000-10-03 | Alkron Manufacturing Corporation | Method for manufacturing heating element |
JP4231990B2 (en) * | 2001-03-21 | 2009-03-04 | 信越化学工業株式会社 | Rare earth oxide spray particles and method for producing the same, thermal spray member and corrosion resistant member |
JP4273292B2 (en) * | 2001-04-06 | 2009-06-03 | 信越化学工業株式会社 | Thermal spray particles and thermal spray member using the particles |
US7470307B2 (en) * | 2005-03-29 | 2008-12-30 | Climax Engineered Materials, Llc | Metal powders and methods for producing the same |
US8197885B2 (en) * | 2008-01-11 | 2012-06-12 | Climax Engineered Materials, Llc | Methods for producing sodium/molybdenum power compacts |
US20090181179A1 (en) * | 2008-01-11 | 2009-07-16 | Climax Engineered Materials, Llc | Sodium/Molybdenum Composite Metal Powders, Products Thereof, and Methods for Producing Photovoltaic Cells |
EP2636763B1 (en) * | 2012-03-05 | 2020-09-02 | Ansaldo Energia Switzerland AG | Method for applying a high-temperature stable coating layer on the surface of a component and component with such a coating layer |
KR102042657B1 (en) * | 2013-08-22 | 2019-11-28 | 재단법인대구경북과학기술원 | Thin film solar cell and method of fabricating the same |
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US3973948A (en) * | 1973-11-12 | 1976-08-10 | Gte Sylvania Incorporated | Free flowing powder and process for producing it |
US3909241A (en) * | 1973-12-17 | 1975-09-30 | Gte Sylvania Inc | Process for producing free flowing powder and product |
US3907546A (en) * | 1974-03-28 | 1975-09-23 | Gte Sylvania Inc | Molybdenum flame spray powder and process |
US4146388A (en) * | 1977-12-08 | 1979-03-27 | Gte Sylvania Incorporated | Molybdenum plasma spray powder, process for producing said powder, and coatings made therefrom |
US4684400A (en) * | 1986-02-20 | 1987-08-04 | Gte Products Corporation | Method for controlling the oxygen content in agglomerated molybdenum powders |
EP0233574B1 (en) * | 1986-02-12 | 1993-05-12 | GTE Products Corporation | Method for controlling the oxygen content in agglomerated molybdenum powder |
US4624700A (en) * | 1986-02-20 | 1986-11-25 | Gte Products Corporation | Method for controlling the oxygen content in agglomerated molybdenum powders |
US4758406A (en) * | 1987-11-25 | 1988-07-19 | Amax Inc. | Molybdenum addition agent and process for its production |
-
1988
- 1988-11-08 DE DE3837782A patent/DE3837782A1/en active Granted
-
1989
- 1989-10-26 ES ES198989119866T patent/ES2040964T3/en not_active Expired - Lifetime
- 1989-10-26 EP EP89119866A patent/EP0368082B1/en not_active Expired - Lifetime
- 1989-10-26 AT AT89119866T patent/ATE90242T1/en not_active IP Right Cessation
- 1989-10-26 DE DE8989119866T patent/DE58904628D1/en not_active Expired - Fee Related
- 1989-10-27 US US07/427,582 patent/US4976779A/en not_active Expired - Fee Related
- 1989-11-07 JP JP1288068A patent/JPH02185902A/en active Pending
-
1990
- 1990-09-20 US US07/585,802 patent/US5037705A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
ES2040964T3 (en) | 1993-11-01 |
ATE90242T1 (en) | 1993-06-15 |
US5037705A (en) | 1991-08-06 |
DE3837782C2 (en) | 1991-02-14 |
JPH02185902A (en) | 1990-07-20 |
DE3837782A1 (en) | 1990-05-10 |
DE58904628D1 (en) | 1993-07-15 |
US4976779A (en) | 1990-12-11 |
EP0368082A3 (en) | 1990-07-25 |
EP0368082A2 (en) | 1990-05-16 |
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